一种新型无色DAR成色剂的合成与应用

以N，N’-双-(2-氯-5-正十二烷氧基羰基)苯基丙二酰胺为母体，以2，5-二巯基-1，3，4-噻二唑为吸附基团，以2-三氟乙酰基苯肼作为增强基团合成了一种新型无色DAR成色剂，通过了IR，^1HNMR和MS的认证．实验证明，该DAR成色剂能够提高感光度，并且耐老化性能良好．     

基于PBO共聚物改性纤维的制备及其耐紫外光老化性能的研究

本文首先探索聚对亚苯基苯并二噁唑(PBO)前置单体4,6-二硝基间苯二酚(DNR)及4,6-二氨基间苯二酚盐酸盐(DAR)的最佳合成方法及条件,合成高纯DAR(99.796%);其次从分子设计出发,即通过DAR单体制备复合盐(引入对苯二甲酸TA),以复合盐的自聚制备常规PBO;再次基于PBO结构通过设计引入第三单体2,5噻吩二甲酸即以复合盐间的共聚成功制得含噻吩结构的聚苯并噁唑树脂,通过干喷湿纺法制备纤维,对其进行特性黏度测试(可达8.46 d L·g-1),同时对影响黏度的因素:固含量、反应器类型等进行探讨分析;最后进行光稳定性测试,使得PBO树脂性能得以显著改善。     

新型DAR成色剂的合成与照相性能研究

本文合成了两个新型DAR成色剂,其结构经IR,1H-NMR和MS得到确证.照相性能试验结果表明:DAR成色剂D1能提高感光度20%,而DAR成色剂D2在目前的显影条件下没有提高感光度的作用.通过分析其结构,找到了结构与照相性能之间的关系.     

苯并[1,2-d:5,4-d']二(噁唑)-2,6-二硫醇的合成及表征

苯并噁唑类化合物是一类重要的杂环化合物,不仅在生物、医药等方面有着广泛应用,而且在光学材料、高性能复合材料等诸多领域也显现出独特的性能。以间苯二酚为原料,经过酯化反应和Fries重排、肟化反应、Beckmann重排和水解反应合成4,6-二氨基间苯二酚盐酸盐(DAR·HCl)。然后以4,6-二氨基间苯二酚盐酸盐和二硫化碳为原料合成标题化合物,并且优化了过程的工艺条件,过程的总收率为37.3%。利用红外光谱、核磁共振谱、质谱和元素分析等分析手段对中间产物及目标化合物进行了表征。     

PBO纤维中间体DAR合成工艺开发成功

2006年2月8日大连化工研究设计院开发成功聚对苯撑苯并双噫唑（PBO）纤维关键中间体4，6-二氨基间苯二酚（DAR）合成新工艺。     

苯并[1,2-d:5,4-d']二((口恶)唑)-2,6-二硫醇的合成及表征

苯并(口恶)唑类化合物是一类重要的杂环化合物,不仅在生物、医药等方面有着广泛应用,而且在光学材料、高性能复合材料等诸多领域也显现出独特的性能.以间苯二酚为原料,经过酯化反应和Fries重排、肟化反应、Beckmann重排和水解反应合成4,6-二氨基间苯二酚盐酸盐(DAR· HCl).然后以4,6-二氨基间苯二酚盐酸盐和二硫化碳为原料合成标题化合物,并且优化了过程的工艺条件,过程的总收率为37.3％.利用红外光谱、核磁共振谱、质谱和元素分析等分析手段对中间产物及目标化合物进行了表征.     

中间体与精细化工文摘

4,6-二氨基间苯二酚研究进展及合成工艺 文摘:4,6-二氨基问苯二酚(DAR)是新型高分子材料顺式聚对苯撑苯丙二恶唑(PBO)的必不可少的中间体。由于PBO具有极高的抗拉强度、弹性模量、68级的极限氧指数和650℃以下的稳定性等性能指标均属目前有机和无机纤维之最,并开始应用于军事、航空航天厦汽车等工业高     

聚对亚苯基苯并二(噁)唑合成新路线及其制备新技术

为进一步提升聚对亚苯基苯并二噁唑（PBO）材料的性价比并促进其工业化,研究了以4,6-二硝基间苯二酚为原料,先选择还原制得4-氨基-6-硝基间苯二酚盐酸盐,进而与对甲氧羰基苯甲酰氯进行缩环合获得苯并噁唑化合物,再催化加氢合成AB型PBO新单体2-(对甲氧羰基苯基)-5-氨基-6-羟基苯并噁唑（MAB）,最后自缩聚反应制备PBO的新路线和新方法.结果表明：该方法具有原料易得、反应条件缓和、中间体稳定等新技术优势.合成的PBO树脂总收率达64%、特性黏数η>10 dl&#8226;g^-1,新单体MAB的纯度>98%,具有稳定性优异和缩聚基团完全等当比等性质,以及均缩聚时间<20 h和过程易操作等技术特点,均为4,6-二氨基间苯二酚（DAR）共缩聚路线所难以比拟的.其综合经济性优于三氯化苯经DAR共缩聚的工业化路线,有望发展成易于实施PBO产业化的一项新技术.     

4,6-二氨基间苯二酚盐酸盐的合成研究

以间苯二酚为起始原料,通过间苯二酚2位磺化保护法,即采用30%的发烟硫酸对间苯二酚进行2,4,6位磺化,再采用65%的发烟硝酸对磺化产物进行4,6位硝化,最后水解脱除2位磺基,还原4,6位硝基,制得纯度高于99.8%的4,6-二氨基间苯二酚(DAR)盐酸盐,并通过对各步骤目标产物的纯度分析,探讨了这一合成路线的技术可行性和技术优势。     

DAR黄成色剂的合成

本文以α-新戊酰基-2-氯-5-[3-(2，4-二特戊基苯氧基)丁酰胺基]乙酰苯胺为母体，以2，5-二巯基-1，3，4-噻二唑为吸附基团，分别以1-甲酰基-2-(4-氨基)苯肼，1-乙酰基-2-(4-氨基)苯肼和1-三氟乙酰基-2-(4氨基)苯肼为增强基团合成了3种DAR黄成色剂．并通过IR，^1HNMR，MS确证了它们的结构．     

DAR成色剂结构与性能的关系

通过分析DAR成色剂的结构和作用机理，讨论了其结构与照相性能之间的关系．DAR成色剂的结构可表示为：Cp—L—A，其中Cp代表成色剂母体，A代表促进显影的功能基团即增强基团，L代表连接基团同时也有吸附功能即吸附基团．本文指出：当吸附基团和增强基团相同时，母体对照相性能影响不大；当母体及增强基团相同时，吸附基团的吸附性越强，照相性能越好；当母体及吸附基团相同时，增强基团的感染显影作用越强，照相性能越好．     

不同显影促进基团对DAR成色剂照相性能的影响

研究了带有不同取代基的显影促进基团对DAR成色剂照相性能的影响．通过比较3个母体及吸附基团相同而显影促进基团不同的DAR成色剂的照相性能，发现不同酰基取代的显影促进基团对DAR成色剂的照相性能有较大的影响，其中带三氟乙酰基取代的显影促进基团的DAR成色剂的照相性能最佳．     

DAR成色剂研究进展

本文综述了DAR成色剂的研究进展，特别是DAR成色剂的结构和作用机理。     

聚对苯二甲酰对苯二胺共缩聚工艺研究

通过添加第三单体3,4'-二氨基二苯醚(3,4'-ODA)对聚对苯二甲酰对苯二胺(PPTA)进行改性,能够使其溶于一般的极性有机溶剂中,得到的聚合物溶液可以直接纺丝。研究了PPTA共聚合工艺,探讨了反应时间、反应温度、单体摩尔浓度、CaCl2含量以及第三单体含量和初始投料比对共聚物比浓对数黏度的影响。     

Wet flue gas desulfurization performance of 330 MW coal-fired power unit based on computational fluid dynamics region identification of flow pattern and transfer process

Wet Flue Gas Desulfurization (WFGD) unit based upon spray scrubber has been widely employed to control SO₂ emissions from flue gas in coal-fired power plant. To clarify the dependence of desulfurization performance on inter-phase transfer behaviors with non-ideal contacting patterns of flue gas and slurry droplets, three regions in spray scrubber are distinguished in terms of gas-slurry flow structures using CFD method in the Eulerian-Lagrangian framework. A comprehensive model is established by involving the transfer process between two phases and chemical reactions in aqueous phase, which is validated with the measured data from a WFGD scrubber of 330 MW coal-fired power unit. Numerical results show that the overall uniformity degree of flue gas in whole scrubber is largely determined by the force-balanced droplets in the middle part of scrubber, which is dominated by counter-current mode. Both momentum transfer behavior and SO₂ chemical absorption process present the synchronicity with the evolution of gas-slurry flow pattern, whilst the heat transfer together with H₂O evaporation has little effect on overall absorption process. Three regions are firstly defined as Gas Inlet Region (GIR), Dominant Absorption Region (DAR) and Slurry Dispersed Region (SDR) from the bottom to top of scrubber. SO₂ is mainly scrubbed in DAR, which provides much more intensive interaction between two phases compared to GIR or SDR. A better understanding of the desulfurization process is obtained from the fundamental relationship between transport phenomena and chemical reactions based upon the complicated hydrodynamics of gas-slurry two-phase flow, which should be useful for designing and optimizing the scrubber in coal-fired power unit.     

等离子体引发炭黑 接枝聚合的溶剂效应

用等离子体处理炭黑发现,这些等离子体黑颗粒经辉发放电后会产生不同种类的活性种,如高能电子、光子、自由基等,这些活性能引发乙烯基单体进行接枝聚合反应。等离子体炭黑对不同的乙烯基单体具有较强的选择性,当选用不同的溶剂时会产生明显的溶剂效应,产生溶剂效应的原因与等离子体引发聚合的机理有关。等离子体的位阻排斥引发机理会对乙烯基单体的接枝聚合产生较强的选择性。等离子体的溶剂化活性引发机理会对乙烯基单体的接枝聚合产生较强的溶剂效应。当等离子体炭黑与甲基丙烯酸甲脂、甲基丙烯酸丁酯接枝聚合时,溶剂采用二甲基甲酰胺,可得到较高的树枝率。同时讨论了接枝反应的的影响因素。在炭黑颗粒上接枝不同的乙烯基单体会对炭黑体系的分散稳定性产生不同的影响。     

Enhancement of Fat Oxidation during Submaximal Exercise in Sedentary Persons: Variations by Medium-Chain Fatty Acid Composition and Age Group

Previous studies in recreational and trained athletes aged mostly in their 20s have reported that short-term ingestion of medium-chain triacylglycerols (MCT) enhances fat oxidation (FAO) during submaximal exercise. However, whether the FAO-enhancing effect of MCT with a different composition of medium-chain fatty acids (MCFA) occurs in older sedentary persons is unclear. The present study investigated the effect of MCT ingestion with different proportions of MCFA in sedentary participants in their 40's and 50's. Participants ingested 0 g of MCT (control), 6 g of octanoic acid-rich MCT (OAR), or 6 g of decanoic acid-rich MCT (DAR) for 14 days separated by a 14-day washout period in random order. Cumulative FAO (F_cv) during submaximal, fixed, and incremental exercise was evaluated at workload from 20 W to the appearance of a ventilation threshold (VT). During the 20 W fixed-load exercise, F_cv was significantly (p < 0.05) higher in the OAR than in the control. At appearance of VT, intervention effect of power output was significantly higher in the OAR and DAR than in the control. In a subgroup analysis by age, intervention effects of maximal FAO rate and oxygen uptake in the upper age subgroup were higher in the OAR and DAR than in the control. In a pooled analysis with age subgroup and diet, the integrated pooled estimate of F_cv during submaximal exercise was significantly higher in 6 g of MCT ingestion than 0 g ingestion. Our data show that the effect of MCT might differ depending on the age group and the proportion of MCFA, while MCT could enhance FAO during submaximal exercise.     

Novel condensation functional polymers having highly basic groups

The cardo polyimides and polyamides having highly nucleophilic quinuclidine groups have been synthesized with the usage of 3,3-bis(4-aminophenyl)quinuclidine as amine monomer. The latter has been obtained by the condensation of quinuclidone-3 with aniline. The characterization of such amine, including quaternization reaction, is performed. Polyimides have been derived from this monomer and various tetracarboxylic dianhydrides by one- and two-step polycyclization. Quinuclidine moieties enhance the one-step polyimide formulation leading to high molecular polymers including corresponding poly- 1,4,5,8-naphthoyleneimides even without any added catalyst. It is stated that polyamic acid formation is hindered by the side tertiary-amine-COOH salt formation. The latter reaction is eliminated by the preliminary quaternization of amine monomer. The high molecular polyamides have been prepared by low-temperature solution polycondensation of cited monomer and diacid chlorides. The obtained polymers are characterized by high thermal properties, solubility in organic solvents and represent the quite efficient catalysts for polyamic acid imidation in homo- and heterogeneous systems.     

对位芳香族聚酰胺共缩聚工艺研究

聚对苯二甲酰对苯二胺(PPTA)是一种全芳香族聚酰胺,由其制备的纤维具有高强、高模、耐高温等优异的性能而广泛应用于特种服装、航空航天、通讯电缆以及复合材料中。但PPTA树脂难溶难熔,只能在浓硫酸中溶解,纺丝工艺复杂。通过添加第三单体对其进行改性,能够使其溶于一般的极性有机溶剂中,得到的聚合物溶液可以直接纺丝。本实验采用3,4'-二氨基二苯醚(3,4'-OD A)为第三单体,分别在N,N-二甲基乙酰胺(DMAc)/CaCl和N-甲基-2-吡咯烷酮(NMP)/CaCl溶剂体系中,对其共聚合工艺进行了研究。探讨了反应时间、反应温度、单体摩尔浓度、CaCl含量以及3单体含量和初始投料比对共聚物比浓对数粘度的影响。     

Poly(p‐phenylene benzoxazole) fiber chemically modified by the incorporation of sulfonate groups

Two kinds of modified poly(p‐phenylene benzoxazole) (PBO), the copolymer of TPA (SPBO) and p‐SPBO, containing ionic groups in the macromolecular chains were obtained by copolymerization from 1,3‐diamino‐4,6‐dihydroxybenzene dihydrochloride (DAR) and terephthalic acid (TPA), with the addition of selected amounts (1.5–5.0% molar ratio over DAR) of 5‐sulfoisophthalic acid monosodium salt or sulfoterephthalic acid monopotassium salt in place of the TPA, respectively, in poly(phosphoric acid) (PPA). The resultant PBO/PPA, SPBO/PPA, and p‐SPBO/PPA lyotropic liquid‐crystalline solutions were spun into fibers by a dry‐jet wet‐spinning technique. Chemically modified PBO fibers with sulfonate salt pendants in the polymer chains were obtained for the first time. The surface wetting behavior and interfacial shear strength between the fiber and epoxy resin were investigated. The interference of sulfonate salt pendants on the crystalline morphology was measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008