In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use o...In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use of different precursors and the addition to gold of a secondary metal as methods which attempt to improve these catalysts, and consider the nature of the active gold species. The vast majority of poly vinyl chloride (PVC) produced globally still uses a mercuric chloride as a cata‐lyst, despite the environmental problems associated with it. Due to the agreement by the Chinese government to remove mercury usage in the PVC industry over the course of the next few years there is an obvious need to find a replacement catalyst;the potential use of gold for this process has been well known for several decades and to date gold seems to be the best candidate for this, pri‐marily due to its superior selectivity when compared to other metals.展开更多
AIM: To analyze occupational health hazards exposure to doses lower than the Chinese occupational health standard in a selected VC polymerization plant in China, and also to elucidate the relationship between genetic...AIM: To analyze occupational health hazards exposure to doses lower than the Chinese occupational health standard in a selected VC polymerization plant in China, and also to elucidate the relationship between genetic polymorphisms and genetic susceptibility on liver lesions of workers exposed to vinyl chloride monomer (VCM). METHODS: In order to explore the mechanism of VCM- related health effects, we used a case-control design to investigate the association between the genetic polymorphisms of metabolic enzymes and liver lesions in workers occupationally exposed to VCM. Genotypes of CYP2E1, GSTT1, GSTM1, ALDH2 and ADH2 were identified using PCR and PCR-RFLP. RESULTS: Even when the concentration of VCM was lower than the current Chinese occupational health standard, neurasthenia, pharyngeal irritation, liver ultrasonography abnormalities and hemoglobin disorders were significantly higher in exposure subjects compared to non-exposure subjects, and the relative risks (RRand 95% C1) were 1.74 (1.06-2.85), 1.97 (1.56-2.48), 10.69 (4.38-26.12), and 2.07 (1.20-3.57). CYP2E1 c1c2/c2c2 genotype was significantly associated with liver damages (OR 3.29, 95% CI 1.51-7.20, P〈0.01). CONCLUSION: The incidences of neurasthenia and liver ultrasonography abnormalities significantly increase when the cumulative exposure dose increases. The genotypes of metabolic enzymes (CYP2E1 c1c2/c2c2, null GSTT1 and ADH2 1-1) play important roles in VCM metabolism. Polymorphisms of CYP 2E1, GSTT1 and ADH2 may be a major reason of genetic susceptibility in VCM-induced hepatic damage.展开更多
The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride (VBSC) with styrene was investigated by a simple mathematic model. Chain transfer constan...The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride (VBSC) with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the 1H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis, the obtained poIy(VBSC) and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer, which was in agreement with the theoretical results. The glass transition temperature, number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers, VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally, the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macro- initiators or reactive intermediates to synthesize functional polymers with complex structure.展开更多
自制了多单体接枝物PP g (St co MMA) ,并利用其增容PP/PVC共混体系。讨论了共混物组成、相容剂用量在不同温度、不同压力下对其流变行为的影响。实验结果表明 ,在所研究的温度和压力范围内 ,加入PP g (St co MMA)增容PP/PVC共混体系后 ...自制了多单体接枝物PP g (St co MMA) ,并利用其增容PP/PVC共混体系。讨论了共混物组成、相容剂用量在不同温度、不同压力下对其流变行为的影响。实验结果表明 ,在所研究的温度和压力范围内 ,加入PP g (St co MMA)增容PP/PVC共混体系后 ,共混物熔体呈典型的假塑性流体特性 ,粘流活化能增加 ,非牛顿性有增大的趋势。共混体系的力学性能提高 。展开更多
文摘In this review we discuss the history of research into the use of gold for the acetylene hydrochlorin‐ation reaction, and describe the recent developments which have led to its commercialisation. We discuss the use of different precursors and the addition to gold of a secondary metal as methods which attempt to improve these catalysts, and consider the nature of the active gold species. The vast majority of poly vinyl chloride (PVC) produced globally still uses a mercuric chloride as a cata‐lyst, despite the environmental problems associated with it. Due to the agreement by the Chinese government to remove mercury usage in the PVC industry over the course of the next few years there is an obvious need to find a replacement catalyst;the potential use of gold for this process has been well known for several decades and to date gold seems to be the best candidate for this, pri‐marily due to its superior selectivity when compared to other metals.
基金Supported by the National Natural Science Foundation of China, No. 30070650 and National Key Basic Research and Development Program of China, No. 2002CB512909
文摘AIM: To analyze occupational health hazards exposure to doses lower than the Chinese occupational health standard in a selected VC polymerization plant in China, and also to elucidate the relationship between genetic polymorphisms and genetic susceptibility on liver lesions of workers exposed to vinyl chloride monomer (VCM). METHODS: In order to explore the mechanism of VCM- related health effects, we used a case-control design to investigate the association between the genetic polymorphisms of metabolic enzymes and liver lesions in workers occupationally exposed to VCM. Genotypes of CYP2E1, GSTT1, GSTM1, ALDH2 and ADH2 were identified using PCR and PCR-RFLP. RESULTS: Even when the concentration of VCM was lower than the current Chinese occupational health standard, neurasthenia, pharyngeal irritation, liver ultrasonography abnormalities and hemoglobin disorders were significantly higher in exposure subjects compared to non-exposure subjects, and the relative risks (RRand 95% C1) were 1.74 (1.06-2.85), 1.97 (1.56-2.48), 10.69 (4.38-26.12), and 2.07 (1.20-3.57). CYP2E1 c1c2/c2c2 genotype was significantly associated with liver damages (OR 3.29, 95% CI 1.51-7.20, P〈0.01). CONCLUSION: The incidences of neurasthenia and liver ultrasonography abnormalities significantly increase when the cumulative exposure dose increases. The genotypes of metabolic enzymes (CYP2E1 c1c2/c2c2, null GSTT1 and ADH2 1-1) play important roles in VCM metabolism. Polymorphisms of CYP 2E1, GSTT1 and ADH2 may be a major reason of genetic susceptibility in VCM-induced hepatic damage.
基金supported by the National Natural Science Foundation of China(No.51003091)the Education Research Foundation of Yunnan Province(No.2010Y240)+1 种基金the Research Foundation of Yunnan University(No.2009B06Q)the Backbone Teacher Training Program of Yunnan University(No.21132014)
文摘The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride (VBSC) with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the 1H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis, the obtained poIy(VBSC) and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer, which was in agreement with the theoretical results. The glass transition temperature, number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers, VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally, the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macro- initiators or reactive intermediates to synthesize functional polymers with complex structure.
文摘自制了多单体接枝物PP g (St co MMA) ,并利用其增容PP/PVC共混体系。讨论了共混物组成、相容剂用量在不同温度、不同压力下对其流变行为的影响。实验结果表明 ,在所研究的温度和压力范围内 ,加入PP g (St co MMA)增容PP/PVC共混体系后 ,共混物熔体呈典型的假塑性流体特性 ,粘流活化能增加 ,非牛顿性有增大的趋势。共混体系的力学性能提高 。