This study investigates the aftermath of a significant train derailment and vinyl chloride release incident in East Palestine, Ohio, with a particular focus on the analysis of precipitation acidity changes and the con...This study investigates the aftermath of a significant train derailment and vinyl chloride release incident in East Palestine, Ohio, with a particular focus on the analysis of precipitation acidity changes and the concentration of vinyl chloride in samples. The research seeks to elucidate the complex relationship between industrial accidents, atmospheric chemistry, and their potential implications for human health and the environment. Through meticulous examination of variations in precipitation acidity patterns, this study provides valuable insights into the dispersion and impact of toxic agents in the environment following industrial mishaps. The results underscore the intricate interplay between these factors, highlighting the need for a multidisciplinary approach that bridges the realms of environmental science and biomedical concerns. This research contributes to a growing body of knowledge that addresses the broader consequences of industrial incidents on public health. It underscores the importance of proactive measures, such as enhanced monitoring and surveillance, risk assessment, public education, and regulatory reform, to mitigate the environmental and health risks associated with industrial activities involving hazardous materials. By fostering collaboration between experts and stakeholders, this study advocates for a holistic approach to safeguarding both our environment and the well-being of communities affected by industrial accidents.展开更多
Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vi...Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vital to explore alternative catalysts without mercury. We report here that N-doped carbon can catalyze directly transformation of acetylene to vinyl chloride. Particularly, N-doped high surface area mesoporous carbon exhibits a rather high activity with the acetylene conversion reaching 77% and vinyl chloride selectivity above 98% at a space velocity of 1.0 mL.min-l.g-1 and 200 ~C. It delivers a stable performa℃nce within a test period of 100h and no obvious deactivation is observed, demonstrating potentials to substitute the notoriously toxic mercuric chloride catalyst.展开更多
A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The res...A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The resulted revealed the higher stabilizing efficiency of the investigated rare-earth stearates as thermal stabilizers for rigid PVC compared with the thermal stabilizers for industry: calcium stearate, zinc stearate, butyl stannum mercaptide, phosphite esters, β-diketone and epoxidized sunflower oil. This was well illustrated by longer incubation period (T_S) values and lower rate of dehydrochlorination. The stable efficiency was affected by the nature of rare-earth element's individual electronic shell. The mechanism for the stabilizing effect of rare-earth stearates was proposed. The result was experimentally proved based on IR spectrum.展开更多
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
Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases an...Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.展开更多
The experimental creep data were focused on wood-flour (WF)/poly vinyl chloride (PVC) composites with the variations in additive concentrations of wood flour, silane coupling agent, organomodified montmorillonite ...The experimental creep data were focused on wood-flour (WF)/poly vinyl chloride (PVC) composites with the variations in additive concentrations of wood flour, silane coupling agent, organomodified montmorillonite (OMMT) and nano-cacium carbonate (nano-CaCO3). Their effects were analyzed using the Four-element Burger Model incorporating microscopic mechanisms. Total creep strain was low with increasing WF while elastic strain was high and plastic flow strain was low in modeling. Modification of WF with silane was beneficial to creep resistance, so did adding low ratio of OMMT (1.5 wt%) and nano-CaCO3 in composites. Thus, it was effective in reducing creep either by stiffening the PVC matrix using rigid nano-particles or by improving their adhesion with resin. However, superfluous quantity of any additament did not benefit the improvement owing to either earlier destruction of their agglomerates or stress-concentrated cracks in the over-incrassated interface.展开更多
LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X...LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X‐ray diffraction(XRD),Raman spectroscopy(Raman),O2temperature programmed desorption(O2‐TPD),H2temperature programmed surface reaction(H2‐TPR)and X‐ray photoelectron spectroscopy(XPS)were used to characterize the physicochemical properties of the LaMnO3samples.The preparation methods had obvious effects on the distribution of oxygen and manganese species on the catalyst surface.The reaction followed the suprafacial mechanism;the activity corresponded with the high amount of Mn4+and adsorbed oxygen species.LaMnO3prepared by the citrate sol‐gel method had the best performance for vinyl chloride combustion with T90of182°C.The optimal activity was attributed to the improved redox capability of Mn4+/Mn3+.More available adsorbed oxygen and Mn4+species on the surface were mainly responsible for the remarkable enhancement of the catalytic activity.展开更多
An obvious antiplasticizing effect has been observed in PVC with small amount of MOCA, 3,3’-dichloro-4,4’-diamino-diphenylmethane. PVC-MOCA interaction and crystallization behavior of PVC/MOCA blends were investigat...An obvious antiplasticizing effect has been observed in PVC with small amount of MOCA, 3,3’-dichloro-4,4’-diamino-diphenylmethane. PVC-MOCA interaction and crystallization behavior of PVC/MOCA blends were investigated in detail to explain the mechanism of antiplasticization on the basis of a series of techniques including DMA, FTIR, and DSC. The results of mechanical properties tests show that the tensile strength of PVC with 5 phr of MOCA reaches a maximum value, 69.5 Mpa, which is about 23 % higher than that of pure PVC. The rise in tensile strength was attributed to an antiplasticizing effect of MOCA on PVC as confirmed by DMA measurements. The evidences from FTIR reveal that a strong hydrogen-bonding interaction takes place between the nitrogen atom of –NH2 groups in MOCA and the methine proton of PVC repeat units. The results of DSC analysis indicate that crystallization behavior of MOCA is suppressed completely and the crystallinity of PVC decreases with the increase of MOCA amount.展开更多
Portal hypertension,liver fibrosis,and angiosarcoma of the liver(ASL)have been reported among workers exposed to vinyl chloride monomer(VCM)since the 1970s.In 2007,the International Agency for Research on Cancer estab...Portal hypertension,liver fibrosis,and angiosarcoma of the liver(ASL)have been reported among workers exposed to vinyl chloride monomer(VCM)since the 1970s.In 2007,the International Agency for Research on Cancer established the association of VCM with hepatocellular carcinoma(HCC),though only on the basis of the few cases available.Thereafter,recent reports from the United States cohort and a European sub-cohort of vinyl chloride workers provided compelling evidence of a strong association between cumulative VCM exposure and HCC risk.Further areas of research include the risk of liver cancer at lower levels of exposure and different patterns of risk of ASL and HCC with the time since exposure.The evidence of interaction between VCM exposure and other known liver carcinogens such as alcohol and chronic viral infection provides clues for the health surveillance of exposed workers.Notably,also the risk of VCM-associated chronic liver disease is modulated by alcohol consumption,viral infection,and genetic polymorphism.A counter-intuitive finding from cohort studies of exposed workers is the lower mortality from liver cirrhosis with respect to the general population;this can be attributed to the healthy worker effect and to the selection of liver cancer as the cause of death in the presence of concomitant chronic liver disease.Studies designed to overcome these intricacies confirmed an association between cumulative VCM exposure and the risk of liver cirrhosis.展开更多
Acetanilide (AC), adipic acid (AA) and potassium hydrogen phthalate (PHP) were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and ann...Acetanilide (AC), adipic acid (AA) and potassium hydrogen phthalate (PHP) were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and annealing on the crystallization behavior, micromorphology and the tensile properties were investigated by the thermal analysis, scanning electron microscopy (SEM) and the tensile test. Based on the analysis results, it was concluded that the melting peaks ranging from 110 to 200 ℃ and 200 to 240 ℃ were caused by the fusion of the fringed micelle crystals and chain-folded crystals respectively. AC advanced the fringed micelle crystal to develop, while AA and PHP promoted obviously the chain-folded crystal to grow. The addition of the foreign additives did not change the growth pattern ofPVC crystallites, the growth of the micelle crystal was favorable at 110 ℃, and the chain-folded crystal was developed at higher temperature. For PVC/ AA and PVC/PHP, when annealed at 110 ℃, a regular nest like network was formed, the crystallinity and the crystallite size were increased as well, and as a result, the tensile strength, Young's modulus and the elongation at break point were improved simultaneously and greatly.展开更多
Suspended emulsion polymerization of vinyl chloride was carried out in a 5 L autoclave. The influence of agitation, polymerization conversion, dispersant and surfactant on the average particle size (PS) and particle s...Suspended emulsion polymerization of vinyl chloride was carried out in a 5 L autoclave. The influence of agitation, polymerization conversion, dispersant and surfactant on the average particle size (PS) and particle size distribution (PSD), particle morphology and porosity of polyvinyl chloride (PVC) resin was investigated. It showed that the agitator had great influence on the smooth operation of polymerization, PS and PSD. The PS increased and PSD became narrow as polymerization conversion became high. The porosity decreased with the increase of conversion. A convenient choice of additives, both dispersants and non-ionic surfactants, allows one to adjust PS and PSD. The PS decreased with the addition of polyvinyl alcohol or hydroxypropyl methylcellulose dispersants,and increased with the addition of Span surfactants. The addition of dispersants or surfactants also affected the morphology and porosity of resin, and PVC resin with looser agglomeration and homogeneous distribution of primary particles was prepared.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
MgAl-NH3 LDHs (layered double hydroxides), ZnAl-LDHs and ZnAl-NH3 LDHs with different molar ratio of Al/ammonia were synthesized by co-precipitation method. The synthetic LDHs samples were characterized by XRD, FT-IR,...MgAl-NH3 LDHs (layered double hydroxides), ZnAl-LDHs and ZnAl-NH3 LDHs with different molar ratio of Al/ammonia were synthesized by co-precipitation method. The synthetic LDHs samples were characterized by XRD, FT-IR, TGA-DTG and SEM techniques and tested by Congo red method. In addition, after PVC (Poly vinyl chloride) and DOP (Dioctylphthalate) were added to LDHs, the thermal stability for PVC was characterized by TGA-DTG. The results indicated that LDHs intercalated with ammonia improved thermal stability for PVC significantly, MgAl-NH3 LDHs (Mg2+:Al3+: NH3·H2O = 3:1:0.5) and ZnAl-NH3 LDHs (Zn2+:Al3+:NH3·H2O=2:1:1.5) showed the best thermal stability for PVC, interlayered space of LDHs became larger by intercalating ammonia.展开更多
Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equatio...Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.展开更多
Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as ...Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV light was affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly.Different affiliation methods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature(Tg) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.展开更多
In this work,hydrothermal method was used to prepare the CaZnAl-CO3 ternary layered double hydroxides(CaZnAl-CO3-LDHs)with various Ca/Zn/Al molar ratios,which were characterized by X-ray diffraction(XRD),Fourier trans...In this work,hydrothermal method was used to prepare the CaZnAl-CO3 ternary layered double hydroxides(CaZnAl-CO3-LDHs)with various Ca/Zn/Al molar ratios,which were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscope(FT-IR)and scanning electron microscopy(SEM)techniques.The obtained results demonstrate that the samples were well-crystallized and flake-structured.The CaZnAl-CO3-LDHs used alone for thermal stability of poly(vinyl chloride)(PVC)resin,with different Ca/Zn/Al molar ratios and varying additive amounts,were investigated through the tests such as static thermal aging,mass loss and congo red,respectively.The optimum Ca/Zn/Al molar ratio and additive amount were 3.6:0.4:2 and 5 phr(parts per hundred PVC resin),respectively.In addition,the synergistic effects of Ca3.6Zn0.4Al2-CO3-LDHs and CaSt2 were discussed in detail,showing better thermal stability compared with Ca3.6Zn0.4Al2-CO3-LDHs used alone,and the optimum additive amounts of Ca3.6Zn0.4Al2-LDHs and CaSt2 were 6 and 1.0 phr,respectively.展开更多
Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was inves...Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.展开更多
The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl ...The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl chloride) was evaluated by Congo red method, thermoaging test and Thermogravimetric-differential Scanning Calorimetry (TG-DSC). The results showed that the addition of the phosphite or epoxy soybean oil improved the thermal stability of PVC with the calcium/zinc isocaprylates stabilizing system, especially epoxidied soybean oil exhibited a remarkable effect, and the synergism on PVC thermal stability for 3:2 phenyl dioctyl phosphite to epoxidized soybean oil weight ratio was acquired. Accordingly, the rapid mass loss in TG curve occured between 258.9 ℃ and 334.4 ℃, which corresponded to the enthalpy of the pyrogenation of 609.2 J/g. It was also found that the stabilized PVC of the best ratio gave better mechanical and processing properties.展开更多
MgAl LDHs intercalated with CO(NH2)2, NH4Cl and NH3·H2O were prepared by co-precipitation and XRD, FT-IR, TGA-DTA and SEM techniques were employed for characterization. The results indicated that the layer-layer ...MgAl LDHs intercalated with CO(NH2)2, NH4Cl and NH3·H2O were prepared by co-precipitation and XRD, FT-IR, TGA-DTA and SEM techniques were employed for characterization. The results indicated that the layer-layer spacing of LDHs was enlarged by 0.169, 0.285 and 0.227 Åwith the intercalation of CO(NH2)2, NH+4 and NH3, separately. The effects on thermal stability and degradation behavior of synthesized LDHs where mole ratios of Mg/Al/urea = 3:1:1, Mg/Al/NH4Cl = 3:1:1.5 and Mg/Al/NH3·H2O = 3:1:0.5 were investigated by Congo Red Method and thermogravimetric analysis (TGA) from 25°C - 800°C under N2. The TGA and DTA results showed, by incorporating 5% MgAl-CO(NH2)2 LDH, the dehydrochlorination temperature of PVC composites is 12°C higher than MgAl-NH+4 and MgAl-NH3 LDHs. MgAl-NH3 LDH enhances the ending temperature of the first degradation stage of PVC composites by 8°C compared with MgAl LDH. The LDH intercalated with CO(NH2)2 is proved to be an effective thermal stabilizer for PVC processing.展开更多
This research explored replacing acrylic core-shell impact modifier (AIM) by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM (8 phr) were substituted by silica fume in PVC respectively, and then processe...This research explored replacing acrylic core-shell impact modifier (AIM) by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM (8 phr) were substituted by silica fume in PVC respectively, and then processed by dry blending and twin-screw extrusion. Severe silica fume agglomeration was observed by scanning electron microscope (SEM) in the PVC matrix when 8 phr pure silica fume was used and processed by screw speed of 20 rpm. Its tensile strength was thereby reduced by 38% comparing to unmodified PVC. The silica fume was successfully dispersed while the screw speed was slowed down to 10 rpm to give a stronger screw torque and a longer melt residential time in the extruder. The tensile strength was ’recovered’ to a level comparable to unmodified PVC. Impact test were performed on all formulations extruded at 10 rpm screw speed and synergetic toughening effect was found with 50% substitution and it had the impact strength that was comparable to 8 phr pure AIM toughened PVC.展开更多
文摘This study investigates the aftermath of a significant train derailment and vinyl chloride release incident in East Palestine, Ohio, with a particular focus on the analysis of precipitation acidity changes and the concentration of vinyl chloride in samples. The research seeks to elucidate the complex relationship between industrial accidents, atmospheric chemistry, and their potential implications for human health and the environment. Through meticulous examination of variations in precipitation acidity patterns, this study provides valuable insights into the dispersion and impact of toxic agents in the environment following industrial mishaps. The results underscore the intricate interplay between these factors, highlighting the need for a multidisciplinary approach that bridges the realms of environmental science and biomedical concerns. This research contributes to a growing body of knowledge that addresses the broader consequences of industrial incidents on public health. It underscores the importance of proactive measures, such as enhanced monitoring and surveillance, risk assessment, public education, and regulatory reform, to mitigate the environmental and health risks associated with industrial activities involving hazardous materials. By fostering collaboration between experts and stakeholders, this study advocates for a holistic approach to safeguarding both our environment and the well-being of communities affected by industrial accidents.
基金supported by the Natural Science Foundation of China(No.11079005 and 21033009)the Ministry of Science and Technology of China(2011CBA00503 and 2012CB720302)
文摘Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vital to explore alternative catalysts without mercury. We report here that N-doped carbon can catalyze directly transformation of acetylene to vinyl chloride. Particularly, N-doped high surface area mesoporous carbon exhibits a rather high activity with the acetylene conversion reaching 77% and vinyl chloride selectivity above 98% at a space velocity of 1.0 mL.min-l.g-1 and 200 ~C. It delivers a stable performa℃nce within a test period of 100h and no obvious deactivation is observed, demonstrating potentials to substitute the notoriously toxic mercuric chloride catalyst.
文摘A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The resulted revealed the higher stabilizing efficiency of the investigated rare-earth stearates as thermal stabilizers for rigid PVC compared with the thermal stabilizers for industry: calcium stearate, zinc stearate, butyl stannum mercaptide, phosphite esters, β-diketone and epoxidized sunflower oil. This was well illustrated by longer incubation period (T_S) values and lower rate of dehydrochlorination. The stable efficiency was affected by the nature of rare-earth element's individual electronic shell. The mechanism for the stabilizing effect of rare-earth stearates was proposed. The result was experimentally proved based on IR spectrum.
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The project is supported by the National Natural Science Foundation of China (No. 29906009)
文摘Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.
文摘The experimental creep data were focused on wood-flour (WF)/poly vinyl chloride (PVC) composites with the variations in additive concentrations of wood flour, silane coupling agent, organomodified montmorillonite (OMMT) and nano-cacium carbonate (nano-CaCO3). Their effects were analyzed using the Four-element Burger Model incorporating microscopic mechanisms. Total creep strain was low with increasing WF while elastic strain was high and plastic flow strain was low in modeling. Modification of WF with silane was beneficial to creep resistance, so did adding low ratio of OMMT (1.5 wt%) and nano-CaCO3 in composites. Thus, it was effective in reducing creep either by stiffening the PVC matrix using rigid nano-particles or by improving their adhesion with resin. However, superfluous quantity of any additament did not benefit the improvement owing to either earlier destruction of their agglomerates or stress-concentrated cracks in the over-incrassated interface.
基金supported by the National Basic Research Program of China (2013CB933201)the National Natural Science Foundation of China (21207037,21577035)the Commission of Science and Technology of Shanghai Municipality (15DZ1205305)~~
文摘LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X‐ray diffraction(XRD),Raman spectroscopy(Raman),O2temperature programmed desorption(O2‐TPD),H2temperature programmed surface reaction(H2‐TPR)and X‐ray photoelectron spectroscopy(XPS)were used to characterize the physicochemical properties of the LaMnO3samples.The preparation methods had obvious effects on the distribution of oxygen and manganese species on the catalyst surface.The reaction followed the suprafacial mechanism;the activity corresponded with the high amount of Mn4+and adsorbed oxygen species.LaMnO3prepared by the citrate sol‐gel method had the best performance for vinyl chloride combustion with T90of182°C.The optimal activity was attributed to the improved redox capability of Mn4+/Mn3+.More available adsorbed oxygen and Mn4+species on the surface were mainly responsible for the remarkable enhancement of the catalytic activity.
基金Funded by National Natural Science Foundation of China(No.50673080)
文摘An obvious antiplasticizing effect has been observed in PVC with small amount of MOCA, 3,3’-dichloro-4,4’-diamino-diphenylmethane. PVC-MOCA interaction and crystallization behavior of PVC/MOCA blends were investigated in detail to explain the mechanism of antiplasticization on the basis of a series of techniques including DMA, FTIR, and DSC. The results of mechanical properties tests show that the tensile strength of PVC with 5 phr of MOCA reaches a maximum value, 69.5 Mpa, which is about 23 % higher than that of pure PVC. The rise in tensile strength was attributed to an antiplasticizing effect of MOCA on PVC as confirmed by DMA measurements. The evidences from FTIR reveal that a strong hydrogen-bonding interaction takes place between the nitrogen atom of –NH2 groups in MOCA and the methine proton of PVC repeat units. The results of DSC analysis indicate that crystallization behavior of MOCA is suppressed completely and the crystallinity of PVC decreases with the increase of MOCA amount.
文摘Portal hypertension,liver fibrosis,and angiosarcoma of the liver(ASL)have been reported among workers exposed to vinyl chloride monomer(VCM)since the 1970s.In 2007,the International Agency for Research on Cancer established the association of VCM with hepatocellular carcinoma(HCC),though only on the basis of the few cases available.Thereafter,recent reports from the United States cohort and a European sub-cohort of vinyl chloride workers provided compelling evidence of a strong association between cumulative VCM exposure and HCC risk.Further areas of research include the risk of liver cancer at lower levels of exposure and different patterns of risk of ASL and HCC with the time since exposure.The evidence of interaction between VCM exposure and other known liver carcinogens such as alcohol and chronic viral infection provides clues for the health surveillance of exposed workers.Notably,also the risk of VCM-associated chronic liver disease is modulated by alcohol consumption,viral infection,and genetic polymorphism.A counter-intuitive finding from cohort studies of exposed workers is the lower mortality from liver cirrhosis with respect to the general population;this can be attributed to the healthy worker effect and to the selection of liver cancer as the cause of death in the presence of concomitant chronic liver disease.Studies designed to overcome these intricacies confirmed an association between cumulative VCM exposure and the risk of liver cirrhosis.
基金Supported by the Fundamental Research Funds for the Central University(No.2012-Ia-040)the Scientific and Technological Project of Hubei Province(No.2002AA105A01)
文摘Acetanilide (AC), adipic acid (AA) and potassium hydrogen phthalate (PHP) were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and annealing on the crystallization behavior, micromorphology and the tensile properties were investigated by the thermal analysis, scanning electron microscopy (SEM) and the tensile test. Based on the analysis results, it was concluded that the melting peaks ranging from 110 to 200 ℃ and 200 to 240 ℃ were caused by the fusion of the fringed micelle crystals and chain-folded crystals respectively. AC advanced the fringed micelle crystal to develop, while AA and PHP promoted obviously the chain-folded crystal to grow. The addition of the foreign additives did not change the growth pattern ofPVC crystallites, the growth of the micelle crystal was favorable at 110 ℃, and the chain-folded crystal was developed at higher temperature. For PVC/ AA and PVC/PHP, when annealed at 110 ℃, a regular nest like network was formed, the crystallinity and the crystallite size were increased as well, and as a result, the tensile strength, Young's modulus and the elongation at break point were improved simultaneously and greatly.
基金Supported by the National Natural Science Foundation of China (No. 29906009).
文摘Suspended emulsion polymerization of vinyl chloride was carried out in a 5 L autoclave. The influence of agitation, polymerization conversion, dispersant and surfactant on the average particle size (PS) and particle size distribution (PSD), particle morphology and porosity of polyvinyl chloride (PVC) resin was investigated. It showed that the agitator had great influence on the smooth operation of polymerization, PS and PSD. The PS increased and PSD became narrow as polymerization conversion became high. The porosity decreased with the increase of conversion. A convenient choice of additives, both dispersants and non-ionic surfactants, allows one to adjust PS and PSD. The PS decreased with the addition of polyvinyl alcohol or hydroxypropyl methylcellulose dispersants,and increased with the addition of Span surfactants. The addition of dispersants or surfactants also affected the morphology and porosity of resin, and PVC resin with looser agglomeration and homogeneous distribution of primary particles was prepared.
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.
文摘MgAl-NH3 LDHs (layered double hydroxides), ZnAl-LDHs and ZnAl-NH3 LDHs with different molar ratio of Al/ammonia were synthesized by co-precipitation method. The synthetic LDHs samples were characterized by XRD, FT-IR, TGA-DTG and SEM techniques and tested by Congo red method. In addition, after PVC (Poly vinyl chloride) and DOP (Dioctylphthalate) were added to LDHs, the thermal stability for PVC was characterized by TGA-DTG. The results indicated that LDHs intercalated with ammonia improved thermal stability for PVC significantly, MgAl-NH3 LDHs (Mg2+:Al3+: NH3·H2O = 3:1:0.5) and ZnAl-NH3 LDHs (Zn2+:Al3+:NH3·H2O=2:1:1.5) showed the best thermal stability for PVC, interlayered space of LDHs became larger by intercalating ammonia.
基金This project is supported by National Natural Science Foundation of China
文摘Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.
基金Supported by the National Science and Technology Key Supporting Project(2013BAF08B05)the National Natural Science Foundation of China(21176137)
文摘Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV light was affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly.Different affiliation methods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature(Tg) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.
基金Project(21371180)supported by the National Natural Science Foundation of ChinaProject(K1303015-11)supported by the Science and Technology Project of Changsha City,ChinaProject(20130162110018)supported by the Specialized Research Fund for the Doctoral Program of Higher Education,China。
文摘In this work,hydrothermal method was used to prepare the CaZnAl-CO3 ternary layered double hydroxides(CaZnAl-CO3-LDHs)with various Ca/Zn/Al molar ratios,which were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscope(FT-IR)and scanning electron microscopy(SEM)techniques.The obtained results demonstrate that the samples were well-crystallized and flake-structured.The CaZnAl-CO3-LDHs used alone for thermal stability of poly(vinyl chloride)(PVC)resin,with different Ca/Zn/Al molar ratios and varying additive amounts,were investigated through the tests such as static thermal aging,mass loss and congo red,respectively.The optimum Ca/Zn/Al molar ratio and additive amount were 3.6:0.4:2 and 5 phr(parts per hundred PVC resin),respectively.In addition,the synergistic effects of Ca3.6Zn0.4Al2-CO3-LDHs and CaSt2 were discussed in detail,showing better thermal stability compared with Ca3.6Zn0.4Al2-CO3-LDHs used alone,and the optimum additive amounts of Ca3.6Zn0.4Al2-LDHs and CaSt2 were 6 and 1.0 phr,respectively.
基金This work was subsidized for improving medical service and security capacity in 2019“national survey of traditional Chinese medicine resources”(Financial Society[2019]Number 39).
文摘Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.
文摘The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl chloride) was evaluated by Congo red method, thermoaging test and Thermogravimetric-differential Scanning Calorimetry (TG-DSC). The results showed that the addition of the phosphite or epoxy soybean oil improved the thermal stability of PVC with the calcium/zinc isocaprylates stabilizing system, especially epoxidied soybean oil exhibited a remarkable effect, and the synergism on PVC thermal stability for 3:2 phenyl dioctyl phosphite to epoxidized soybean oil weight ratio was acquired. Accordingly, the rapid mass loss in TG curve occured between 258.9 ℃ and 334.4 ℃, which corresponded to the enthalpy of the pyrogenation of 609.2 J/g. It was also found that the stabilized PVC of the best ratio gave better mechanical and processing properties.
文摘MgAl LDHs intercalated with CO(NH2)2, NH4Cl and NH3·H2O were prepared by co-precipitation and XRD, FT-IR, TGA-DTA and SEM techniques were employed for characterization. The results indicated that the layer-layer spacing of LDHs was enlarged by 0.169, 0.285 and 0.227 Åwith the intercalation of CO(NH2)2, NH+4 and NH3, separately. The effects on thermal stability and degradation behavior of synthesized LDHs where mole ratios of Mg/Al/urea = 3:1:1, Mg/Al/NH4Cl = 3:1:1.5 and Mg/Al/NH3·H2O = 3:1:0.5 were investigated by Congo Red Method and thermogravimetric analysis (TGA) from 25°C - 800°C under N2. The TGA and DTA results showed, by incorporating 5% MgAl-CO(NH2)2 LDH, the dehydrochlorination temperature of PVC composites is 12°C higher than MgAl-NH+4 and MgAl-NH3 LDHs. MgAl-NH3 LDH enhances the ending temperature of the first degradation stage of PVC composites by 8°C compared with MgAl LDH. The LDH intercalated with CO(NH2)2 is proved to be an effective thermal stabilizer for PVC processing.
文摘This research explored replacing acrylic core-shell impact modifier (AIM) by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM (8 phr) were substituted by silica fume in PVC respectively, and then processed by dry blending and twin-screw extrusion. Severe silica fume agglomeration was observed by scanning electron microscope (SEM) in the PVC matrix when 8 phr pure silica fume was used and processed by screw speed of 20 rpm. Its tensile strength was thereby reduced by 38% comparing to unmodified PVC. The silica fume was successfully dispersed while the screw speed was slowed down to 10 rpm to give a stronger screw torque and a longer melt residential time in the extruder. The tensile strength was ’recovered’ to a level comparable to unmodified PVC. Impact test were performed on all formulations extruded at 10 rpm screw speed and synergetic toughening effect was found with 50% substitution and it had the impact strength that was comparable to 8 phr pure AIM toughened PVC.