Synthesis and Properties of Novel Cationic Maleic Diester Polymerizable Surfactants

Three new cationic polymerizable surfactants are synthesized by the reaction of alkylmaleic hemiester with glycidyltrimethylammonium chloride. Their structures are confirmed by H-1 NMR, IR and elements analysis. The values of CMC and gamma (CMC) of these surfactants have been measured. One can obtain nearly monodisperse polystyrene latex by emulsion polymerization using the polymerizable surfactant.

Synthesis and Characterization of Alkoxy and Phenoxy-substituted Ferrocenium Salt Cationic Photoinitiators

Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopendadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4. and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoinitiating activities in epoxy resins.

Photoinitiating Characteristics of Benzophenone Derivatives as Type II Macromolecular Photoinitiators Used for UV Curable Resins

Dodecyl-benzophenone（DBP） and hexadecoxyl-benzophenone（HDBP） as type 11 photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%（mass fraction） tripropyleneglycol diacrylate （TPGDA）, resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry（photo-DSC）. DBP initiates the curing of acrylate more efficiently than HDBP, showing higher photopolymerization rate and unsaturation conversion, resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.

Application of Polymerizable Surfactant in the Preparation of Polystyrene/Nano-Fe_3O_4 Composite

Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano-Fe3O4 particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe3O4 particles into styrene monomer, and the polystyrene/nano-Fe3O4 composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano-Fe3O4 particles were studied by Fourier transform infrared （FTIR） spectrometry, X-ray diffraction （XRD） and transmission electron microscopy （TEM）, respectively. The experimental results show that the nano-Fe3O4 particles modified by monooctadecyl maleate with the size of about 7-10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis （TGA） and vibrating sample magnetometry （VSM） indicate that the thermal stability of polystyrene/nano-Fe3O4 composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials.

PHOTOPOLYMERIZATION OF PROPARGYL ACETATE WITH MICHLER’S KETONE AS PHOTOINITIATOR

Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator is described.

Nonionic Polymerizable Emulsifier in High-Solids-Content Acrylate Emulsion Polymerization

Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.

Synthesis and Characterization of Alkoxy and Phenoxy-substituted Ferrocenium Salt Cationic Photoinitiators

Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF6, [Cyclopen- dadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenylether]PF6, [Cyclopendadien-Fe-diphenylether]BF4, and [Cyclopendadien-Fe-diethoxybenzene] PF6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoini- tiating activities in epoxy resins.

Holographic property of photopolymers with different amine photoinitiators

Holographic parameters and photobleaching kinetics of the photopolymers with five different amine photoinitiators are studied. The maximum values of diffraction efficiency, photobleaching coefficient and quantum yield follow the sequence： Triethanolamine （TEA）〉 Diethanolamine （DEA）〉 Ethanolamine （EA）〉 Triethylamine （TETN）〉 Diethylamine （DETN）. The holographic capabilities of photopolymer performances are determined by the number of functional groups in the amine molecular structure. There is an optimum proportion of the photoinitiator, the photosensitizer and the monomer in the test of holographic parameters with different amine concentrations. The maximum diffraction efficiency is 59.26／%, sensitivity is 1.72／times 10^{ - 3}~cm^{2}/mJ, and the maximum refractive modulation index is 4.64／times 10^{ - 4}.

SYNTHESES AND ACTIVE BEHAVIOR OF NOVEL UV PHOTOINITIATORS

A series of novel hybrid photoinitiators(YPhCOPhXPhI^+PhPF_6^-,Y = 4-NO_2,4-MeO or 3-Cl,X = O,OCH_2,or nothing),which contain multiple aromatic rings(PhCOPhXPh),were prepared by reaction of easily available aryl ketones (YPhCOPhXPh) with iodosobenzene diacetate[PhI^+OCOCH_3(CH_3CO_2)^-].The inset of an aromatic ring into p-benzoyldiphenyliodonium hexafluorophophate(PhCOPhI^+PhPF_6^-)(BDPIH,He-type photoinitiator) between diphenyliodonium and benzoyl is propitious both to the preparation and the photoinitiat...

Electrochemical Studies on the Photolysis of Iron-Arene Complex Photoinitiator

Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electrochemical study reported in this note provides further evidence for the photolysis process which is crucial for the understanding of the photoinitiation mechanism.

PREPARATION OF POLYSTYRENE/SiO_2 COMPOSITE NANOPARTICLES BEARING SULFONIC GROUPS ON THE SURFACE VIA EMULSION COPOLYMERIZATION USING A POLYMERIZABLE EMULSIFIER

Functionalized PS/SiO_2 composite nanoparticles bearing sulfonic groups on the surface were successfully synthesized via emulsion copolymerization using a polymerizable emulsifierαolefin solfonate(AOS).As demonstrated by transmission electron microscopy and atomic force microscopy,well-defined core-shell PS/SiO_2 composite nanoparticles with a diameter of 50 nm were obtained.Sulfonic groups introduced onto the surface of the composite nanoparticles were quantified by FTIR,and can be controlled to some exten...

Photorheologically reversible micelle composed of polymerizable cationic surfactant and 4-phenylazo benzoic acid

A photorheologically reversible micelle composed of polymerizable cationic surfactant n-cetyl dimethylallyl am- monium chloride （CDAAC） and trans-4-phenylazo benzoic acid （trans-ACA） was prepared. The effects of molar ratio of CDAAC/trans-ACA, time of UV and visible light irradiation and temperature on the rheological properties of micellar system were investigated. The results show that before UV irradiation the system with an optimum CDAAC/trans-ACA molar ratio of 1.4 forms viscoelastic micelles at 45 ℃. After 365 nm UV irradiation, the viscos- ities of micelle systems with different concentrations at fixed molar ratio of 1.4 are decreased by 85%-95%. The CDAAC/trans-ACA （14 mmol. L- 1/10 mmol. L- 1 ） micelle system exhibits shear thinning property and its viscos- ity is decreased obviously with the increases of UV irradiation time less than I h. The rheological process during LIV irradiation for CDAAC/trans-ACA （14 mmol- L- 1/10 mmol. L 1） micelle proves that viscosity, elastic modulus G＇ and viscous modulus G＂ will reduce quickly with the UV light. Furthermore, the micelle system after 1 h UV- irradiation is able to revert to its initial high viscosity with 460 nm visible light irradiation for 4 h, and the micelle can be cycled between low and high viscosity states by repetitive UV and visible light irradiations. The LIV-Vis spectra of CDAAC/trans-ACA micelle indicate that its photosensitive theological properties are related closely to photoisomerization of trans-ACA to c/s-ACA.

Biphenyl Bis [π-cyclopentadienyl ） iron] Dication as an Efficient Cationic Photoinitiator for Epoxy Polymerization

Ferrocenium monocations as photoinitiators for cationic photopolymerization suffer from a limitation of low absorption and low reactivity under high-pressure Hg lamp. Here, a ferrocenium dication salt, biphenyl bis [π-cyclopentadienyl）iron] hexafluorophosphate （[bis（Cp-Fe）-biphenyl] （PF6）2 was synthesized by the ligand exchange reaction between ferrocene and biphenyl. The chemical structure was characterized with FTIR and ^1HNMR. The separation of ferrocenium monocation cyclopentadien-iron-biphenyl hexafluorophosphate （[Cp-Fe-biphenyl] PF6） and dication [bis（Cp-Fe）-biphenyl] （PF6）2 was carried out by column chromatography. The photoactivity of initiating photopolyinerization of epoxide ER14221 was studied as a cationic photoinitiator. [Bis（Cp-Fe）-biphenyl] （PF6）2 can efficiently absorb radiation above 300nm and its photoactivity is higher than that of its monocation.

具有抗紫外线功能的光固化涂料组合物的制备与性能研究

以羟基二苯甲酮、2-巯基苯并噁唑、芳基酰氯为原料,采用简单、温和的方法合成了新型二苯甲酮衍生物和含苯并噁唑的硫酯类衍生物,采用核磁氢谱1H NMR、核磁碳谱13C NMR和高分辨质谱HRMS等测试手段对目标化合物进行表征,并对其进行了光学性能测试,并用其制备了具有抗紫外线功能的光固化涂料。结果表明:两类衍生物能有效吸收220~350 nm的紫外光,与低聚物、单体相容性好,无气味。新合成的二苯甲酮衍生物作为光引发剂可使涂层固化时间大幅缩短到9 s,固化膜的外观、附着力和凝胶率相较于市售光引发剂BP有明显提高;硫酯类衍生物作为紫外吸收剂不仅能够增加光固化涂层的抗紫外线功能,且易于光固化涂料的制造、贮存。该组合物在罩面剂、油墨、胶黏剂等领域也有良好的应用前景。

光引发聚合制备P(AA-MA)高吸水性树脂及性能研究

以丙烯酸(AA)、马来酸酐(MA)为聚合单体,亚甲基双丙烯酰胺(MBA)为交联剂,安息香异丙醚为光引发剂,采用紫外光辐射聚合法合成了P(AA-MA)高吸水树脂。讨论了AA中和度、MA氨化度、单体质量比、交联剂的使用量等因素对吸水树脂吸水性能的影响。通过红外光谱(FT-IR)、扫描电子显微镜(SEM)和热重分析(TG)对树脂的分子结构、微观形貌和热稳定性进行了表征。结果表明,优化实验条件下所制备的高吸水树脂在蒸馏水中的最大吸水倍率为1112.5g/g,在0.9%盐水中的最大吸水倍率为100.8g/g。

二苯甲酮LED光引发剂的合成及性能研究

为了延长二苯甲酮光引发剂的吸收波长,使其与LED光源更好的匹配,本研究将苄氨基基团引入二苯甲酮结构,合成了3种4-双苄胺基二苯甲酮衍生物,其吸收波长延长至400 nm,与不同波长(365~405 nm)的LED光源能较好的匹配。利用实时红外对其光聚合动力学进行测试,通过电化学测试以及光降解测试等对其作用机理进行研究。结果表明:双苄胺基二苯甲酮衍生物是一类高效的LED光引发剂,其可作为单组分光引发剂引发1,6-己二醇二丙烯酸酯发生自由基聚合,双键转化率可达80%~83%。与碘鎓盐复配,引发阳离子聚合时环氧单体转化率可达45%,引发自由基-阳离子混杂光固化时双键转化率为69%~71%,环氧单体转化率为58%~61%,在自由基聚合及互穿网络聚合物结构光固化材料制备方面存在潜在应用价值。

低迁移咔唑基肟酯光引发剂的合成与性能研究

为降低光引发剂在光固化涂层中的迁移性,以咔唑为生色团,合成了2种以双键封端的可聚合型肟酯类光引发剂。利用紫外-可见光光度计对其紫外吸收、稳态光解和迁移性进行研究,通过傅立叶变换红外光谱仪(FT-IR)研究光致脱羧和光聚合动力学性能,并利用热重分析仪(TGA)对其热稳定性进行研究。结果表明:肟酯类光引发剂的最大吸收波长在338 nm,尾部吸收延至380 nm。在低光强365 nm LED辐照下(1 mW/cm2),咔唑基肟酯可发生光致脱羧反应,释放的活性自由基能有效引发丙烯酸酯单体和巯基-丙烯酸酯体系聚合。且可聚合型咔唑基肟酯类光引发剂在光固化涂层中显示了较低的迁移性。

光固化3D打印可聚合低共熔导电凝胶

离子凝胶对于柔性电子设备的发展具有重要意义,然而离子液体价格昂贵、有毒易造成环境污染。使用氯化胆碱(CHCL)、丙烯酸羟乙酯(HEA)、丙烯酰胺(AAm)制备了可聚合低共熔溶剂(PDES)替代传统离子液体,利用数字光处理(DLP)3D打印的成型方法,通过紫外光引发自由基聚合制备了P(HEA-co-AAm)-CHCL低共熔凝胶。通过傅里叶变换红外光谱、差示扫描量热分析证明了PDES的成功制备。对P(HEA-co-AAm)-CHCL的导电性能、力学性能、光学性能、传感性能进行了测试分析。结果表明,当CHCL和可聚合单体的物质的量之比为1∶3.5时凝胶的导电性能最好,离子电导率可达1.1×10-2 S/m。然后,固定CHCL和可聚合单体的物质的量之比为1∶3.5,改变HEA和AAm的物质的量之比制备了5种P(HEA-co-AAm)-CHCL,结合导电性能和力学性能测试结果发现,当HEA与AAm的物质的量之比为2.5∶1时,其拉伸强度、断裂伸长率分别为2.81MPa,1200%;具有优异的光学透明性,可见光透过率能够达到90%;应变系数为0.74;此外,具有优异的传感性能、循环稳定性等。

White-light-induced synthesis of injectable alginate-based composite hydrogels for rapid hemostasis

Dear Editor,Timely and effective hemostasis is of great significance for reducing body damage and mortality of patients [1]. Alginate is generally considered to be an excellent hemostatic polymer-based biomaterial and has been approved by the Food and Drug Administration as Generally Recognized as Safe [2]. However, the violent crosslinking reaction and unstable structure at the wound site limit its clinical applications. Hence, we report a biocompatible and injectable composite hydrogel methacrylate alginate (Alg-AEMA)-based Eosin Y/N-phenylglycine (NPG)-initiated composite hydrogel (AEC) composed of photocrosslinkable alginate, viscosity modifiers and novel white light photoinitiator, namely Eosin Y/NPG system, for instant hemorrhage control.

DEPs/木质素复合黏结剂的制备及性能研究

目的低共熔聚合物(DEPs)具有绿色环保、可设计性及生物相容性等特性,通过共混木质素(Lignin)合成制备具有良好的力学性能、热学性能和电化学性能的聚合物复合黏结剂,并探索其在新能源电池电极涂层领域的应用。方法以合成得到的可聚合低共熔溶剂(PDES)单体为基底,共混不同质量分数的木质素得到不同比例的PDES单体/木质素复合材料,通过热引发聚合制备得到DEPs/木质素复合黏结剂,并对复合黏结剂进行结构、力学性能、热学性能、表面形貌的分析,并在锂离子电池应用中探究电化学性能。结果通过实验得出,当选用一水合甜菜碱(betaine)-丙烯酸(AA)型PDES单体,木质素质量分数为6%时,制备的DEPs/木质素复合黏结剂综合各项性能最优,应用在硅(Si)电极中能够较好地控制体积变化问题,获得良好的电化学性能。结论制备获得了DEPs/木质素复合黏结剂,该黏结剂绿色环保、成本低、合成工艺简单、各项性能优异,可应用于新能源锂电池领域以及扩大木质素高价值化利用途径。