溶解沉淀-顶空气相色谱/质谱法测定丙烯酸树脂中残余单体

建立了丙烯酸树脂中13种残余单体的溶解沉淀-顶空气相色谱/质谱检测方法。丙烯酸树脂样品用N,N-二甲基乙酰胺溶解后加去离子水沉淀,采用VF-624 M S毛细管柱分离。13种残余单体能得到较好的分离,检出限(信噪比为3)为0.13~0.67 mg/kg,定量限(信噪比为10)为0.33~2.01 mg/kg,平均回收率为94.7%~113.4%,相对标准偏差(RSD)小于6%。     

衍生化反应-气相色谱法测定聚氨酯胶黏剂中3,3′-二氯-4,4′-二氨基二苯基甲烷北大核心CSCD

采用衍生化反应-气相色谱法测定聚氨酯胶黏剂中3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)的含量。聚氨酯胶黏剂样品0.500g用20mL甲苯超声萃取40min,在离心后的上层清液10mL中加入10.0mg·L^(-1 )3,3′-二氯联苯胺溶液10μL和N-甲基双三氟乙酰胺(衍生化试剂)20μL。用DB-5色谱柱(30m×0.25mm,0.25μm)分离,电子捕获检测器检测。以3,3′-二氯联苯胺为内标物。MOCA的线性范围为0.10~5.00mg·L^(-1),检出限(3S/N)为1.50mg·kg^(-1)。加标回收率为85.4%~96.7%,测定值的相对标准偏差(n=6)均小于2.0%。     

衍生化反应-气相色谱法测定聚氨酯胶黏剂中3,3′-二氯-4,4′-二氨基二苯基甲烷

采用衍生化反应-气相色谱法测定聚氨酯胶黏剂中3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)的含量。聚氨酯胶黏剂样品0.500g用20mL甲苯超声萃取40min,在离心后的上层清液10mL中加入10.0mg·L~(-1 )3,3′-二氯联苯胺溶液10μL和N-甲基双三氟乙酰胺(衍生化试剂)20μL。用DB-5色谱柱(30m×0.25mm,0.25μm)分离,电子捕获检测器检测。以3,3′-二氯联苯胺为内标物。MOCA的线性范围为0.10~5.00mg·L~(-1),检出限(3S/N)为1.50mg·kg~(-1)。加标回收率为85.4%~96.7%,测定值的相对标准偏差(n=6)均小于2.0%。     

液液萃取-气相色谱-质谱联用法同时检测烟用水基胶中的23种酯类化合物

建立了一种同时检测烟用水基胶中23种酯类化合物的液液萃取-气相色谱-质谱联用方法。23种酯类化合物包括乙酸酯类、丙烯酸酯类、甲基丙烯酸酯类、邻苯二甲酸酯类化合物。水基胶样品经水分散后,用含内标物丙酸苯乙酯的正己烷溶液振荡萃取,萃取液离心后过0.45 μm有机相滤膜,用DB-WAXETR气相色谱柱(60 m×0.25 mm×0.25 μm)分离,质谱选择离子模式监测,内标法定量。结果表明,23种酯类化合物在0.4~50.0 mg/L范围内线性关系良好,线性相关系数大于0.998,样品加标回收率为81.8%~109.1%,相对标准偏差(RSD, n=5)小于4%,检出限为0.02~0.76 mg/kg,定量限为0.04~2.52 mg/kg。该方法前处理简便、快速、分析时间短、灵敏度高、重复性好,可用于烟用水基胶中23种酯类化合物的同时检测。     

微波辅助萃取-气相色谱质谱法测定丙烯酸树脂中9种残余单体

建立了丙烯酸树脂中9种残余单体(丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、苯乙烯、丙烯酸、甲基丙烯酸)的微波辅助萃取-气相色谱-质谱检测方法。固体丙烯酸树脂样品用乙酸乙酯微波萃取后加甲醇沉淀(液态丙烯酸树脂样品直接用甲醇稀释)后,采用DB-WAX毛细管柱分离。结果表明,本方法在20 min内同时分离了9种单体,所测物质的定量限(LOQ,以信噪比为10计)为3～50 mg/kg(固体树脂)和1～10 mg/kg(液态树脂);在1～500 mg/L范围内,线性相关系数均在0.995以上;在5个添加水平下平均回收率为84.4%～108.6%,相对标准偏差(n=6)为0.27%～4.97%。方法的灵敏度和回收率高、选择性好,能满足实际工作的要求。     

柱后氨化-超高效液相色谱-串联质谱法测定牛奶和奶粉中的三聚氰酸

建立了一种柱后氨化-超高效液相色谱-串联质谱法(UPLC-MS/MS)测定牛奶和奶粉中三聚氰酸的分析方法。样品用5%三氯乙酸溶液提取,无需净化和浓缩,用Acquity UPLC HSS T3色谱柱(50 mm×2.1 mm, 1.8 μm)进行分离,以乙腈和水作为流动相进行梯度洗脱,柱后氨化,电喷雾负离子(ESI~)模式电离,多反应监测(MRM)模式进行检测。结果表明: 三聚氰酸在10.0～160.0 μg/L范围内线性关系良好(r≥0.99)。牛奶在0.05、0.10、0.20 mg/kg的添加浓度的回收率为60%～118.5%,相对标准偏差(RSD, n=6)为8.2%～12.6%;奶粉在0.25、0.50、1.00 mg/kg的添加浓度的回收率为88%～108%, RSD(n=6)为2.5%～5.7%。牛奶中方法的定量限(信噪比为10)为0.05 mg/kg,奶粉中为0.25 mg/kg。该方法快速、灵敏、准确,适合于牛奶、奶粉等乳及乳制品中三聚氰酸的快速、高灵敏度的分析检测。     

分子印迹固相萃取-高效液相色谱法测定饲料中莱克多巴胺

以莱克多巴胺为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对莱克多巴胺具有高选择性的分子印迹聚合物。考察了甲醇、乙腈、丙酮和氯仿-甲醇与三乙胺构成致孔剂合成的聚合物性能及其形貌特征。通过正交试验优化的聚合反应配方为: 1.0 mmol莱克多巴胺,4.0 mmol丙烯酰胺,20.0 mmol乙二醇二甲基丙烯酸酯,6.0 mL乙腈-三乙胺(30:1, v/v), 50.0 mg偶氮二异丁腈。建立的基于分子印迹固相萃取-高效液相色谱测定饲料试样中莱克多巴胺的方法,在0.50～100 mg/L质量浓度范围内有良好的线性关系(r=0.9994);饲料试样中1.0、10及100 mg/kg 3个添加水平的莱克多巴胺平均回收率大于80%;批内、批间测定的相对标准偏差小于10%;检出限(信噪比为3)达到0.1 mg/kg。该方法灵敏、可靠,用于饲料等复杂基质中莱克多巴胺检测的效果优于相关标准分析方法。     

气相色谱-质谱法测定食品接触塑料制品中的12种甲基丙烯酸酯类单体在水系模拟物中的迁移量

提出了测定食品接触塑料制品中的12种甲基丙烯酸酯类单体在水系模拟物中迁移量的气相色谱-质谱法。样品在100℃水系模拟物中恒温浸泡2 h后,浸泡液经乙酸甲酯振荡萃取10 min,提取液在DB-5MS毛细管色谱柱上分离,质谱分析中选择电子轰击离子源和选择离子监测模式。12种甲基丙烯酸酯类单体在0.600~10.0 mg·L~(-1)范围内呈线性关系,检出限(10S/N)在0.006~0.04 mg·L~(-1)之间。加标回收率在86.6%~115%之间,测定值的相对标准偏差(n=6)在1.2%~9.1%之间。     

高效液相色谱-二极管阵列检测法同时分析兽药粉剂中11种磺胺类药物

建立了高效液相色谱-二极管阵列检测法同时测定兽药粉剂中11种磺胺类药物的分析方法。试样采用95%乙腈提取,经碱性氧化铝固相萃取小柱净化,15%乙腈复溶残渣后用Agilent TC-C18色谱柱分离,0.017 mol/L磷酸溶液和乙腈为流动相进行梯度洗脱,二极管阵列检测器进行检测。结果表明,在优化实验条件下,11种磺胺类药物的色谱分离和相应光谱图匹配理想;在0.25～10.0 mg/L范围内线性关系良好;兽药粉剂中添加0.5～5.0 mg/kg水平的11种磺胺类药物的回收率在67%～97%之间,相对标准偏差为1.5%～9.9%;以3倍信噪比(S/N=3)结合相应光谱图计算得11种磺胺类药物的检出限均为0.25 mg/kg。     

气相色谱质谱法测定胶黏剂中得克隆阻燃剂

建立了通过溶解-沉淀法进行样品预处理,结合气相色谱-电子轰击源质谱仪(GC-EI/MS)检测5种不同类型胶黏剂中得克隆(DP,含syn-DP和anti-DP同分异构体)含量的分析方法。前处理结果表明,以乙酸丁酯溶解胶黏剂后定量加入甲醇或异辛烷,胶黏剂中的高聚物在混合液中析出而形成相分离,经离心后高聚物的去除率在85.3%～96.2%范围内,具有较好的净化效果。通过优化仪器检测参数,syn-DP和anti-DP的质量浓度在0.60～18.0 mg·L^-1范围内与响应值有良好线性关系,相关系数r²>0.998。syn-DP和anti-DP的检出限分别为0.056 mg·L^-1、0.043 mg·L^-1,3个浓度添加水平的回收率在87.5%～102.4%范围内,变异系数在2.2%～6.5%范围内,满足胶黏剂中DP含量检测的分析需求。利用该方法测定市售的14款胶黏剂样品,其中在汽车电路板胶黏剂中检出DP。     

顶空气相色谱法测定烟用胶中残余单体

采用顶空气相色谱(HS-GC)法对卷烟用胶中甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和乙酸乙烯酯7种残余单体进行了分析。方法采用DB-VRX石英弹性毛细管色谱柱分离,氢火焰离子化检测器检测。7种单体能够完全分离,线性良好,线性相关系数在0.9985～0.9992之间,检测限在0.0030～0.0039mg/mL范围,相对标准偏差(RSD)小于1.92%。该方法操作简便、快速、高效、准确、灵敏度高,实用性强,可用于胶粘剂中残余单体的测定。     

Determination of residual (free) monomer in water based polymer emulsions by head space gas chromatography mass spectrometry

A method for determination of residual acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethyl hexyl acrylate, styrene and 2-methyl styrene monomers in polymer emulsions by head space gas chromatography mass spectrometry. Monomers were separated on DB-624 column and detected by MS under SIM (Selected ion monitoring) mode. The linear regression analysis data for the calibration curve for all monomers showed a good linear relationship with a regression coefficient of 0.99 over the concentration range of 5.3 mg/kg to 1172 mg/kg. The limit of detection and limit of quantification for the target analytes were in the range from 0.4 to 2.9 mg/kg and 0.9 to 7.3 mg/kg respectively.     

丙烯酸酯和甲基丙烯酸酯基团转移共聚研究

研究了三种丙烯酸酯分别和四种甲基丙烯酸酯的基团转移共聚，用１Ｈ ＮＭＲ法测定共聚物组成，扩展的Ｋｅｌｅｎ Ｔｕｄｏｓ法测定竞聚率，结果为γＭＡ＝９２３、γＭＭＡ＝００６；γＥＡ＝１４１５、γＭＭＡ＝００１；γＢＡ＝７５１、γＭＭＡ＝００２；γＭＡ＝１４４１、γＥＭＡ＝００１；γＭＡ＝１３９６、γＢＭＡ＝０２３；γＭＡ＝８６６、γｉ ＢＭＡ＝００８，表明基团转移聚合同阴离子聚合有明显的相似之处．     

Thermal degradation of butyl acrylate-methyl acrylate-acrylic acid-copolymers

The thermal degradation of copolymers based on butyl acrylate-methyl acrylate-acrylic acid used as acrylic pressure-sensitive adhesives, especially for bonding of plasticizer containing materials, has been investigated using thermogravimetry and pyrolysis-gas chromatography at 250°C. It was observed that during the pyrolysis of butyl acrylate-methyl acrylate-acrylic acid copolymers unsaturated monomers as methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate were formed. During the side-chain butyl acrylate-methyl-acrylate-acrylic acid-copolymer degradation the presence of methyl alcohol and butyl alcohol was observed.     

Volumetric Properties of Ethylbenzene with Ethyl Acrylate,Butyl Acrylate,Methyl Methacrylate,and Styrene at 298.15 K

Densities of the binary systems of ethylbenzene with ethyl acrylate, butyl acrylate, methyl methacrylate, and styrene have been measured as a function of the composition, at 298.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densitometer. The calculated excess volumes were correlated with the Redlich-Kister equation and with a series of Legendre polynomials. The excess volumes are positive for the systems ethylbenzene + (methyl methacrylate, ethyl acrylate) and negative for the systems ethylbenzene + (butyl acrylate, styrene).     

甲基丙烯酸酯和丙烯酸酯基团转移共聚的竞聚率

甲基丙烯酸酯和丙烯酸酯基团转移共聚的竞聚率邹友思郭金全戴李宗潘容华（厦门大学化工系，厦门，３６１００５）基团转移聚合是制备极性单体的嵌段或无规共聚物的有效方法。如用甲基丙烯酸甲酯（ＭＭＡ）和丙烯酸丁酯（ＢＡ）进行嵌段共聚，可制得热塑性弹性体［１...     

Tricarbonylchromium complexes of styrenes in radical copolymerization

The organometallic monomers styrenetricarbonylchromium and p‐methylstyrenetricarbonylchromium were copolymerized in ethyl acetate solutions with methyl methacrylate and butyl acrylate using azobisisobutyronitrile at 50 °C and a binary system including di‐tert‐butylperoxytriphenylantimony at 30 °C as the free‐radical initiators. Comonomers are proposed to form a molecular complex based on the results of ultraviolet and electron spin resonance spectroscopy. A kinetic study shows that chromium‐containing monomers at high concentrations in the mixture reduce the rate of copolymerization. The addition of styrenetricarbonylchromium to butyl acrylate significantly slows down the autoacceleration. The reactivity ratios of the comonomer pairs, namely, styrenetricarbonylchromium–methyl methacrylate, styrenetricarbonylchromium–butyl acrylate and p‐methylstyrenetricarbonylchromium–methyl methacrylate, were determined using the method of Kelen–Tudos for low conversion polymerizations.Copyright © 2001 John Wiley & Sons, Ltd.     

Volumetric Properties of Toluene with Ethyl Acrylate, Butyl Acrylate, Methyl Methacrylate, and Styrene at 25°C

Densities of the binary systems of toluene with ethyl acrylate, butyl acrylate, methyl methacrylate, and styrene have been measured as a function of the composition, at 25°C and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densitometer. The calculated excess volumes were correlated with the Redlich–Kister equation and with a series of Legendre polynomials. The excess volumes are negative for systems toluene + (ethyl acrylate, butyl acrylate, and styrene) and positive for the system toluene + methyl methacrylate.     

凝胶色谱净化-气相色谱法测定酱油中7种防腐剂

建立了凝胶色谱净化-气相色谱法测定酱油中山梨酸、苯甲酸、脱氢乙酸、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯共7种防腐剂的方法.样品经过乙醚提取,凝胶渗透色谱净化,毛细管柱(Rxi-17,30 m×0.25 mm×0.25μm)分离后,FID检测器检测.7种化合物在10.0～400.0 mg...