GC-MS技术在舰船复合板毒性评价中的应用

海军舰船舱室多为密闭环境,其舱室狭小,设备庞杂,人员密集。舱室内部的防护装饰多系非金属材料,随着现代各种复合、聚合材料的迅速发展和广泛使用,周围环境特别是密闭舱室空气污染的问题也更为突出。本文根据有关军用标准和规程[1],应用GC-MS技术对2种舰船复合板常温释放物和高     

非金属脱出VOC的GC-MS检测方法

在潜艇、航空、航天工业以及居室、坑道等相对密闭的空间中,经常要使用各种非金属材料用来装饰、隔热、密封、绝缘[1],许多材料在常温下就会散发各种挥发性无机或有机污染物(VOC),对狭小的密闭空间来说,它们是重要的化学污染源,如果不控制和清除这些污染物,或空气净化系统不完善,污染物累积起来达到有毒的浓度,将会严重影响人员的健康和工作效率,有些化学污染物还能加速仪器仪表的腐蚀或影响仪器的光学性能和电绝缘性能[2].本文阐述了我们运用GC-MS对载人航天器中使用的非金属材料进行检测的方法.     

气相色谱-质谱法测定聚氯乙烯包装材料和食品模拟物中的46种增塑剂

建立了46种增塑剂在聚氯乙烯(PVC)食品包装材料中的含量及其在水、3%乙酸、10%乙醇和橄榄油4种食品模拟物中迁移量的气相色谱-质谱(GC-MS)测定方法。食品包装材料、水质模拟物和橄榄油中增塑剂分别采用溶解-沉淀法、正己烷液-液萃取和凝胶渗透色谱(GPC)法提取。采用GC-MS法,在选择离子监测模式(SIM)下对46种增塑剂进行定性,采用外标法进行定量测定。各种增塑剂在0.1～2.0 mg/L质量浓度范围内呈线性,相关系数为0.9910～0.9999,各组分检出限均在0.005～0.05 mg/kg之间。在2种食品模拟物中,3个浓度添加水平下46种增塑剂的加标回收率在69.51%～107.21%之间,精密度(RSD, n=6)为3.53%～18.95%。该方法可满足PVC食品接触制品及4种不同性质的食品模拟物中多种类增塑剂的快速筛查和准确定性、定量测定要求。     

热裂解色谱-质谱直接鉴定高聚物中有机添加剂

众所周知,在绝大多数高分子材料中除含有高分子外,为改进高分子性能及满足各种使用上要求,必须加入各种添加剂,如抗氧剂、增塑剂、光敏剂;涂料中需加入混合溶剂等.按通常方法分离此类添加剂需采用溶剂萃取和溶解沉淀方法,以除去高聚物才能得到小分子有机化合物进行GC-MS分析鉴定;对于涂料则需用常压或减压蒸馏方法,将溶剂蒸出,再进行GC-MS分析,步骤繁琐.我们实验室长期实践发现,采用较低温度的居里点裂解片,使高聚物不裂解,仅使低分子化合物挥发,这样不经予分离可直接在GC-MS上分析高聚物中有机添加剂,且不污染色谱柱,从而大大简化了分析步骤.     

舰船用3种特殊胶粘剂常温释放物及高温热解物的定性分析

舰船特殊胶粘剂不仅能把各种造舰材料紧密粘合,还具有某些特殊的性能,如绝缘、防水、防火、防磁、防震等.这些特殊胶粘剂在用于海军舰船之前必须进行使用环境下的毒性评价.模拟使用环境条件下对其常温释放物及高温热解物的定性分析是毒性评价的主要内容.     

中空结构的双金属有机骨架材料作为固相微萃取纤维涂层用于多环芳烃的高灵敏检测

环境样品中多环芳烃(PAHs)含量较低且样品基质复杂,直接利用仪器进行含量测定比较困难,因此在仪器分析之前需要对环境样品进行必要的前处理。大多数前处理技术的萃取效率取决于萃取材料的特性。目前,金属有机骨架材料(MOFs)作为一种由金属离子与有机配体自组装而成的多孔材料,已经被用作固相微萃取(SPME)的涂层材料应用于PAHs的萃取,但是这些MOFs涂层材料由于目标物较难达到其深层的吸附位点,使得萃取过程往往需要较长的平衡时间;此外,大多数MOFs由单金属离子配位构成,能够提供的开放金属活性位点种类比较单一,较难获得最佳的萃取性能。这些问题在一定程度上限制了MOFs材料在SPME领域的应用。该研究制备了一种中空结构的双金属有机骨架材料(H-BiMOF),并将其作为SPME的涂层材料,用于萃取环境样品中痕量的PAHs。由于中空的结构和双金属的组成,H-BiMOF涂层材料拥有比表面积利用率高、传质距离短等优点,可以使萃取过程快速地达到平衡。同时,双金属的引入提供了种类丰富的金属活性位点,提高了对PAHs这类富电子云目标物的萃取效率。与气相色谱-串联质谱(GC-MS/MS)相结合,建立了一种用于环境水样中PAHs分析的新方法。所建立的分析方法具有检出限低(0.01~0.08 ng/L)、线性范围宽(0.03~500.0 ng/L)、重复性良好(相对标准偏差≤9.8%, n=5)等优点,并成功地用于实际湖水样品中7种PAHs的检测。实验结果表明,所建立的分析方法适用于环境样品中PAHs的分析与监测。     

GC-MS法测定发酵食品中氨基甲酸乙酯的含量

建立了发酵食品中氨基甲酸乙酯的GC-MS测定方法.样品经饱和NaCl溶液溶解,超声提取,提取液经硅藻土固相萃取小柱净化,二氯甲烷洗脱,以氨基甲酸丁酯作为内标物,使用GC-MS联用仪选择离子监测模式对其定性定量测量.氨基甲酸乙酯在21 ～ 846ng/mL范围内线性关系良好,相关系数r=0.9999.最低检出限为5.0n...     

GC-MS与GC-FTIR联合测定C9烃馏分组成

混合碳九组成复杂,估计为环状烯烃、芳烃、多环烃、烷烃等,目前该产品主要用于生产石油树脂。随着我国乙烯生产能力的不断扩大,其产量也在不断增加,为充分利用碳九资源,研究开拓其新的应用领域非常必要。而此研究的首要条件在于对其组成进行较为全面、准确地分析。传统的分析方法不能对其组成提供详尽的数据资料,直接影响了对碳九进行综合利用研究。GC-MS兼有GC的高效分离能力与MS很好的定性功能,且灵敏度较高,是分析有机混合物十分有效的手段。本文将GC-MS应用于碳九组成的定性分析中。但由于碳九组分中含有较多的同分异构体如三甲苯与二甲苯等,同分异构体的质谱图几乎相同,GC-MS对其不易鉴别,而红外(FTIR)对有机物同分异构体尤其苯系物的异构体具有非常好的鉴别能力。因此本文将GC-MS与GC-FTIR联合使用,对碳九组成进行定性分析,样品定量采用色谱氢火焰检测器峰面积归一化法得到的各组分峰面积相对百分含量,较好地解决了碳九组分的定性定量问题,为开发碳九新的应用领域提供依据。     

现代仪器分析技术在纺织品及皮革分析中的应用

现代分析技术以仪器分析为主,大量先进的现代仪器分析技术已经广泛地应用于纺织品及皮革分析。介绍了气相色谱（GC）、液相色谱（LC）、色谱质谱联用（GC-MS、LC-MS）、原子吸收（AAS）、电感耦合等离子发射光谱（ICP-OES）等现代仪器分析技术在纺织品及皮革分析中的研究进展与应用。     

噻嗪类利尿剂及其甲基化物的质谱研究

在GC-MS研究中,甲基化反应是经常使用的,它除了增加挥发度外,还可起质量位移作用,以判断母体化合物的结构,因为通常认为原型与其甲基化物的质谱是相似的.但我们在进行体内噻嗪类利尿剂的GC-MS中,却发现甲基化反应对质谱裂解方式还有一定影响.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007     

Modified Silica Filler as a Promoting Agent of Adhesion of Rubber to Metal Cord

In order to increase the strength of the adhesive bonding of rubber based on SKI-3 rubber substance to metal cords, the effect of adhesion-promoting agents, which are silicic filler modified by metal ions of variable valency (Co and Ni), has been investigated. It is shown that such adhesion-promoting agents do not have a significant effect on the technological and physicomechanical properties of rubber at room temperature, but increase the resistance of vulcanizates to elevated temperatures (up to 100°C) and increase the strength of the rubber–metal cord connection under the influence of aggressive factors in the process operation of metal cord products.     

阻燃聚丙烯酸酯胶的合成

通过溶液聚合法制得了阻燃性丙烯酸酯胶。研究了甲基丙烯酸2,4,6-三溴苯酯及引发剂用量,交联单体及反应温度、反应时间等对剥离强度的影响。研究了多元共聚丙烯酸酯胶的单体组成、合成工艺及其产品性能。结果表明,制得的胶粘剂在室温下剥离强度为19．5N／cm。     

Autooxidized Polyunsaturated Oils/Oily Acids: Post-it Applications and Reactions with Fe(III) and Adhesion Properties

Soybean oil, sesame oil, linoleic acid and linolenic acid were epoxidized, peroxidized and hydroperoxidized via autooxidation under air oxygen and sunlight at room temperature to obtain novel post-it materials. Polymeric soybean oil peroxide and sesame oil peroxide were containing soluble part of 60%(w/w) together with crosslinked part of 40%(w/w) while polymeric linoleic and polymeric linolenic acids were completely soluble. The autooxidized soluble products with Mn varying between 800 and 3100 Daltons were used as post-it adhesive. The highest adhesion was observed in the case of polymeric soybean oil (3.0 Newton), while adhesion of commercial epoxidized soybean oil, polymeric linoleic and polymeric linolenic acid were 0.8, 0.5 and 0.5 Newton, respectively. Reactions of the autooxidized soluble products with Fe(NO₃)₃. 4H₂O in the presence of ethanol, glycerol and diethyleneglycol gave the hydroxy functionalized products with the same M_n values and indicating no adhesive properties. When the commercial epoxidized soybean oil was reacted with Fe(NO₃)₃. 4H₂O in the presence of the alcohols, Mn of the hydroxy functionalized polymeric oil was found to be unchanged. ¹H NMR, FT-IR, SEM and GPC techniques were used in the characterization of the products obtained.     

舰船用无溶剂环氧涂料常温释放物及高温热解物分析与评价

涂料作为舰船舱室及其部件的内部防护装饰材料已广泛地应用于舰船舱室,科技的发展使得涂料更新换代的步伐加快。舰船舱室经常处于全封闭状态,为减少舱室空气污染对船员的身心健康和战术技术发挥的不良影响,故对舰船舱室大气环境质量提出了更高更新的要求,因此舰船用涂料的筛选尤为重要。涂料作为常用的一种非金属材料其挥发物具有一定的毒性,尤其是对一些新的、毒性不明的涂料,必须先对其进行使用条件下的安全性评价,以便确定其可否应用于舰船舱室之中。本实验根据有关标准对舰船用低毒无溶剂环氧涂料常温释放物及高温热解物进行分析,并对其作卫生学评价,从而为舰船设计、建造部门在筛选艇用涂料方面提供可靠的科学依据。     

The Chemistry and Properties of the Medical-Grade Silicones

The medical grade silicones are probably the most widely used of all the synthetic polymers for permanently implanted subdermal devices. This paper reviews the chemistry of these materials from the original polymer manufacturing through the various stages necessary to obtain the types of heat vulcanizing silicone rubber, room temperature vulcanizing silicone rubber, and silicone rubber adhesive most commonly used in medical applications.     

The influence of preliminary thioetherification reaction on properties of epoxy adhesives modified by liquid thiocol

It is shown that the preliminary thioetherification reaction between mercaptan groups and oxirane cycles promotes the increase of the complex of deformation-strength and adhesion properties of epoxy-thiocol mixtures cured at room temperature. To a greater degree, the effect is revealed for the factors of a specific impact viscosity and destruction and shear strength of the adhesive joints.     

舰艇用LZN-2型高性能阻尼材料释放物定性定量分析与评价

舰艇舱室多为密闭环境,舱室内使用的非金属材料释放物是舱室污染的主要来源,因此对所选用的非金属材料必须进行常温释放物的定性定量分析。由于舰艇的特殊性,不仅要求非金属材料在常温条件下释放物的浓度符合舰艇舱室容许浓度,还要求材料在高温条件(火灾或爆炸)下不产生高毒性的物质。本文根据有关军用标准和规程对舰船用LZN-2型高性能阻尼材料常温释放物和高温热解物进行定性、定量分析,从而对其使用的安全性进行评估。     

Transitions/relaxations in polyester adhesive/PET system

The correlations between the transitions and the dielectric relaxation processes of the oriented poly(ethylene terephthalate) (PET) pre-impregnated of the polyester thermoplastic adhesive have been investigated by differential scanning calorimetry (DSC) and dynamic dielectric spectroscopy (DDS). The thermoplastic polyester adhesive and the oriented PET films have been studied as reference samples. This study evidences that the adhesive chain segments is responsible for the physical structure evolution in the PET-oriented film. The transitions and dielectric relaxation modes’ evolutions in the glass transition region appear characteristic of the interphase between adhesive and PET film, which is discussed in terms of molecular mobility. The storage at room temperature of the adhesive tape involves the heterogeneity of the physical structure, characterized by glass transition dissociation. Thus, the correlation between the transitions and the dielectric relaxation processes evidences a segregation of the amorphous phases. Therefore, the physical structure and the properties of the material have been linked to the chemical characteristics.