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现行 ASTM D7558-09(2024)
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Standard Test Method for Colorimetric/Spectrophotometric Procedure to Quantify Extractable Chemical Dialkyldithiocarbamate, Thiuram, and Mercaptobenzothiazole Accelerators in Natural Rubber Latex and Nitrile Gloves 天然橡胶乳胶和丁腈手套中可提取化学二烷基二硫代氨基甲酸酯、秋兰姆和巯基苯并噻唑促进剂定量比色/分光光度法的标准试验方法
发布日期: 2024-09-01
1.1 本试验方法旨在量化天然橡胶乳胶(NRL)和丁腈手套中可提取促进剂的总量。该方法可以检测和定量三类常见的橡胶促进剂,巯基苯并噻唑(MBT)、秋兰姆和硫代氨基甲酸酯类化合物。如果手套材料中存在的特定橡胶促进剂未知,则基于二丁基二硫代氨基甲酸锌(ZDBC)当量进行定量。该方法无法检测所有潜在的橡胶促进剂,包括巯基苯并噻唑二硫化物、二吗啉、硫脲和二苯二胺。 1.2 就本试验方法而言,化学促进剂测量范围基于执行实验室建立的检测限(LOD)。 1.3 该测试方法应由经验丰富的分析师进行,或在有使用光谱和使用有机溶剂经验的人的监督下进行。 1.4 该测试方法尚未验证用于测量长链二硫代氨基甲酸酯或其他橡胶制品(如润滑避孕套)中的促进剂( 1. ). 2. 尽管文献中报道了这种测定方法用于评估避孕套中的促进剂水平,但在使用前,测试实验室需要对其他橡胶产品的促进剂测量进行进一步验证。 1.5 本试验方法不是为了评估橡胶材料诱导或引发IV型皮肤致敏反应的潜力(IV型皮肤过敏反应见试验方法 D6355 ). 总可提取促进剂含量不能反映通过这种方法检测和测量的单个促进剂的生物利用度。本试验方法应用于在受控实验室条件下测试和测量NRL和丁腈手套中的总残留化学促进剂水平,不应用于描述、评估或评价这些材料或产品在实际操作中的危害或风险- 使用条件。 1.6 以国际单位制表示的值应被视为标准值。本标准不包括其他计量单位。 1.7 本标准并不旨在解决与其使用相关的所有安全问题(如果有的话)。本标准的使用者有责任在使用前建立适当的安全、健康和环境实践,并确定监管限制的适用性。 1.8 本国际标准是根据世界贸易组织技术性贸易壁垒委员会发布的《关于制定国际标准、指南和建议的原则的决定》中确立的国际公认的标准化原则制定的。 =====意义和用途====== 5.1 二烷基二硫代氨基甲酸酯(DTC)、苯并噻唑和秋兰姆通常用作NRL产品中的硫化促进剂。锌DTC促进剂可以直接添加,也可以在硫化过程中通过秋兰姆和氧化锌之间的反应原位形成。在手套等橡胶制成的医疗器械的渗滤液中检测到DTC、苯并噻唑和秋兰姆。研究表明,这些化学物质会引起过敏性接触性皮炎。一种简单的选择性方法来监测橡胶提取物中的橡胶促进剂水平,将有助于质量控制、产品筛选和研究。 5.2 该比色法测量二烷基二硫代氨基甲酸酯,包括二烷基二硫氨基甲酸锌(ZDTC)、巯基苯并噻唑(MBT)和秋兰姆,作为橡胶制品中总硫醇硫化促进剂水平。使用检测波长为320nm的紫外分光光度计测量ZDTC、巯基苯并噻唑和秋兰姆。在分光光度计上测量之前,以1:20稀释的样品提取物通常足以量化大多数市售橡胶手套的残留促进剂水平;然而,样品稀释度可以调整(从纯提取物到>1: 20稀释)。秋兰姆和ZDTC与钴复合,使提取物变成浓度依赖的绿色。ZDTC反应迅速,而秋兰姆反应非常缓慢(需要热催化剂)。巯基苯并噻唑不与Co(III)络合,但在320nm处有强烈的吸收。它可以与ZDTC和秋兰姆区别开来,因为它在320 nm处具有很强的吸光度,没有钴依赖的可见绿色。钴络合物秋兰姆和ZDTC(而不是MBT)在370 nm处也有吸光度( 2 ).
1.1 This test method is designed to quantify the amount of total extractable accelerators in natural rubber latex (NRL) and nitrile gloves. Three common classes of rubber accelerators, the mercaptobenzothiazole (MBT), thiuram, and thiocarbamate type compounds can be detected and quantified by this method. If the specific rubber accelerator(s) present in the glove material is not known, quantification is based on zinc dibutyldithiocarbamate (ZDBC) equivalents. This method will not detect all potential rubber accelerators, including mercaptobenzothiazole disulfide, dimorpholine, thioureas and diphenyl diamine. 1.2 For the purpose of this test method, the range of chemical accelerator measurement is based on the limit of detection (LOD) established in the performing laboratory. 1.3 This test method should be performed by experienced analysts or under the supervision of those experienced in the use of spectroscopy and working with organic solvents. 1.4 This test method has not been validated for measurement of long chain dithiocarbamates or accelerators from other rubber products, such as lubricated condoms ( 1 ). 2 Although this assay has been reported in the literature for the evaluation of accelerator levels in condoms, further validation for accelerator measurement from other rubber products is required by the testing laboratory prior to use. 1.5 This test method is not designed to evaluate the potential of rubber materials to induce or elicit Type IV skin sensitization reactions (for Type IV skin sensitization reactions see Test Method D6355 ). Total extractable accelerator content does not reflect bioavailablity of individual accelerators that are detected and measured by this method. This test method should be used to test and measure the total residual chemical accelerator level in NRL and nitrile gloves under controlled laboratory conditions, and should not be used to describe, appraise, or assess the hazard or risk of these materials or products under actual in-use conditions. 1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. 1.8 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee. ====== Significance And Use ====== 5.1 Dialkyldithiocarbamates (DTCs), benzothiazoles, and thiurams are often used as vulcanization accelerators in NRL products. Zinc DTC accelerators are added either directly or are formed in situ during the vulcanization process via reaction between a thiuram(s) and zinc oxide. DTCs, benzothiazoles, and thiurams have been detected in leachates from medical devices made of rubber such as gloves. Studies have shown these chemicals can cause allergic contact dermatitis. A simple selective method to monitor rubber accelerator levels in rubber extracts would be useful for quality control, product screening and research. 5.2 This colorimetric assay measures dialkyldithiocarbamates, including zinc dialkyldithiocarbamates (ZDTC), mercaptobenzothiazole (MBT) and thiurams as a total thiol vulcanization accelerator level in rubber products. A UV spectrophotometer with detection at 320 nm is used to measure the ZDTC, mercaptobenzothiazole and thiurams. Sample extracts diluted at 1:20 prior to measurement on the spectrophotometer is usually sufficient to quantify the residual accelerator level from most commercially available rubber gloves; however, sample dilution can be adjusted (from neat extract to > 1:20 dilution) based on analytical needs. Thiurams and ZDTCs complex with cobalt turning the extract to a concentration-dependent shade of green. ZDTCs reacts quickly while thiurams react very slowly (requiring a heat catalyst). Mercaptobenzothiazole does not complex to Co(III), however, it absorbs strongly at 320 nm. It can be distinguished from both ZDTCs and thiurams by its strong absorbance at 320 nm without the cobalt dependent visible green color. Cobalt complexed thiurams and ZDTCs, but not MBT, also have and absorbance at 370 nm ( 2 ).
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