影响水性聚氨酯/丙烯酸酯光固化速度的因素

用甲苯二异氰酸酯、聚己二酸新戊二醇酯、二羟甲基丙酸合成水性聚氨酯,用含双键的甲基丙烯酸羟乙酯封端,制得质量分数为34%的水性聚氨酯/丙烯酸酯水分散液,分别用三种光引发剂固化.结果表明,其中2-羟基-2-甲基-苯丙酮适用于常温固化;1-[4-(2-羟乙氧基-苯基)]-2羟基-2-甲基-丙酮适用于高温条件.当以1-[4-(2-羟乙氧基-苯基)]-2羟基-2-甲基-丙酮为光引发剂,控制光固化温度为80℃,表面光照强度70mW/cm2,引发剂质量分数为4%时,涂膜凝胶化时间为55s,凝胶化程度为 83.4%.此时冲击强度大于50kgcm,吸水率4.69%,附着力1级,耐溶剂性达300次.     

苯并三唑类复合型高分子光稳定剂的合成与性能研究

以2-(2',4'-二羟基苯基)-2H-苯并三唑、聚乙二醇单甲醚丙烯酸酯、丙烯酸十八醇酯、4(甲基丙烯酰氧基)2,2,6,6-四甲基哌啶醇酯为原料,甲苯为溶剂,偶氮二异丁腈为引发剂,在氮气保护下通过溶液共聚合成了三种兼具紫外吸收和捕获自由基两种功能的梳状复合型高分子光稳定剂。采用红外光谱(IR)、紫外光谱(UV)、核磁共振(~1H-NMR)等对产物进行了表征,并通过1H-NMR确定了共聚单体配比;采用热失重对产物的热性能进行了分析。结果表明:产物具有较好的紫外光吸收性能,在220~350 nm范围内有较强的紫外吸收;所合成的高分子光稳定剂的热分解温度明显高于低分子紫外线吸收剂的分解温度。     

一种双端丙烯酸酯类液晶单体的合成

以对羟基苯甲酸、脱氧熊果苷、丙烯酰氯和甲基丙烯酰氯为原料,通过醚化、酯化、加氢、酯化、脱保护和酯化反应制备了双端丙烯酸酯类液晶单体4-甲基丙烯酰氧基苯甲酸-4'-丙烯酰氧基苯酚酯,其液相含量> 99%,总收率为38%。目标化合物经气相-质谱和红外光谱进行了结构鉴定。     

活性稀释剂对乙烯基酯树脂光固化性能的影响

以环氧树脂E53与丙烯酸为原料合成了乙烯基酯,并分别与光活性交联单体甲基丙烯酸羟乙酯(HEMA)、1,6-己二醇二丙烯酸酯(HDDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)及苯乙烯(St)配制成光固化乙烯基酯树脂,采用FT-IR、UV吸收光谱对乙烯基酯的分子结构和吸光性能进行了表征,使用旋转粘度计、紫外光固化箱、万能试验机研究了4种交联单体以及光引发剂对乙烯基酯树脂的粘度,光固化试样厚度及其光固化树脂弯曲性能与硬度的影响。结果表明,选用2-羟基-2-甲基苯丙酮作引发剂,HEMA添加质量分数为40%时,乙烯基酯树脂综合性能最佳,粘度为0.4 Pa·s,5 min内一次性光固化产物厚度可达8 mm,光照面巴氏硬度为45 H,背光面为33 H,弯曲强度可达98.7MPa,弯曲模量达3.4 GPa。     

含共引发剂胺的聚酯型高分子光引发剂的制备及其性能研究

为克服小分子光引发剂的固有缺陷,通过2-(2,3-二羟基)丙氧基硫杂蒽酮(HPTX)、二酰氯及N-甲基二乙醇胺(MDEA)进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构都引入到同一个高分子链上,制备了侧链含有硫杂蒽酮,主链含有共引发剂胺的聚酯型高分子光引发剂。傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)证实了高分子光引发剂的结构。紫外光谱(UV-Vis)证实了高分子的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示扫描量热仪(photo-DSC)研究聚酯型高分子光引发剂引发聚酯丙烯酸酯树脂(PEA)的光聚合反应,结果表明:高分子光引发剂的主链结构对其引发效率有着显著的影响。     

桐油基光引发剂的制备及性能研究

以桐油(TO)、桐酸(TA)和马来酸酐(MA)为原料,经Diels-Alder反应,得到桐油酸酐(TOM1～3)及桐酸酸酐(TAM)。在三乙胺催化下,TOM、TAM分子中酸酐分别与Irgacure2959[2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮]的羟基反应,合成了4种裂解型光引发剂(TOMG1～3,TAMG)。用FTIR、1HNMR及HRMS表征了其结构,利用UV-vis考察了引发剂的光分解过程,用实时红外光谱探究了引发剂引发1,6-己二醇二丙烯酸酯(HDDA)的聚合过程。结果表明,在Irgacure2959和桐油改性的几种光引发剂中,TOMG3光引发性能最优。在紫外光强度为28 mW/cm2的光照下,以HDDA、PUA(聚氨酯丙烯酸酯)及TOMG3按质量比46:46:8复配的胶液的光固化表干时间为60 s,凝胶率为96%,固化膜的硬度及柔韧性分别为6H和5 mm,对玻璃的附着力为0级。     

桐油基光引发剂的制备及性能

以桐油(TO)、桐酸(TA)和马来酸酐(MA)为原料,经Diels-Alder反应,得到桐油酸酐(TOM1～3)及桐酸酸酐(TAM)。在三乙胺催化下,TOM、TAM分子中酸酐分别与Irgacure2959[2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮]的羟基反应,合成了4种裂解型光引发剂(TOMG1～3,TAMG)。用FTIR、1HNMR及HRMS表征了其结构,利用UV-vis考察了引发剂的光分解过程,用实时红外光谱探究了引发剂引发1,6-己二醇二丙烯酸酯(HDDA)的聚合过程。结果表明,在Irgacure2959和桐油改性的几种光引发剂中,TOMG3光引发性能最优。在紫外光强度为28 mW/cm2的光照下,以HDDA、PUA(聚氨酯丙烯酸酯)及TOMG3按质量比46:46:8复配的胶液的光固化表干时间为60 s,凝胶率为96%,固化膜的硬度及柔韧性分别为6H和5 mm,对玻璃的附着力为0级。     

阳离子双酯表面活性剂氯化2,3-二(硬脂酰氧基)丙基三甲基铵的合成

以自制的阳离子单酯表面活性剂氯化2-羟基-3-硬脂酰氧基丙基三甲基铵(CMESA)和硬脂酰氯为原料,经一步反应合成了阳离子双酯表面活性剂氯化2,3-二(硬脂酰氧基)丙基三甲基铵(CDESA)。研究了反应介质、反应时间和缚酸剂吡啶的用量对生成物CDESA收率的影响,通过元素分析、官能团分析和红外光谱确证其化学结构,最佳合成条件为:n(CMESA)∶n(硬脂酰氯)∶n(吡啶)=1∶1∶1,1,4-二氧六环为反应介质,回流加热反应3h,CDESA收率为93.1%。     

紫外光照法合成PPMM-g-HEMA膜及其表征

本文研究利用二苯甲酮(BP)和Fe Cl3的协同光引发作用,双硫代苯甲酸苄酯作为链转移剂,在紫外光照下,将亲水性的甲基丙烯酸羟乙酯(HEMA)接枝到疏水性的聚丙烯微孔膜(PPMM)。探究合成膜的影响因素,并通过FTIR对膜表面进行了表征。     

胰蛋白酶分子表面印迹材料的制备及其大分子识别特性

以交联聚乙烯醇(CPVA)微球为基质,采用接枝聚合和表面印迹同步技术制备碱性蛋白胰蛋白酶(TRY)分子表面印迹材料,甲基丙烯酰氯与CPVA微球表面的羟基发生快速酯化反应,得到表面含大量可聚合双键甲基丙烯酰基(MAO)的改性微球MAO-CPVA. 按一定摩尔比将TRY和单体阴离子单体对苯乙烯磺酸钠(SSS)溶解在水溶液中,加入交联剂N,N'-亚甲基双丙烯酰胺(MBA), MAO-CPVA分散于水介质中,过硫酸铵/亚硫酸氢钠引发体系产生自由基,使包围在TRY周围的单体SSS与MBA在MAO-CPVA表面发生接枝交联聚合,制得TRY表面印迹微球MIP-PSSS/CPVA,对其进行表征,考察了其大分子识别性能. 结果表明,MIP-PSSS/CPVA对TRY有优良的亲和性和特异识别选择性,吸附容量达85.9 mg/g,对TRY的选择性系数相对于蛋白溶菌酶LZM达17.52.     

Novel self-initiating UV-curable acrylate monomers

Based on the addition reaction of hydroxyl groups and the isocyanate groups in the bi-functional monomer acroyloxyethyl isocyanate (AOI), two novel self-initiating ultraviolet (UV)-curable acrylate monomers were synthesized from benzoin and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (commercial-available Irgacure® 2959), and the products were denoted as Benzoin-AOI and 2959-AOI, respectively. The chemical structures of the products were confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The UV–visible absorption spectrum showed that the self-initiating acrylates exhibited similar maximum absorption wavelengths to both benzoin (250 nm) and Irgacure® 2959 (270 nm). When the products were continually exposed to a mercury lamp, the maximum absorption peak gradually blue shifted, showing that the products decomposed under the UV radiation. The photo differential scanning calorimetry (Photo-DSC) analysis showed that the self-initiating monomers could initiate the polymerization of 1,6-hexanediol diacrylate (HDDA) as quickly as the original photo-initiator, and the efficiency of Benzoin-AOI was slightly lower than that of benzoin, while for 2959-AOI, the efficiency remained stable after being linked to the AOI moiety. The cytotoxicity assay against fibroblasts cell line L929 showed that 2959-AOI exhibited lower cytotoxicity at low dosages but higher cytotoxicity at high dosages compared to Irgacure® 2959 after the introduction of the AOI structure.     

Photoinitiability of a water-borne polysiloxane-modified benzophenone macromolecular photoinitiator

This paper reported a water-borne polysiloxane-modified benzophenone macromolecular photoinitiator (WPSHBP), whose characteristics of the photopolymerization, the migration of photolysis fragments, the volatility, and reduction of oxygen inhibition were discussed in detail. WPSHBP has a maximum absorption peak at 286 nm, and the molar extinction coefficient (ε_286 nm) is 23200 M^?1 cm^?1. The photopolymerization rate and final double bond conversion of the system initiated by WPSHBP were enhanced with the increasing contents of triethanolamine (TEOA) and WPSHBP and irradiation intensity. WPSHBP exhibits a low migration of photolysis fragments and volatility compared with small-molecular photoinitiator benzophenone (BP). The cured films initiated by WPSHBP have good mechanical properties and thermostability compared with that by 2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959). More importantly, the water-borne polysiloxane-modified photoinitiator can mitigate the oxygen inhibition in radical photopolymerization due to its enrichment on the surface of the photopolymerization system.     

Synthesis of UV‐curable hyperbranched polyurethane (meth)acrylate oligomers via thiol‐ene “click” chemistry

First, the second‐generation hyperbranched poly(amine‐ester) (G2‐OH) was successfully prepared by thiol‐ene “click” chemistry. Subsequently, a series of photosensitive hyperbranched oligomers (G2‐ORs) were synthesized by facile modifications of the G2‐OH with acryloyl chloride, methacryloyl chloride, IPDI‐HEA, and IPDI‐HEMA, respectively. The structures of hyperbranched oligomers were characterized by element analysis, FT‐IR, ¹H NMR, GPC and viscosity measurement. It was shown that these synthesized oligomers have narrow molecular weight distribution and low intrinsic viscosity at 30°C. UV–vis spectra results showed that the G2‐ORs had sharp absorption bands at around 202 nm. The results of photosensitivities measurement indicated that the G2‐Macr shows the highest photosensitive than other hyperbranched oligomers in the absence of photoinitiator. In addition, these UV‐cured photosensitive G2‐ORs had good thermal properties. The solubilities of the synthesized hyperbranched oligomers were also examined. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

含甲基丙烯酰氧基的甲基丙烯酰胺单体的合成与性能研究

用甲基丙烯酰氯分别与乙醇胺和二乙醇胺反应合成了两种单体。以实时红外光谱(RT-IR)法分别研究了两种单体和三缩乙二醇双甲基丙烯酸酯(SR209)混合物的光聚合动力学性质,考察了不同引发剂对聚合性能的影响,并采用动态力学分析仪(DMA)测试了光固化后材料的力学性能。结果表明,与二苯甲酮(BP)相比,2-羟基2-甲基-1-苯基丙酮(1173)对两种单体具有较好的引发效果。两种单体加入三缩四乙二醇双甲基丙烯酸酯(SR209)中后,对体系光固化后的产物力学性能有不同影响。     

一种含硅大分子光引发剂的合成及其性能研究

以2-羟基-2-甲基-1-苯基丙酮(HMPP)、异佛尔酮二异氰酸酯(IPDI)、羟基封端聚硅氧烷HOSiOH为原料,通过两步反应,合成了一种含硅大分子光引发剂HMPP-IPDI-HOSiOH-IPDI-HMPP(HISiIH)。用IR对反应过程进行了监测。通过配备有紫外光点光源的差动热分析仪(Photo-DSC)研究了HISiIH引发三丙二醇双丙烯酸酯(TPGDA)光聚合动力学。与小分子光引发剂HMPP复配,解决氧阻聚对光聚合反应的影响。     

Preparation and properties of UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate monomers with high refractive indices

We synthesized UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate with high refractive indices. The structures of monomers were confirmed by nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR). The formulation of UV-curable coating film was prepared by thioacrylate monomer, thiourethane acrylate monomer, α-hydroxy-α-methylpropiophenone as the photoinitiator, and bisphenol A epoxy acrylate as the oligomer. The cured coating films were investigated using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Taber abraser tests, transmittance, and refractive index. The value of refractive index for all coating films increased after UV-curing. Transparent, photocurable coating films with high abrasion resistance were prepared. The monomers showed high refractive index. The refractive indices of synthesized monomers (thioacrylate and thiourethane acrylate monomer) are 1.623 and 1.577, respectively.     

Dendritic carbosilane‐based macrophotoinitiator: synthesis,characterization, and photoinitiating behavior

A novel radical dendritic macrophotoinitiator, bearing alkyl pheone moieties linked to the surface of the dendrimer, was synthesized via alcoholysis of carbosilane dendrimer and the small‐molecule photoinitiator 2‐hydroxy‐2‐methyl‐1‐(4‐tert‐butyl)phenylpropane‐1‐one. The structure of the dendritic carbosilane‐based macrophotoinitiator (MPI) was characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, ²⁹Si NMR, elemental analysis, size exclusion chromatography/multi‐angle laser light scattering, UV‐visible spectroscopy, and differential photocalorimetry (DPC). UV‐visible analysis indicates that the absorption band of photosensitive moieties shifts towards high wavelength by introducing the carbosilane dendrimer core. The DPC results demonstrate that the initiating efficiency of MPI is effective when using epoxy acrylate (EA) as a model resin. Furthermore, thermogravimetric analysis of cured EA resin indicates that the thermal stability can be improved markedly by the incorporation of MPI in the curing formulation. Copyright © 2007 Society of Chemical Industry     

Photocuring activity of several commercial, near UV activated photoinitiators in clear and pigmented systems

Some of the most important commercial near UV photoinitiators have been analyzed by UV spectroscopy to evaluate the type of electronic transitions occurring upon absorption of light. Photocuring studies have been undertaken by real time infrared spectroscopy (RTIR) in clear and pigmented (black, magenta, cyan, and yellow) systems with UV and visible light at different photoinitiator concentrations in the presence of air. Generally, the Type I photofragmenting photoinitiators appear to operate more effectively under UV excitation when compared with the Type II thioxanthones, especially in pigmented systems. There is a reasonable correlation between the UV and visible absorption properties of the respective initiators and their overlap with the excitation source. Department of Chemistry and Materials, John Dalton Building, Chester Street, Manchester M1 5GD.     

基于聚酯织物的超亲水涂层的制备及其油水分离行为

将聚酯织物先后在水性聚氨酯胶黏剂溶液以及由乙烯基三乙氧基硅烷改性纳米二氧化硅、2-甲基丙烯酰氧乙基三甲基氯化铵、聚乙二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯和2-羟基-2-甲基苯丙酮组成的乙醇混合溶液中浸泡,再经紫外固化,得到基于聚酯织物的无机有机复合超亲水涂层。红外光谱、扫描电镜和接触角测试结果确认了织物表面超亲水涂层的形成,水滴在织物表面完全铺展的时间最短仅为301 ms。利用超亲水聚酯织物可以进行油水分离,其分离效率达99.4%。在经过50次循环分离后,其分离效率仍可保持在98%以上。     

Synthesis and properties of UV-curable hyperbranched polyurethane acrylate oligomers containing photoinitiator

The hyperbranched polyurethane acrylate oligomers containing photoinitiator were synthesized by modifying the second-generation hyperbranched poly(amine-ester) with isophorone diisocyanate-2-hydroxyethylacrylate and isophorone diisocyanate-2-hydroxy-2-methylpropiophenone at different feed ratio. The elemental analysis, FT-IR and NMR methods are used for structural characterization, molecular weights, and polydispersities, photosensitive groups and thermal properties of the oligomers were analyzed by gel permeation chromatography, UV–Vis spectra and thermogravimetric analysis, respectively. UV-curing properties were characterized by FT-IR at different curing time. In addition, the solubilities of the oligomers were also examined.