芳香叔胺引发丙烯腈光聚合的引发机理

芳香叔胺引发丙烯腈(AN)光聚合是通过形成激基复合物(exciPlex)进行的。紫外光谱和荧光光谱表明,芳香叔胺在基态可以和AN形成电荷转移复合物(CTC),而在激发态可和AN形成exciplc(称定域激发)。CTC经光照亦可激发(称CTC激发)。 定域激发引起光聚合速率为CH_3C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2>HOCH_2·C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2,与芳胺荧光被AN淬灭的Stern-Vo-lmer常数顺序一致。CTC激发引起的光聚合顺序为:CH_3C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2>HOCH_2C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2,与芳胺上取代基推电子能力一致。端基分析表明聚合物有芳胺端基。     

希土元素异硫氰酸盐与苄胺配合物的制备、性质及标准生成焓的测定

制备了Pr、Yb两种希土元素异硫氰酸(?)与苄胺的固体配合物.并对其进行了组成分析、红外光谱分析、X射线衍射物相分析和热重分析.测量了298.15K时两种固体配合物RE(NCS)_3·4C_6H_5CH_2NH_2在HCl水溶液中的反应热和相应的两种希土元素异硫氰酸盐水合物RE(NCS)_3·n_1H_2O(RE为Pr时,n_1=7;RE为Yb时,n_1=6)在C_6H_5CH_2NH_2-HCl-H_2O溶液中的积分溶解热以及苄胺C_6H_5CH_2NH_2在HCl水溶液中的反应热.藉助本文所设计的热化学循环,求得了这两种配合物的标准生成焓,还计算了它们的晶格能.     

添加剂对镍系催化丁二烯聚合的影响

对正辛酸一三氟化硼乙酸络合物（n－C_8H_(17)0H－B）预混、乙酸正丁酯一三氟化硼乙醚络合物（CH_3COOC_4H_9－B）预混和稀三氟化硼乙醚络合物（B）单加三种体系的丁二烯聚合行为进行了比较。结果表明；B组分中加入n－C_8H_(17)OH，能在不拓宽三异丁基铝（Al）／B摩尔比范围的情况下，有效地提高聚丁二烯的分子量；B组分中加入CH_3COOC_4H_9，能适当地拓宽Al／B比，但对聚丁二烯分子是不产生影响。对n－C_8H_(17)0H－B在聚合体系中的作用机理进行了探讨，提出了在n－C_8H_(17)0H－B预混体系中存在两种活性中心。     

硼化合物的研究——Ⅺ.氢硼酸π-环戊二烯基-烷撑双(二苯基膦)合镍(Ⅱ)的合成和性质

本文以C_5H_5NiPPh_3Cl与Ph_2P(CH_2)_nPPh_2为起始物合成了C_5H_5NiPh_2P(CH_2)nPPh_2Cl·C_6H_6,再进一步与氢硼酸季铵盐反应,合成了12个氢硼酸π-环戊二烯基-烷撑双(二苯基膦)合镍(Ⅱ)化合物。对这些化合物进行了元素分析、红外光谱鉴定,并测定了氯化物的~1H NMR谱。所有含硼化合物于室温下对空气是稳定的,而它们的热稳定性与阳离子中螯合环的大小和氢硼酸根结构有关,即氢硼酸根相同的化合物,热稳定性随着螯合环的增大而降低;阳离子相同时,热稳定性次序是:[C_5H_5NiPh_2P(CH_2)_nPPh_2]_2B_(12)H_(12)>[C_5H_5NiPh_2P(CH_2)_nPPh_2]_2B_(10)H_(10)>C_5H_5NiPh_2P(CH_2)_nPPh_2B_(11)H_(14)>C_5H_5NiPh_2P(CH_2)_nPPh_2B_3H_8。     

二元羧酸二(二茂镱)的合成

本文报道了五个新的二元羧酸二(二茂镱)的合成:(COO)_2Yb_2(C_5H_5)_4(1),CH_2(COO)_2Yb_2(C_5H_5)_4(2),(CH_2COO)_2Yb_2(C_5H_5)_4(3),o-C_6H_4(COO)_2Yb_2(C_5H_5)_4(4),p-C_6H_4(COO)_2Yb_2(C_5H_5)_4(5),并考察了它们对空气的稳定性。     

苄基环戊二烯基稀土二氯化物的合成和表征

合成了苄基环戊二烯基稀土二氯化物,经元素分析、热分析、红外光谱、质谱及核磁共振谱分析,证实其组成为C_6H_5CH_2C_5H_4LnCl_2·nTHF(C_6H_5CH_2C_5H_4=苄基环戊二烯,Ln=Nd,Sm,Gd,n=1,2)。对新化合物苄基环戊二烯进行了表征,同时还测定了中间物C_6H_5CH_2C_5H_4Na·THF的晶体结构。     

高位阻有机磷萃取剂的研究 Ⅲ.叔丁基膦酸单烷基酯的合成及其结构与萃取镱、镥性能的关系

合成了一系列具有高位阻特征的叔丁基膦酸单烷基酯t-C_4H_9P(O)(OR)OH(R分别为n-C_8H_(17),—CH_2CH(C_2H_5)C_4H_9,—CH(CH_3)C_6H_(13),—CH_3CH_2CH(CH_3)CH_2C(CH_3)_3和n-C_(12)H_(25))。初步探讨了它们的结构与萃取重稀土元素Yb(Ⅲ)和Lu(Ⅲ)性能的关系。萃取能力随着酯烷基空间位阻的增大而显著降低。在ph_(1/2)值与酯烷基的Charton空间参数v间存在着近似的直线关系。叔丁基膦酸单烷基酯对Yb、Lu的反萃性能优于2-乙基己基膦酸单2-乙基己酯(P-507)。     

聚有机硅氧烷的研究——Ⅲ.甲基苯基硅氧烷的平衡化反应

(1)研究了甲基苯基硅氧烷在碱及酸存在下的平衡化反应,得到有机硅氧烷的反应性的顺序如下:在碱的催化下, [(CH_3)(C_6H_5)SiO]_3>[(CH_3)_2SiO]_3>[(CH_3)(C_6H_5)_2Si]_2O (?) 在酸的催化下, [(CH_3)_2SiO]_3>[(CH_3)(C_6H_5)SiO]_3 [(CH_3)_2SiO]_4>[(CH_3)(C_6H_5)SiO]_4 [(CH_3)_2SiO]_4>[(CH_3)(C_6H_5)_2Si]_2O (2)由CH_3SiCl_3与(CH_3)_2SiCl_2共水解及共缩合所得的环状聚合体在平衡化反应中出现了特殊的现象,就是聚合体的粘度低于平衡时的粘度,而且达到平衡的时间很长。其原因系环状聚合体中合有SiOH。这羟基可用大量溶剂在碱催化下加热去掉。这种含有三官能度的环状聚合体与MD_2M或MM进行平衡化时容易出现凝胶。改用M″M″可以避免凝胶。     

碳氟醇与阴离子表面活性剂的相互作用

测定了不同比例的C_(10)_H_(21)SO_4Na-C_3F_7CH_2OH、C_7F_(15)COONa-C_3H_7CH_2OH混合水溶液的表面张力,加入C_3F_7CH_2OH可增加阴离子表面活性剂的表面活性;在表面层中,C_3F_7CH_2OH与C_(10)H_(21)SO_4Na间分子相互作用比C_3F_7CH_2OH-C_7F_(15)COONa体系弱;这是由于CF链与CH链间“互疏”作用的结果;随着C_3F_7CH_2OH浓度增加,对C_(10)H_(21)SO_4Na胶团反离子结合度也随之增加。     

四氯乙烯光解活泼自由基及其与烃或醇的夺氢反应的ESR研究

本文用自由基捕捉剂2,3,5,6-四甲基亚硝基苯(ND)与ESR相结合的方法研究了四氯乙烯光解活泼自由基及其与烃或醇的夺氢反应, 结果表明:1. Cl_2C=CCl_2光解首先产生Cl_2C=CCl及Cl, 而又可进一步加成为Cl_2C-CCl_3.2. 对于CH_3(CH_2)_nOH(n=3,7)及(CH_3)_2CH(CH_2)_nOH(n=1,2)而言, Cl_2C=CCl(或Cl)分别夺取其α-碳及叔碳上的氢, 以形成CH_3(CH_2)_(n-1)CHOH及(CH_3)_2C(CH_2)_nOH, 并为ND所捕获。3. Cl_2C=CCl(或Cl)分别夺取CH_3(CH_2)_nCH3(n=3,4,5,6), C_6H_5-CH_2CH_3及(CH_3)_2CH(CH_2)_nCH_3(n=1,4), (C_2H_5)_2CHCH_3, C_6H_5CH(CH_3)_2中亚甲基及叔碳上的氢, 以形成CH_3(CH_2)_mCH(CH_2)_(n-m-1)CH_3, C_6H_5CHCH_3及(CH_3)_2C(CH_2)_nCH_3, (C_2H_5)_2CCH_3, C_6H_5C(CH_3)_2.     

Comparison of three methods for natural gas dehydration

This paper compares three methods for natural gas dehydration that are widely applied in industry:(1) absorption by triethylene glycol, (2) adsorption on solid desiccants and (3) condensation. A comparison is made according to their energy demand and suitability for use. The energy calculations are performed on a model where 105 Nm3/h water saturated natural gas is processed at 30 °C. The pressure of the gas varies from 7 to 20 MPa. The required outlet concentration of water in natural gas is equivalent to the dew point temperature of -10 °C at gas pressure of 4 MPa.     

用天然气气相色谱分析仪快速分析天然气组分及性能参数

介绍用天然气气相色谱分析仪分析天然气中无机组分、有机组分和热值的方法,确定了分析方法和条件,该方法测量结果的相对标准偏差小于1%。采用该方法对制备的标准气体进行了考察,并将该方法用于天然气气体标准物质的性能评价和国际实验室间的比对,天然气组分含量比对相对误差在±1%之内,热量值比对相对误差在±3%之内,取得了国际等效性。     

气敏新材料MXenes在呼出气体传感器中的应用

电子鼻结合人工智能对呼出气进行检测、分析和识别已成为非侵入性医疗检测领域的研究热点.然而,目前已报道的气体传感材料尚不能同时满足高灵敏度、高选择性和稳定的室温检测,阻碍了气体传感器在医疗健康领域的应用及发展,寻找合适的传感材料具有重要的意义和挑战.新型二维层状纳米材料MXenes具有种类多、比表面积大、导电性能强、表面...     

Polypyrrolones for membrane gas separations. I. Structural comparison of gas transport and sorption properties

Despite efforts by the membrane community to develop polymeric materials with improved O₂/N₂ separation performance, limited progress has occurred for almost a decade. Molecular sieving media, which can exhibit gas separation properties superior to polymers, tend to be brittle and uneconomical to produce for large‐scale membrane separation processes. Considering this, the polymer structures investigated in this work were designed to mimic aspects of the structure of molecular sieving media such as zeolites and carbon molecular sieves while maintaining the processability associated with polymers. Significantly attractive gas separation material properties were obtained using hyper rigid polypyrrolone copolymers with controlled packing disruptions between flat, packable segments. The gas transport properties in the materials changed dramatically as a result of different average interchain spacing. Moreover, all of the polypyrrolones studied in this work exhibited performance lying on or above the existing O₂/N₂ upper bound trade‐off line between permselectivity and permeability. These results, therefore, may point the way to a new cycle of membrane materials improvements for gas separations. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1235–1249, 1999     

用低温气相色谱分析火焰气体

本文采用低温气相色谱法分析了火焰气体的成份和深度，色谱柱固定相为ＰｏｒａｐａｒｋＱ，柱温范围－９９－２５０℃氦气作载气。在所选择的实验条件下，火焰气体中的Ｎ２和Ｏ２有效地得到分离，可迅速精确地分析确定Ｎ２的浓度以及其他成份和浓度。     

A novel correlation for estimation of hydrate forming condition of natural gases

An inherent problem with natural gas production or transmission is the formation of gas hydrates, which can lead to safety hazards to production/ transportation systems and to substantial economic risks. Therefore, an understanding of conditions where hydrates form is necessary to overcome hydrate related issues. Over the years, several models requiring more complicated and longer computations have been proposed for the prediction of hydrate formation conditions of natural gases. For these reasons, it is essential to develop a reliable and simple-to-use method for oil and gas practitioners. The purpose of this study is to formulate a novel empirical correlation for rapid estimation of hydrate formation condition of sweet natural gases. The developed correlation holds for wide range of temperatures (265–298 K), pressures (1200 to 40000 kPa) and molecular weights (16−29). New proposed correlation shows consistently accurate results across proposed pressure, temperature and molecular weight ranges. This consistency could not be matched by any of the widely accepted existing correlations within the investigated range. For all conditions, new correlation showed average absolute deviation to be less than 0.2% and provided much better results than the widely accepted existing correlations.     

Prediction of water content of sour and acid gases

Estimating the feasibility of acid gas geological disposal requires the knowledge of the water content of the gas phase at moderate pressures and temperatures (typically below 50 MPa, below 380 K) and up to 6 mol NaCl. In this paper, a non-iterative model is developed to predict the water content of sour and acid gases at equilibrium with pure water and brine. This model is based on equating the chemical potential of water and using the modified Redlich–Kwong equation of state to calculate the fugacity of the gas phase. The water content of pure CH₄, CO₂ and H₂S are represented with average absolute deviations of less than 3.36, 7.04 and 8.4%, respectively. Experimental data of the water content of mixtures of the acid gases were reproduced with average absolute deviations of less than 6.32%.     

WO3基气敏传感器*

气敏传感器已在生物、化学、航空、军事等领域获得了广泛的应用。鉴于WO₃基气敏传感器是检测H₂S、NO_x、O₃和NH₃等气体最有前景的新型氧化物气敏传感器之一,本文以不同的敏感气体为分类依据系统阐述了近年来WO₃基气敏传感器的研究进展,详细探讨了制备方法及贵金属掺杂对上述各种气体气敏性能的影响,并指出了目前WO₃基气敏传感器在研究过程中存在的问题。     

大气本底温室气体测量标准物质研究进展

综述了温室气体标准物质的制备技术与研究进展。归纳了温室气体标准物质种类和量值不确定度的要求,考察了各种配气技术对温室气体监测需求的适用性。综合讨论了配气技术中的稀释操作、钢瓶处理方式及阀门管线材质对温室气体标准物质量值稳定性的影响,并比较了BIPM和WMO量传体系的差异。     

非晶硅太阳能电池生产工艺用氣分析方法研究

本文对非晶硅太阳能电池制造工艺过程所用的无机氢化物烷类气体硅烷、硼烷、磷烷、甲烷和氢及其混合气的配制与分析方法进行了研究,以微机控制配气、检测程序、气相色谱法分成分析杂质,电容法测水分,方法已应用于工艺过程分析。