硫杂蒽酮类光产碱剂的合成及其光化学性能研究

以硫代水杨酸和苯硫乙酸为原料,通过两步法成功合成了一种新型的单组分硫杂蒽酮类光产碱剂。利用核磁氢谱、核磁碳谱和高分辨率质谱对光产碱的结构进行了表征,通过稳态光解及电子自旋共振波谱等对光解产物进行了系统研究。该光产碱剂在400nm附近有较强的吸收,可有效引发巯基-环氧光聚合,其引发活性优于文献报道的高效光产碱体系。     

新型水溶性硫杂蒽酮类光引发剂的光引发性能研究

利用红外光谱技术对六种新型水溶性硫杂蒽酮类光引发剂在紫外光聚合反应中的引发性能进行了测试,用相对峰面积法计算了聚合反应的转化率,并据此对引发剂结构与光化学性能之间的关系做了一定的探讨。结果表明该类光引发剂具有很高的光化学活性,而引发剂的结构直接影响引发性能。研究发现硫杂蒽酮母体上甲基的引入使引发剂的引发效率增大,而引发剂侧链上羟基的引入,则由于降低了质量转移的有效性并有可能使引发剂分子缔合,致命引     

季铵盐光产碱剂的光物理与光化学性能

季铵盐光产碱剂的光物理与光化学性能;季铵盐;四苯硼盐;光产碱剂;光物理;光化学     

新型水溶性硫杂蒽酮类光引发剂的光化学性能研究

本文对8种水溶性硫杂蒽酮类光引发剂进行了紫外 可见光谱、荧光光谱以及电子自旋共振光谱(ESR)等测试。测定了最大吸收波长,计算了摩尔消光系数,荧光量子产率,测定了ESR信号强度等。并对其结构与光化学性能之间的关系进行了讨论。     

硫杂蒽酮类光引发剂的紫外光谱特性及量子化学研究

本文研究了十四种烷基、烷氧基取代的硫杂蒽酮类光引发剂的紫外光谱特性，利用量子化学的分子轨道理论圆满地解释了硫杂蒽酮类化合物的紫外吸收波长与其结构的关系。利用具有分子结构逻辑识别功能和分子结构编辑功能的ＣＡＭＴＣ软件，及ＰＰＰ计算程序对十四种硫杂蒽酮类化合物的吸收波长进行了计算，计算的结果和实测值能够很好的吻合。计算得到的线性回归方程对于预测硫杂蒽酮类化合物的最大吸收波长是十分有用的。     

新型水性硫杂蒽酮类光引发剂的合成与性质

合成了１２ 种新的水性硫杂蒽酮类光引发剂,并经红外光谱、质谱、核磁共振以及元素分析等手段确证了化合物的结构,测定了其最大紫外吸收波长,计算了摩尔消光系数和荧光量子效率,并对化合物结构及其光化学性能之间的关系作了初步的探索．     

含硫杂蒽酮类光引发剂的聚合体系的光固化研究

首次应用N121型紫外光固化测试仪研究以硫杂蒽酮为光引发剂的光聚合体系的光固化性能。为测定以硫杂蒽酮为光引发剂的光聚合体系的光聚合速度提供了新的方法,同时讨论了光源的发射波长与光引发剂的吸收波长之间的关系。     

苯乙酮衍生物四苯硼季铵盐光产碱剂的合成

以苯乙酮衍生物、杂环叔胺和四苯硼盐为原料,合成了2个新的具有光活性的季铵盐光产碱剂,其结构经元素分析、IR和^1H NMR确证。     

硫杂蒽酮类光引发剂的电子自旋共振研究

本文采用ESR手段对五种硫杂蒽酮类光引发剂2-甲基硫杂蒽酮(MTX)2,4-二甲基硫杂蒽酮(DMTX)、1,2,4-三甲基硫杂蒽酮(TMTX)、2-甲氧基硫杂蒽酮(MOTX),2-戊氧基硫杂蒽酮(AOTX)和三乙胺引发体系进行了研究,提出了该类光引发剂和三乙胺暗反应的机理。     

新型苯乙酰脒类化合物的合成及其感光性能

以氢化铝锂为还原剂,甲基叔丁基醚为溶剂,1,5-二氮杂双环[4.3.0]-5-壬烯(1)于55℃反应9 h制得1,5-二氮杂双环[4.3.0]壬烷(2),收率87.9%,纯度95.0%。2分别与溴代苯乙酮(3a),对甲氧基溴代苯乙酮(3b)和对溴基溴代苯乙酮(3c)进行消除反应合成了3个新型的苯乙酰基潜双环脒类化合物(4a~4c),其结构经1H NMR和LC-MS表征。采用正交实验对合成4a~4c的反应条件进行了优化。在最佳反应条件[以甲苯为溶剂,3a 25.2 mmol,n(3a)∶n(K2CO3)∶n(2)=1.0∶2.0∶1.4,于15℃反应24 h]下,1,5-二氮杂双环[4.3.0]-5-苯乙酰基壬烷(4a)收率89.0%,纯度87.9%。感光性能研究结果表明,1,5-二氮杂双环[4.3.0]-5-(4-甲氧基)苯乙酰基壬烷(4b)经紫外曝光400 mJ·cm-1,其引发性能最强,分解转化近45%;曝光2 000 mJ·cm-1,4b分解转化近90%。     

h-线敏感光致产碱剂PNCDP的合成与表征

设计并合成了一种对高压汞灯发射光谱中的h-线(405 nm)敏感的新型光致产碱剂(PBG)——N-{[(5-哌啶-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(PNCDP).通过红外(IR)、核磁(NMR)以及元素分析对PNCDP的结构进行了表征.紫外-可见光谱(UV-Vis)测试结果表明,与传统的i-线(365 nm)敏感PBG——N-{[(4,5-二甲氧基-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(DNCDP)相比,PNCDP的最大紫外吸收波长为395.5 nm,较DNCDP红移了52.5 nm.初步光刻实验表明,PNCDP对h-线具有较好的敏感度.     

Photobase generation from amineimide derivatives and their use for curing an epoxide/thiol system

The structural effects of amineimide derivatives on photobase generation and the use of the resultant base for thermal curing of an epoxide/thiol system are investigated. The results of UV spectral change and gas chromatographic‐mass spectrometric analysis indicated that amineimide derivatives undergo photolysis by UV irradiation and generate bases. The order of conversion of the photolysis for the functional groups introduced to amineimide derivatives was NO₂ > N(CH₃)₂ > CN > OCH₃ > H. By using aminimide derivatives with NO₂ and N(CH₃)₂ groups, the curing of the epoxide/thiol system was shifted to lower temperature after UV irradiation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4045–4052, 2002     

Recent Advances and Challenges in the Design of Organic Photoacid and Photobase Generators for Polymerizations

Photopolymerization, or the use of light to trigger polymerization, is one of the most exciting technologies for advanced manufacturing of polymers. One of the key components in the photopolymerization processes is the photoactive compound that absorbs the light, generating the active species that promotes the polymerization and largely determines the final properties of the material. The field of photopolymerization has been dominated by photoradical generators to mediate radical reactions. In the last decade, to expand the number of polymers that can be prepared by photopolymerization, intensive research has been devoted to the synthesis and utilization of photoactive molecules that are able to generate a base or an acid upon irradiation. These organic compounds are known to promote not only the ring‐opening polymerization of various heterocyclic monomers such as lactones, carbonates, or epoxides but also to trigger the step‐growth synthesis of polyurethanes. This Minireview highlights the recent advances in the development of organic photobase and photoacid generators, with the aim of encouraging the wider application of these photoactive compounds in the photopolymerization area and to expand the use of these polymers in advanced manufacturing processes.     

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¹1HNMR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.     

磺酸肟酯类光产酸剂的制备及性能研究

本文合成了4种磺酸肟酯类非离子型光产酸剂,用核磁氢谱确认了产物结构,并测试了其热稳定性、紫外吸收特性及产酸效率.结果表明,合成的4种磺酸肟酯类光产酸剂在350-450 nm和深紫外区(DUV,248 nm)都有很好的吸收,在420 nm波段曝光下,(5-对三氟甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-2)产酸率最高,可达0.96;(5-对甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-1)在365 nm和420 nm两个波段下,均有较高的产酸率.利用实时红外(RT-IR)研究了相同浓度下4种光产酸剂对乙烯基醚化合物引发的光聚合动力学,同时研究了光产酸剂浓度对光聚合反应的影响,发现产酸剂浓度为2%时,光照30 s乙烯基醚化合物的双键转化率(DC%)即能达到80%.     

光敏性季铵盐的合成与性能研究

制备了α-二乙氨基苯乙酮并在醋酸环境下将该化合物与苯基缩水甘油醚（PGE）反应合成了以醋酸根为配对阴离子的、具有芳酮结构的光敏性季铵盐（α-PGE－A），通过红外吸收光谱，核磁共振谱及热重分析对α-PGE－A紫外光辐照前后的结构进行了研究。红外光谱显示α-PGE－A经紫外辐照后，其羰基吸收峰显著增强，醋酸根离子吸收峰消失；核磁共振研究表明样品光照后可能生成频胺及醋酸酯。α-PGE-A与环境树脂复配合的热固化研究显示，经紫外光辐照后的样品热固化较易进行完全。表明α-PGE-A具有一定光产碱活性。     

Image formation by dyeing of copolymers bearing photogenerated acid and base groups with dye bath containing acid and basic dyes

Copolymers bearing photoacid generating groups and/or photobase generating groups were dyed after UV irradiation with a dye bath containing both an acid dye and a basic dye. Acetophenone O‐acryloyloxime (AAPO) was used as a monomer bearing acyloxyimino (AOI) group that generates a primary amino group upon irradiation, which is followed by hydrolysis. Phenacylsulfonylstyrene (PSSt) and 1,2,3,4‐tetrahydronaphthylideneamino p‐styrenesulfonate (NISS) were chosen as monomers having β‐keto sulfone (β‐KS) and iminosulfonate (IS) groups, respectively, which yielded acid groups when irradiated. Copolymers of AAPO and methyl methacrylate (MMA) were dyed with only the acid dye, and those of PSSt or NISS were dyed with only the basic dye after irradiation. AAPO‐PSSt‐MMA films became dyeable with the acid dye when irradiated for a short time and with the basic dye with further irradiation. However, AAPO‐NISS‐MMA copolymers showed the reverse dyeing behavior. IR spectra revealed that AOI groups were photochemically decomposed prior to the β‐KS groups for AAPO‐PSSt‐MMA, and AOI and IS groups decomposed simultaneously for AAPO‐NISS‐MMA. These results suggested the possibility of adsorption of different ionic dyes on the films by a change of irradiation time; in fact, color patterns could be obtained in a single staining process using the dye bath. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3043–3051, 2000