Poly(vinyl chloride)(PVC)materials are produced with high smoke and toxic gases during combustion,when commercial flame-retardant additives are incorporated.Here,rare-earth yttrium stannate(Y_(2)Sn_(2)O_(7)),which is ...Poly(vinyl chloride)(PVC)materials are produced with high smoke and toxic gases during combustion,when commercial flame-retardant additives are incorporated.Here,rare-earth yttrium stannate(Y_(2)Sn_(2)O_(7)),which is superior to commercial flame retardants,was designed to enhance the smoke suppression and toxicity reduction performance of PVC materials without damaging their mechanical properties.After the addition of 15 wt%Y_(2)Sn_(2)O_(7)(PVC/Y_(2)Sn_(2)O_(7)),the PVC composites achieved a V-0 rating,whereas the pure PVC material achieved a V-2 rating.The peak heat release rate of PVC/Y_(2)Sn_(2)O_(7) composite was reduced from 282.7 kW/m^(2)(pure PVC)to 243.6 kW/m^(2).In addition,the maximum smoke density(Ds-max)of PVC/Y_(2)Sn_(2)O_(7) was 263 m^(2)/m^(2),a decrease of 48.5%compared to pure PVC materials(511 m^(2)/m^(2)),indicating its outstanding ability for smoke suppression.Compared to Sb_(2)O_(3),Y_(2)Sn_(2)O_(7) can effectively reduce the release of the toxic gas CO(decreasing by 37.5%).Furthermore,the tensile strength of PVC can reach as high as 16.1 MPa.Compared with five widely used commercial flame retardants,Y_(2)Sn_(2)O_(7) demonstrates superior performance,positioning it as a promising alternative to prospective candidates.Therefore,this study developed a rare-earth flame retardant and offers a promising design to improve the fire safety of PVC composites.展开更多
The production of C_(2)H_(3)Cl from CH_(3)Cl(MCTV)represents a promising non-petroleum route for synthesizing C_(2)alkenes from C_(1)molecules.Exploration of new MCTV catalysts is crucial for advancing sustainable che...The production of C_(2)H_(3)Cl from CH_(3)Cl(MCTV)represents a promising non-petroleum route for synthesizing C_(2)alkenes from C_(1)molecules.Exploration of new MCTV catalysts is crucial for advancing sustainable chemical production.In this study,we present NaVO_(3)as a surface-confined coupling center for·CH_(2)Cl radicals,demonstrating its superior performance in the selective coupling of methyl chloride to synthesize vinyl chloride.By incorporating NaVO_(3)onto the surface of CeO_(2),the catalyst enables effective capture of·CH_(2)Cl radicals during the CH_(3)Cl oxidative pyrolysis and their subsequent conversion into C_(2)H_(3)Cl.We experimentally validate the capability of highly dispersed Na-VO_(3)to controllably couple·CH_(2)Cl radicals through in-situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry.The results demonstrate that the dispersion of NaVO_(3)on the catalyst surface has a considerable impact on the reaction efficiency of·CH_(2)Cl radicals and the overall MCTV performance.This discovery holds substantial implications for the controlled C_(1)radical transformation and provides a guidance for the design of catalysts for sustainable production of C_(2)H_(3)Cl.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
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
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
In order to improve mechanical properties of soft poly(vinyl chloride)(PVC) films,we used commercial multi-layer graphene(MLG) with large size and high structural integrity as reinforcing fillers,and prepared MLG/PVC ...In order to improve mechanical properties of soft poly(vinyl chloride)(PVC) films,we used commercial multi-layer graphene(MLG) with large size and high structural integrity as reinforcing fillers,and prepared MLG/PVC composite films by using conventional melt-mixing methods.Microstructures,static and dynamic mechanical properties of the MLG/PVC composite films were investigated.The results showed that a small amount of MLG loading could greatly increase the mechanical properties of the MLG/PVC composites.The tensile modulus of the 0.96 wt%MLG/PVC composites was up to 40 MPa,increasing by31.3%in comparison to the neat PVC.Such a significant mechanical reinforcement was mainly attributed to uniform dispersion of the large-size MLG,good compatibility and strong interactions among MLG and plasticizers and PVC.展开更多
The synergistic stabilization effect of different metal lanolin fatty acids as natural-based thermal stabilizers for poly（vinyl chloride） （PVC） including calcium lanolin fatty acid （Calan2）,zinc lanolin fatty ac...The synergistic stabilization effect of different metal lanolin fatty acids as natural-based thermal stabilizers for poly（vinyl chloride） （PVC） including calcium lanolin fatty acid （Calan2）,zinc lanolin fatty acid （Znlan2） and lanthanum lanolin fatty acid （Lalan3） were studied through Congo red testing,color measurements,FTIR analyses and thermal behavior in this paper. The results showed that Lalan3/Calan2/Znlan2 stabilizers exhibited more excellent thermal stabilization efficiency to PVC than Calan2/Znlan2 thermal stabilizers,and the optimal mass ratio of Lalan3/Calan2/Znlan2 was 8：9：3. At last,the effect of degradation mechanism on PVC and synergistic stabilization was also investigated by FTIR analyses and thermal behavior.展开更多
Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA...Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA） chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process. Membrane morphologies were observed by scanning electron microscopy （SEM）, and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy （XPS）. Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes. It was found that, the blend membranes containing longer PMAA arm length showed lower static protein adsorption, higher water permeation flux and better protein solution flux recovery.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
Spherical CeO_(2)synthesized by the hydrothermal process was used as support to prepare Pt/WO_(3)/CeO_(2),and the effects of tungsten(W)contents on activity,stability and polychlorinated by-products were investigated ...Spherical CeO_(2)synthesized by the hydrothermal process was used as support to prepare Pt/WO_(3)/CeO_(2),and the effects of tungsten(W)contents on activity,stability and polychlorinated by-products were investigated to understand the role of W for vinyl chloride(VC)catalytic oxidation.The introduction of12 wt%W to Pt/CeO_(2)(P12 WC)exhibits the highest catalytic activity with 90%conversion of VC at 250℃,meanwhile the stability improves and the polychlorinated by-products in the tail gas significantly decrease due to the removal of dissociated Cl species in the formation of HCl.The beneficial effects of W on Pt/CeO_(2)are closely related to the chemical state of Pt,redox and surface acid sites distribution.The doped W not only makes Pt disperse evenly on the support with the high valence,but also weakens the interaction between Pt and CeO_(2)by the formation of Pt-O-W and Pt-O-W-O-Ce species,which facilitates oxygen mobility.In addition,the modification of W species also significantly increases the surface acidity amount and changes the distribution of acid sites.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
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
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
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
A series of Co_(3) O_(4) catalysts was prepared by ammonia(Co-AP) and oxalate(Co-OP) precipitation,solgel(Co-SG),and urea hydrothermal(Co-UH) methods,and their physicochemical properties were characterised by numerous...A series of Co_(3) O_(4) catalysts was prepared by ammonia(Co-AP) and oxalate(Co-OP) precipitation,solgel(Co-SG),and urea hydrothermal(Co-UH) methods,and their physicochemical properties were characterised by numerous techniques including X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen sorption,X-ray photoelectron spectroscopy(XPS),temperature-programmed reduction of H_(2)(H_(2)-TPR),temperature-programmed desorption of O_(2)(O_(2)-TPD),and temperature-programmed desorption of NH_(3)(NH_(3)-TPD).The catalytic activity of each catalyst was estimated for the catalytic combustion of vinyl chloride(VC) emissions.The crystallite size of the Co_(3) O_(4) catalyst was found to be well correlated with the amounts of surface-adsorbed oxygen species and number of acid sites on the catalyst surface,and consequently,determined several physicochemical properties of the catalyst.Of the catalysts studied here,the Co-AP catalyst exhibits the smallest crystallite size,which increases the specific surface area and the concentration of Co^(2+) on the catalyst surface.This,in turn,enhances the redox property,oxygen mobility,and the number of acid sites associated with the Co-AP catalyst.In fact,the Co-AP catalyst exhibits the best catalytic activity for VC combustion at 360℃and does not produce any chlorinated by-products.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
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
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
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
基金financially supported by the Science and Technology Breakthrough Project of Inner Mongolia(Nos.2024KJTW0006 and 2023B2551)Central Guiding Science and Technology Development Fund of Inner Mongolia(No.2022ZY0100)+3 种基金Natural Science Foundation of Anhui Province(No.2408085ME140)National Key Laboratory of Baiyunobo Rare Earth Resource Research and Comprehensive UtilizationExperimental Center of Engineering and Material Science from the University of Science and Technology of ChinaInstruments Center for Physical Science,University of Science and Technology of China。
文摘Poly(vinyl chloride)(PVC)materials are produced with high smoke and toxic gases during combustion,when commercial flame-retardant additives are incorporated.Here,rare-earth yttrium stannate(Y_(2)Sn_(2)O_(7)),which is superior to commercial flame retardants,was designed to enhance the smoke suppression and toxicity reduction performance of PVC materials without damaging their mechanical properties.After the addition of 15 wt%Y_(2)Sn_(2)O_(7)(PVC/Y_(2)Sn_(2)O_(7)),the PVC composites achieved a V-0 rating,whereas the pure PVC material achieved a V-2 rating.The peak heat release rate of PVC/Y_(2)Sn_(2)O_(7) composite was reduced from 282.7 kW/m^(2)(pure PVC)to 243.6 kW/m^(2).In addition,the maximum smoke density(Ds-max)of PVC/Y_(2)Sn_(2)O_(7) was 263 m^(2)/m^(2),a decrease of 48.5%compared to pure PVC materials(511 m^(2)/m^(2)),indicating its outstanding ability for smoke suppression.Compared to Sb_(2)O_(3),Y_(2)Sn_(2)O_(7) can effectively reduce the release of the toxic gas CO(decreasing by 37.5%).Furthermore,the tensile strength of PVC can reach as high as 16.1 MPa.Compared with five widely used commercial flame retardants,Y_(2)Sn_(2)O_(7) demonstrates superior performance,positioning it as a promising alternative to prospective candidates.Therefore,this study developed a rare-earth flame retardant and offers a promising design to improve the fire safety of PVC composites.
文摘The production of C_(2)H_(3)Cl from CH_(3)Cl(MCTV)represents a promising non-petroleum route for synthesizing C_(2)alkenes from C_(1)molecules.Exploration of new MCTV catalysts is crucial for advancing sustainable chemical production.In this study,we present NaVO_(3)as a surface-confined coupling center for·CH_(2)Cl radicals,demonstrating its superior performance in the selective coupling of methyl chloride to synthesize vinyl chloride.By incorporating NaVO_(3)onto the surface of CeO_(2),the catalyst enables effective capture of·CH_(2)Cl radicals during the CH_(3)Cl oxidative pyrolysis and their subsequent conversion into C_(2)H_(3)Cl.We experimentally validate the capability of highly dispersed Na-VO_(3)to controllably couple·CH_(2)Cl radicals through in-situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry.The results demonstrate that the dispersion of NaVO_(3)on the catalyst surface has a considerable impact on the reaction efficiency of·CH_(2)Cl radicals and the overall MCTV performance.This discovery holds substantial implications for the controlled C_(1)radical transformation and provides a guidance for the design of catalysts for sustainable production of C_(2)H_(3)Cl.
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.
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.
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.
基金financial supports from the Ministry of Science and Technology of China(No.2012AA030303)the Hundred Talents Program of Chinese Academy of Sciences(No.CAS2012)the Fund for Creative Research Groups(No.51221264)
文摘In order to improve mechanical properties of soft poly(vinyl chloride)(PVC) films,we used commercial multi-layer graphene(MLG) with large size and high structural integrity as reinforcing fillers,and prepared MLG/PVC composite films by using conventional melt-mixing methods.Microstructures,static and dynamic mechanical properties of the MLG/PVC composite films were investigated.The results showed that a small amount of MLG loading could greatly increase the mechanical properties of the MLG/PVC composites.The tensile modulus of the 0.96 wt%MLG/PVC composites was up to 40 MPa,increasing by31.3%in comparison to the neat PVC.Such a significant mechanical reinforcement was mainly attributed to uniform dispersion of the large-size MLG,good compatibility and strong interactions among MLG and plasticizers and PVC.
基金Project supported by the Natural Science Foundation of Fujian Province (2007HZ0001-2)
文摘The synergistic stabilization effect of different metal lanolin fatty acids as natural-based thermal stabilizers for poly（vinyl chloride） （PVC） including calcium lanolin fatty acid （Calan2）,zinc lanolin fatty acid （Znlan2） and lanthanum lanolin fatty acid （Lalan3） were studied through Congo red testing,color measurements,FTIR analyses and thermal behavior in this paper. The results showed that Lalan3/Calan2/Znlan2 stabilizers exhibited more excellent thermal stabilization efficiency to PVC than Calan2/Znlan2 thermal stabilizers,and the optimal mass ratio of Lalan3/Calan2/Znlan2 was 8：9：3. At last,the effect of degradation mechanism on PVC and synergistic stabilization was also investigated by FTIR analyses and thermal behavior.
基金supported by the National 973 Program(No.2009CB623402)the National Natural Science Foundation of China(No.20974094)
文摘Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA） chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process. Membrane morphologies were observed by scanning electron microscopy （SEM）, and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy （XPS）. Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes. It was found that, the blend membranes containing longer PMAA arm length showed lower static protein adsorption, higher water permeation flux and better protein solution flux recovery.
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Project supported by the National Key Research and Development Program of China(2016YFC0204300)the National Natural Science Foundation of China(21976057,21922602)+1 种基金the"Shanghai Science and Technology Innovation Plan"Program(19DZ1208000)Innovation plan for college students。
文摘Spherical CeO_(2)synthesized by the hydrothermal process was used as support to prepare Pt/WO_(3)/CeO_(2),and the effects of tungsten(W)contents on activity,stability and polychlorinated by-products were investigated to understand the role of W for vinyl chloride(VC)catalytic oxidation.The introduction of12 wt%W to Pt/CeO_(2)(P12 WC)exhibits the highest catalytic activity with 90%conversion of VC at 250℃,meanwhile the stability improves and the polychlorinated by-products in the tail gas significantly decrease due to the removal of dissociated Cl species in the formation of HCl.The beneficial effects of W on Pt/CeO_(2)are closely related to the chemical state of Pt,redox and surface acid sites distribution.The doped W not only makes Pt disperse evenly on the support with the high valence,but also weakens the interaction between Pt and CeO_(2)by the formation of Pt-O-W and Pt-O-W-O-Ce species,which facilitates oxygen mobility.In addition,the modification of W species also significantly increases the surface acidity amount and changes the distribution of acid sites.
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.
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.
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financially supported by the National Key Research and Development Program of China(No.2016YFC0204300)the National Natural Science Foundation of China(Nos.21922602 and 21577035)the Fundamental Research Funds for the Central Universities(No.222201717003)。
文摘A series of Co_(3) O_(4) catalysts was prepared by ammonia(Co-AP) and oxalate(Co-OP) precipitation,solgel(Co-SG),and urea hydrothermal(Co-UH) methods,and their physicochemical properties were characterised by numerous techniques including X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen sorption,X-ray photoelectron spectroscopy(XPS),temperature-programmed reduction of H_(2)(H_(2)-TPR),temperature-programmed desorption of O_(2)(O_(2)-TPD),and temperature-programmed desorption of NH_(3)(NH_(3)-TPD).The catalytic activity of each catalyst was estimated for the catalytic combustion of vinyl chloride(VC) emissions.The crystallite size of the Co_(3) O_(4) catalyst was found to be well correlated with the amounts of surface-adsorbed oxygen species and number of acid sites on the catalyst surface,and consequently,determined several physicochemical properties of the catalyst.Of the catalysts studied here,the Co-AP catalyst exhibits the smallest crystallite size,which increases the specific surface area and the concentration of Co^(2+) on the catalyst surface.This,in turn,enhances the redox property,oxygen mobility,and the number of acid sites associated with the Co-AP catalyst.In fact,the Co-AP catalyst exhibits the best catalytic activity for VC combustion at 360℃and does not produce any chlorinated by-products.
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.
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.
