新型锍鎓盐类光生酸剂的合成及产酸性能研究

成功合成了两种新型锍鎓盐类光生酸剂,其结构经1HNMR和MS分析确认,并对其基本物性及在405、365nm光下乙腈溶液中的分解及产酸性能进行了研究,通过计算得出了分解及产酸量子产率.结果表明,两种化合物有较高的热分解温度和在常用有机溶剂中有较好的溶解性;在405nm光源下,4-（9′-苯基蒽基）苯基三氟甲磺酸锍鎓盐（PAGS1）和4-（4′-N,N-二乙基-1′-苯乙烯基）苯基三氟甲磺酸锍鎓盐（PAGS2）的分解量子产率分别为10%和15%,产酸量子产率为8.1%和13%;但在365nm光源下,分解及产酸量子产率均很低,说明两种光生酸剂对于405nm波长的光较敏感,适宜作为405nm光源下的光生酸剂.     

三嗪类化合物的合成及其产酸性能研究

合成了一系列的三嗪类光生酸剂1a-1e，确定了它们的结构，并对1e在乙腈溶剂中365和405nm光下的曝光分解产酸性能进行了初步的定量研究．结果表明，在测定浓度范围内分解量子产率和产酸量子产率基本上都不随浓度的变化而变化，在405nm光下比在365nm光下有更高的分解和产酸量子效率．有关这类化合物的光生酸性能与曝光波长的关系正在进一步研究中．     

405nm成像体系用三嗪类光生酸剂的制备、性质和应用研究

制备了5种三氯甲基取代的三嗪类光生酸化合物,其结构经1HNMR、IR等分析确认,分别考察了它们在有机溶剂中的溶解性,通过TG测定确定了其热分解性能,并测定了它们的紫外可见吸收光谱,以及对在405、365 nm光源下的光分解及产酸性能进行了研究.成像实验表明,它们可用于405 nm的成像组成物中.     

2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪光引发剂的合成与聚合动力学研究

本研究以4-甲氧基苯甲醛和2,4-双(三氯甲基)-6-甲-基1,3,5-三嗪为原料合成了一种引发剂2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪(BMT),并利用红外光谱、紫外光谱、核磁共振等手段对其结构进行表征.利用实时红外光谱研究其光聚合动力学性能,结果表明,不同引发剂浓度,不同单体和不同光强对单体双键转化率都有一定的影响.     

一种UVA型光产酸剂

本文合成了一种以硫杂蒽酮为基核的光产酸剂,该光产酸剂对UVA段紫外光敏感,光解可以产生超强酸,且在365、385、395 nm LED光源下具有良好的光产酸效率,光产酸量子产率Φa为0.10～0.11。     

活性酯法合成来氟米特

2-氯-4,6-二甲氧基-1,3,5-三嗪和N-甲基吗啉反应得到氯化4-(4,6-二 甲氧基-1,3,5-三嗪-2-基)-4-甲基吗啉,其与5-甲基异(噁)唑-4-甲酸反应制备2-(5-甲基异(噁)唑-4-甲酰氧基)-4,6-二甲氧基-1,3,5-三嗪,所得化合物与4-三氟甲基苯胺反应合成标题化合物,总收率约72％(以...     

一种基于三苯胺类光生酸剂的制备与表征

成功合成了1种以三苯胺为主体的硫盐光生酸剂,其结构经1HNMR、IR分析确证,并对其物性进行了基本考察,有较高的热分解温度和在常用有机溶剂中有较好的溶解性。并考察了其在相同浓度、相同光强、相同曝光波长(405 nm)下在3种不同溶剂(乙腈、四氢呋喃、二氯甲烷)中的分解及产酸性能,计算出分解量子产率和产酸效率。     

酸敏变色记录材料的光谱特性及其光量子产率

本文研究了由偏二氯乙烯－丙烯酸甲酯共聚合物（VdCl2-MA）和五甲氧基红指示剂组成的酸敏变色记录材料的光谱特性,测定了其光分解量子产率,通过添加光敏剂使原来只有在254nm紫外光下曝光才能发生光分解反应的酸敏变色材料在365nm紫外光下曝光也可发生光分解而变色。酸敏变色材料在254nm处紫外光曝光量子产率为0.032-0.020;在365nm处紫外光曝光量子产率为0.110-0.034。光敏剂的加入使酸敏变色材料量子产率提高了2－4倍。     

光稳定剂中间体2-氯-4,6-二(N-丁基-1-环己氧基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪的合成研究

采用单因素法,以2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪、环己烷、叔丁基过氧化氢为原料,三氧化钼为催化剂合成2-氯-4,6-二(N-丁基-1-环己氧基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪。结果表明,最佳工艺条件为反应温度95℃,反应时间14 h,原料物质的量比n(2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪)∶n(环己烷)∶n(叔丁基过氧化氢)为0.01∶0.45∶0.2,催化剂三氧化钼用量为0.4 g (相对0.01 mol2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪),产品收率为93.50%。     

用于水性车漆的受阻胺光稳定剂的合成及性能

设计、合成了一种受阻胺光稳定剂（HALS）TM-3。首先,三聚氯氰和N-丁基-2,2,6,6-四甲基-4-哌啶胺通过亲核取代反应合成了N-丁基-4,6-二氯-N-(2,2,6,6-四甲基-4-哌啶基)-1,3,5-三嗪-2-胺（中间体Ⅰ）;中间体Ⅰ再与N,N-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺反应生成了N2,N2’-(己烷-1,6-二基)双[N4-丁基-6-氯-N2,N4-双(2,2,6,6-四甲基哌啶-4-基)-1,3,5-三嗪-2,4-二胺]（中间体Ⅱ）;最后,中间体Ⅱ水解生成目标化合物6,6’-{己烷-1,6-二基双[(2,2,6,6-四甲基哌啶-4-基)氮二基]}双{4-[丁基(2,2,6,6-四甲基哌啶-4-基)氨基]-1,3,5-三嗪-2-醇}（TM-3）。采用1HNMR、13CNMR、HRMS表征了TM-3的结构,通过UV-Vis、TGA考察了其性能,比较了TM-3和双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯（HALS770）在汽车清漆涂料中的光稳定性。结果表明,TM-3在210nm处具有强烈的UV-Vis吸收;热稳定性能良好,在400℃以前能...     

A positive‐working photosensitive polyimide based on thermal cross‐linking and acidolytic cleavage

A novel positive‐working photosensitive polyimide (PSPI) based on a poly(hydroxyimide) (PHI), a crosslinking agent having vinyl ether groups, and a photoacid generator (PAG) was prepared. The PHI as a base resin of the three‐component PSPI was synthesized from 4,4′‐oxydiphthalic anhydride and 2,2′‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane through ring‐opening polymerization and subsequent thermal cyclization. 2,2′‐bis(4‐(2‐(vinyloxy)ethoxy)phenyl)propane (BPA‐DEVE) was used as a vinylether compound and diphenyliodonium 5‐hydroxynaphthalene‐1‐sulfonate was used as a PAG. The phenolic hydroxyl groups of the PHI and the vinyl ether groups of BPA‐DEVE are thermally crosslinked with acetal structures during prebake step, and the crosslinked PHI becomes completely insoluble in an aqueous basic solution. Upon exposure to UV light (365 nm) and subsequent postexposure bake (PEB), a strong acid generated from the PAG cleaves the crosslinked structures, and the exposed area is effectively solubilized in the alkaline developer. The dissolution behavior of the PSPI containing each 11.5 wt % of BPA‐DEVE and of the PAG was studied after UV exposure (365 nm) and PEB. It was found that the difference in dissolution rates between exposed and unexposed areas was enough to get high resolution. A fine positive pattern with a resolution of 5 μm in a 3.7‐μm‐thick film was obtained from the three‐component PSPI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

DMACM-caged adenosine nucleotides: ultrafast phototriggers for ATP,ADP, and AMP activated by long-wavelength irradiation

The development of new photocleavable adenosine nucleotides based on the photochemistry of [7-(dimethylamino)coumarin-4-yl]methyl (DMACM) esters is described. The phototriggers liberate adenosine triphosphate (ATP), diphosphate, and monophosphate upon UV/Vis irradiation between 334 and 405 nm. The efficiency of photocleavage at long wavelengths is high as a result of a combination of appropriate quantum yields and intensive absorptivities. By using time-resolved fluorescence spectroscopy, we determined a lower limit of 1.6 x 10(9) s(-1) for the rate constant of the release of ATP from DMACM-caged ATP. The favorable properties of DMACM-caged ATP were confirmed in physiological studies by confocal laser scanning microscopy. We were able to uncage DMACM-caged ATP in cultures of mouse astrocytes and in brain tissue slices from mice and were also able to measure the effect of photoreleased ATP on the cellular response of astrocytes, namely the ability of the ATP to evoke Ca(2+) ion waves.     

New positive-type photosensitive polyimide having sulfo groups

A new positive-working photosensitive polyimide (PSPI) has been developed, which is based on polyimide bearing sulfo groups (PIS) and 1-{1,1-bis[4-(2-diazo-1-(2H)naphthalenone-5-sulfonyloxy)phenyl]ethyl}-4-{1-[4-(2-diazo-1(2H)naphthalenone-5-sulfonyloxy)phenyl]methylethyl}benzene (S-DNQ) as a photosensitive compound. PIS was prepared by ring-opening polyaddition of 1,3-phenylenediamine-4-sulfonicacid (PDAS), 4,4′-oxydianiline (ODA), and 4,4′-hexafluoropropylidenebis(phthalic anhydride) (6FDA), followed by thermal cyclization in m-cresol. PIS containing 30 wt% of S-DNQ showed a sensitivity of 100 mJ cm⁻² and a contrast of 1.7, when it was exposed to 365 nm light followed by developing with 2.38 wt% aqueous tetramethylammonium hydroxide (TMAH) solution at room temperature. A fine positive image featuring 10 μm line and space patterns was observed on the film of the photoresist exposed to 200 mJ cm⁻² of UV-light at 365 nm by the contact mode. The positive image was successfully converted to the polyimide pattern by thermal treatment.     

i-Line sensitive photoacid generators for UV curing

UV curing systems based on cationic processes are very significant because the systems have several advantages compared to the radical process. Photoacid generator (PAG) is essential for the cationic UV curing system including epoxides and vinyl ethers. Although many types of PAG have been developed, most of them are not sensitive to i-line (365 nm) from a high-pressure mercury lamp. In this study, non-ionic PAG that is thermally stable and highly sensitive to i-line was designed and synthesized. Imino sulfonate and N-hydroxyimide sulfonate compounds were prepared as PAG. Fluorenone, thioxanthone, and thianthrene skeletons were used as chromophores for PAG. Furthermore, photochemistry of the PAG and its applications to photocrosslinking systems based on epoxy-containing polymers were studied.     

Synthesis and characterization of highly fluorescent phenylene vinylene containing perfluorocyclobutyl (PFCB) aromatic ether polymers

4-(Trifluorovinyloxy)benzaldehyde was treated under Wittig conditions with 4-dihexyloxy-2,5-xylenebis(triphenylphosphoniumbromide) to form 1,4-bis(2′-(4-trifluorovinyloxyphenyl)ethenyl)-2,5-dihexyloxybenzene, a novel phenylene vinylene-bistrifluorovinyl ether monomer. Cyclopolymerization afforded an insoluble, non-luminescent material likely due to cross-addition reactions between phenylene vinylene olefin and trifluorovinyl ether (TFVE). However, 1,2-bis(4-formylphenoxy)hexafluorocyclobutane was polymerized with 1,4-dihexyloxy-2,5-xylenebis(triphenylphosphoniumbromide) and 1-methoxy-4-(2-ethylhexyloxy)-2,5-xylenebis(triphenylphosphoniumbromide) under Wittig conditions to yield two novel poly(perfluorocyclobutyl-co-phenylene vinylene) polymers. The polymers are of moderate molecular weight (8600-8700 M_n), show excellent thermal stability (T_d = 390-405 °C), and are readily soluble in common organic solvents. The materials are highly fluorescent in both solution and thin film with solution quantum yields of 68 and 71%.     

Spectroscopic investigations of vinyl-substituted 10H-phenothiazine

Different 10H-phenothiazine derivatives modified at their 3- and 3,7-positions with conjugated electron-deficient pyridine or pyridinium groups using ethenyl linkers are described. Spectral variations of 3-((E)-2-(Methylpyridium-4-yl)vinyl)-10H-phenothiazine iodide and 3,7-bis((E)-2-(Methylpyridium-4-yl)vinyl)-10H-phenothiazine diiodide, which are attributed to intramolecular charge transfer, electronic rearrangement and contact ion-pair mechanisms, were observed to be either base or ion dependent. Depending on the extent of deprotonation of the nitrogen atom in the 10-position of the phenothiazine core, donor–acceptor or push–pull systems provide fluorophore-switching and potential near infrared sensor application.     

Synthesis,characterization, and properties of a novel positive photoresist polyimide

An aqueous base-soluble polyimide (BAPAF/6FDA) was obtained from the polycondensation of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAPAF) and 4,4′-(hexafluoroisopropylidene)–bis(phthalic anhydride (6FDA). It exhibits high thermal stability and high transparency at 365 nm. A novel positive photoresist was prepared by protecting BAPAF/6FDA with a trimethylsilyl group while using diazonaphthoquinone as the photosensitizer. In addition, the silylated polyimide was converted to aqueouse base-soluble polyimide in the presence of an acid and a slight amount of water. This photoresist yields a sensitivity of 110 mJ/cm² and a contrast of 3.24. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 67:1313–1318, 1998