萘酚基酚醛树脂的合成及其在lift-off光刻胶中的应用

首先以α-萘酚、间甲酚、甲醛为单体,通过缩聚反应合成了萘酚基酚醛树脂NAPR,随后与二碳酸二叔丁酯(DBDC)反应制备了一系列t-BOC改性的萘酚基酚醛树脂NAPR-BOC。用红外(FT-IR)、核磁(~1H NMR)、凝胶色谱(GPC)、热失重分析(TGA)对其结构及性能进行了表征。以NAPR-BOC-2为基体树脂配制成lift-off光刻胶,测试了光刻胶的分辨率、形貌和耐热性,得到的光刻胶分辨率最大为0.6μm,耐热可达130℃。     

间乙炔基苯偶氮线性酚醛泡沫的结构与性能研究

采用高温化学发泡法制备了一种间乙炔基苯偶氮酚醛树脂泡沫(EPANF).采用傅里叶红外光谱(FTIR)、凝胶渗透色谱(GPC)、光学显微镜、扫描电子显微镜(SEM)、导热系数分析仪、临界氧指数分析仪和热重分析(TG)等表征了间乙炔基苯偶氮酚醛树脂(EPAN)结构和EPANF的泡孔结构、压缩强度、隔热性能、阻燃性能和热性能.研究结果表明,当所用发泡剂含量为18%,泡沫体的表观密度为0.179 g/cm~3时,EPANF泡孔均匀微细,闭孔率高,泡孔平均粒径为350μm左右.随着表观密度增加,泡沫体压缩强度增大,热导率系数增大,隔热性能略有下降,但其临界氧指数变大,阻燃性能提高.当表观密度为0.363 g/cm~3时,EPANF的压缩强度达到最大为5.63 MPa.EPANF的5%和10%热失重温度分别为333、381℃,其700℃的残炭率和1000℃的残炭率分别为65.8%和58.2%,耐热性和耐烧蚀性较普通线性酚醛树脂有明显提高.EPANF作为热结构材料和烧蚀材料有望在航天航空等领域应用.     

L-聚乳酸固相缩聚的工艺研究

以L-乳酸单体为原料,采用复合催化剂通过直接熔融法合成低聚左旋聚乳酸(PLLA),然后分段控温进行固相缩聚(SSP).对固相缩聚的工艺条件进行了详细的研究.采用粘度法和凝胶渗透色谱法(GPC)对固相缩聚产物PLLA的特性粘数([η])和分子量进行了表征.用差示扫描量热(DSC)研究了固相缩聚产物的熔融行为和结晶度.结果...     

甾核基酯类化合物的合成与液晶性能

分别以胆固醇、胆酸为原料,合成了5种甾核基酯类化合物,采用红外光谱（FTIR）和紫外光谱（UV）对其结构进行表征,并用偏光显微镜（POM）和示差扫描量热法（DSC）研究其液晶行为。结果表明,合成的小分子产物丙酸胆固醇酯、苯甲酸胆固醇酯具有一定的液晶性能,而乳酸胆固醇酯和高分子的聚乳酸胆固醇酯、聚乳酸-胆酸共聚物在熔融状态下不具有液晶性质。     

生物降解材料胆酸-乳酸共聚物的热性能研究

通过直接熔融共聚法合成了系列的不同乳酸／胆酸组成比（LA／CA）的胆酸．乳酸共聚物,用DSC、TG等手段研究生物降解材料胆酸-乳酸共聚物的热性能。结果表明,共聚物的热性能与其组成、结构有关。LA／CA小的多核共聚物无明显熔融峰,热失重分两步进行;LA／CA大的单核共聚物出现明显双头熔融峰,其热失重一步进行,其Tg随着LA／CA增加而升高。     

聚(4-三甲基硅基)苯乙炔膜的气体透过性

合成了4-三甲基硅基苯乙炔(SPA)单体,采用核磁共振谱(1H-NMR)和傅里叶变换红外光谱(FT-IR)对其进行了表征.在Pd(PPh3)2Cl2和金属共催化剂催化下制备了聚4-三甲基硅基苯乙炔(PSPA).PSPA易溶于氯仿、甲苯等有机溶剂,成膜性较好,具有较高的强度和热稳定性.热重分析(TGA)表明其5%失重温度为300～310℃.PSPA膜对CO2气体透过系数达到848 Barrer,并具有较高的透过选择性,分离系数达到12.68,摆脱了"Robeson"上限的限制.     

热分析技术研究疏水缔合微区对含氟丙烯酸酯共聚物凝胶中水状态的影响

丙烯酸 (AA)与不同含量的 2 (N 乙基全氟辛烷基磺酰胺 )乙基甲基丙烯酸酯 (FMA)在叔丁醇中进行自由基共聚 ,合成了一系列疏水改性共聚物凝胶 .用示差扫描量热法 (DSC) ,热失重分析 (TGA)研究了含氟疏水改性凝胶中水的状态 ,证明FMA改性凝胶中存在 3种状态的水 ,即不可冻结水 ,可冻结结合水和自由水 .对于未改性凝胶和FMA含量为 1mol%的疏水改性凝胶 ,在凝胶中水含量分别低于 0 60 9mol%和 0 698mol%时 ,DSC升温曲线上观察不到熔融峰 ,说明凝胶中存在不可冻结水 .提出计算凝胶中 3种状态的水含量和熔融焓的理论假设 .计算出FMA含量为 1mol%的疏水改性凝胶中自由水和可冻结结合水的摩尔熔融焓分别为75 89 0 3和 6864 0 6J mol.计算结果表明疏水改性后 ,单位聚合物单元上结合的可冻结水数目 (n1 )和非冻结水的数目 (n0 )都增加     

耐高温含氟磺化聚苯并咪唑的合成及表征

采用5-磺酸钠间苯二甲酸、双(苯甲酸)六氟丙烷与3,3',4,4'-四氨基联苯在多聚磷酸中通过共缩聚反应, 合成了一系列磺化度(定义为100个重复单元中所含的磺酸基个数, SD)可控的含氟磺化聚苯并咪唑(sPBI), 并利用红外光谱、核磁共振、凝胶色谱和热失重分析等手段对其结构、分子量与热稳定性进行了表征, 还考察了其溶解性和成膜性. 结果表明, sPBI的数均分子量(M_n)为61300～86000, 多分散指数介于1.96～2.34之间, 并且sPBI具有良好的成膜性和优异的热稳定性能, 其5%和10%热失重对应温度均随着SD的增加而有所提高, 在SD为70%时分别为549和576 ℃. 此类聚合物在质子交换膜材料方面具有一定的应用前景.     

DSC研究高吸水树脂吸水性能与分子结构的关系

以丙烯酸(AA)、丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为共聚单体合成了聚丙烯酸-丙烯酰胺-2-丙烯酰胺基-2-甲基丙磺酸(PAA-AM-AMPS)三元共聚物高吸水树脂.利用茶叶袋法测定了其最大吸水倍率,通过差示扫描量热仪(DSC)测定并比较了含水量为50%,75%和91%的各种水凝胶的自由水和结合水含量.结果表明在蒸馏水和生理盐水中高吸水树脂的最大吸水倍率分别为1900g/g和185g/g,共聚物的结合水含量随着AMPS和AA含量增加及AM含量的减少而增大;在0.9%生理盐水中,结合水含量随着AMPS和AM含量增加及AA含量的减少而增大,共聚物和均聚物高吸水树脂的最大吸水倍率呈现出与结合水含量相同的变化规律.     

以纳米笼形POSS为交联剂的PHEMA水凝胶的制备及其对诺氟沙星的缓释行为

以甲基丙烯酸β-羟乙酯(HEMA)为单体、笼形八聚(乙烯基)倍半硅氧烷(OVPS)为交联剂,通过溶液自由基聚合方法制备了一系列P(OVPS-co-HEMA)水凝胶。采用核磁共振氢谱(1 H-NMR)、傅里叶红外光谱(FT-IR)、扫描电镜(SEM)、差示扫描量热仪(DSC)、热重分析仪(TG)、动态黏弹谱仪(DMA)和紫外可见分光光度计对其结构与性能进行了研究。结果表明:通过控制投料比可以调节P(OVPS-co-HEMA)水凝胶中OVPS的含量;随着OVPS投料比例的增加,水凝胶的交联密度变大,孔洞直径由10~15μm逐渐减小至5~10μm;OVPS的引入增强了水凝胶的力学强度;P(OVPS-co-HEMA)水凝胶对药物诺氟沙星具有良好的控释作用,达到释药平衡的时间为96h,累计释药率最高可达99.56%,可用于接触镜片、人工角膜和组织工程材料。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.