In this study,as the plasticizer,Camellia oleifera seed-oil-based cyclohexyl ester(COSOCE)was prepared by the reaction of cyclohexene oxide and refined C.oleifera seed oil(RCOSO)obtained by acidification hydrolysis af...In this study,as the plasticizer,Camellia oleifera seed-oil-based cyclohexyl ester(COSOCE)was prepared by the reaction of cyclohexene oxide and refined C.oleifera seed oil(RCOSO)obtained by acidification hydrolysis after saponification.In addition,the structure of the target product was confirmed by Fourier transform infrared(FTIR)spectroscopy,nuclear magnetic resonance(NMR)spectroscopy,and Raman spectroscopy.COSOCE was used as plasticizer-modified polyvinyl chloride(PVC)membranes.The structure of the COSOCE-modified PVC membranes were characterized by Raman spectroscopy and scanning electron microscopy(SEM).The properties of the COSOCE-modified PVC membrane were characterized by contact angle measurements,universal testing machine,thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).The results revealed that(1)The COSOCE-modified PVC membranes exhibit a good microscopic morphology.Combined with energy-dispersive X-ray spectroscopy(EDS)and contact angle measurement results,the COSOCE-modified PVC membranes are confirmed to be a hydrophilic material.(2)The modified PVC membrane with 60%COSOCE exhibited the best mechanical properties.The tensile strength reached 23.56±2.94 MPa.(3)COSOCE-modified PVC material exhibited better thermal stability,with a loss rate of less than 75%at the end of the first decomposition stage.Compared with that of the dioctyl-phthalate(DOP)-modified PVC membrane,the initial decomposition temperature of PVC was increased by 1.17°C–8.17°C,and the residual rate was increased by 0.67%–5.75%.The carbon–carbon double bond in the COSOCE molecular structure can remove the free radicals generated during the degradation of PVC material and slow down the decomposition rate of PVC.In addition,the double bond can be cross-linked partially with the PVC molecular chain containing the conjugated polyene structure,thereby increasing the movement resistance of the PVC molecular chain segment.Hence,COSOCE can replace DOP as a PVC plasticizer.展开更多
An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was c...An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.展开更多
In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distri...In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.展开更多
Plasticizers in plasticized polyvinyl chloride (PVC) are generally physically added into PVC by compounding so that they can be rapidly leached from PVC articles during service. This results in their migration into th...Plasticizers in plasticized polyvinyl chloride (PVC) are generally physically added into PVC by compounding so that they can be rapidly leached from PVC articles during service. This results in their migration into the human environment with potentially serious consequences and lower effectiveness of the additives in PVC. Potentially the chemical modification of PVC during processing via reactive processing procedure is one of the most attractive solutions to these problems. In this paper, we will report our work in exploring an environmentally friendly and cost-effective reactive processing approach for chemically binding plasticizer into PVC chains. Our research results indicate that it is possible to reduce the plasticizer migration from a plasticized PVC by chemically binding of a certain plasticizer into PVC chains via reactive processing. Thus, high levels of binding of DBM,a maleate plasticizer, to PVC may be reached in less than 10 min under prevailing reactive processing conditions. The extent of binding of DBM as a function of the loading shows two peaks: one at a relatively low loading (less than 0.12 mol·kg^-1 PVC) tends to 100%, the other in the high loading region (more than 1.5 mol·kg^-1 PVC) approaches around 50%. The DBM modified PVC polymer exhibits behaviours as a plasticized PVC but its bound plasticising groups would not be leached by solvent extraction.展开更多
This aim of this work is to study the partial replacement of the plasticizer ordinarily used di-octyl phtalate (DOP) by the permanent plasticizers ethylene-vinyl-acetate (EVA) and acrylonytrile-bu- tadiene-styrene (AB...This aim of this work is to study the partial replacement of the plasticizer ordinarily used di-octyl phtalate (DOP) by the permanent plasticizers ethylene-vinyl-acetate (EVA) and acrylonytrile-bu- tadiene-styrene (ABS) in order to reduce migration of additives initially contents in polyvinyl chloride (PVC) stabilized with expoxidized sunflower oil (ESO). Migration tests with agitation to 40°C in sunflower oil and ethanol at 15% were made. Migration phenomenon was studied on the basis of the PVC samples mass variations, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) analysis. The results showed the effectiveness of the approach consisting in the partial substitution of DOP by plasticizers of polymeric nature. The following order concerning the migration of additives was found: DOP (40) > DOP:EVA > (30/10) DOP:ABS (30/10). Furthermore, all the measured values of overall migrations were lower than the maximum allowable overall migration: 10 mg-dm-2.展开更多
Plasticizers are essential additives in the processing of polyvinyl chloride(PVC),with phthalate plasticizers being widely used.However,these conventional plasticizers have been shown to be harmful to human health and...Plasticizers are essential additives in the processing of polyvinyl chloride(PVC),with phthalate plasticizers being widely used.However,these conventional plasticizers have been shown to be harmful to human health and environmentally unfriendly,necessitating the exploration of eco-friendly bio-based alternatives.In this study,Camellia oleifera seed oil,a specialty resource in China,was utilized as a raw material and reacted with 4,4′-Methylenebis(N,N-diglycidylaniline)(AG-80)to synthesize Phenyl Camellia seed Oil Ester(PCSOE).PCSOE was employed as a plasticizer to prepare modified PVC films with varying concentrations,with the conventional plasticizer dioctyl phthalate(DOP)serving as a control.Experimental results demonstrate that PSCOE-plasticized PVC films exhibit enhanced hydrophilicity,tensile strength,and thermal stability compared to DOP-modified PVC films.The contact angle of PSCOE-plasticized PVC films ranges from 66.26°to 78.48°,which is generally lower than the contact angle of DOP-modified PVC films at 78.40°,indicating improved hydrophilicity due to the modification with PCSOE.The tensile strength of PSCOE-plasticized PVC films ranges from 17.73 to 20.17 MPa,all surpassing the value of 16.41 MPa for DOP-modified PVC films.Moreover,the temperatures corresponding to 5%,10%,and 50%weight loss for PVC samples modified with PCSOE are higher than those for DOP.Hence,PCSOE presents a viable alternative to DOP as a plasticizer for PVC materials.展开更多
Systemic toxicity caused by repeated exposure to both polar and nonpolar leachables of di(2-ethylhexyl)-1,2-cyclohexane plasticized polyvinyl chloride(PVC)was evaluated with dual routes of parenteral administration me...Systemic toxicity caused by repeated exposure to both polar and nonpolar leachables of di(2-ethylhexyl)-1,2-cyclohexane plasticized polyvinyl chloride(PVC)was evaluated with dual routes of parenteral administration method on rats in the study.Experimental group and control group were designed by researchers.Tail intravenous injection with 0.9%sodium chloride injection extracts and intraperitoneal injection with corn oil extracts were conducted to the experimental rats while tail intravenous injection with 0.9%sodium chloride Injection and intraperitoneal injection with corn oil were conducted to the control rats.After 14 days,blood specimens were collected for clinical pathology(hematology and clinical chemistry)analysis.Selected organs were weighed and a histopathological examination was conducted.As a result,compared with the control animals,there were no toxicity-related changes on the parameters above.The results show that the rats do not show obvious systemic toxicity reaction caused by repeated exposure with dual routes of parenteral administration method on rats after administration with both polar and nonpolar exacts of di(2-ethylhexyl)-1,2-cyclohexane plasticized PVC simultaneously up for 14 days.展开更多
Waste cooking oil was modified to prepare bio-base plasticizers(a,b and c)with terephthalic acid,adipic acid and benzoic acid by transesterification,epoxidation and ring opening reactions,respectively.The polyvinyl ch...Waste cooking oil was modified to prepare bio-base plasticizers(a,b and c)with terephthalic acid,adipic acid and benzoic acid by transesterification,epoxidation and ring opening reactions,respectively.The polyvinyl chloride(PVC)films(a/PVC,b/PVC and c/PVC)were prepared using a,b and c as bio-base plasticizers.The epoxidation and ring opening reactions were mainly investigated through GC-MS analysis.The structures of bio-base plasticizers(a,b and c)were confirmed by Fourier transform infrared spectroscopy(FT-IR),^(1)H NMR and ^(13)C NMR.The mechanical properties of a/PVC were as good as those of PVC films with the dioctyl phthalate(DOP)plasticizer.Meanwhile,the elongation at break of c/PVC reached 422%.The glass transition temperature(Tg)from dynamic mechanical analysis(DMA)was reduced to 30.6℃,45.3℃,23.6℃and 40.6℃,respectively when 40 phr of a,b,c and DOP plasticizer were added.Results of thermogravimetric analysis(TGA)illustrated that the thermal degradation stabilitiy of a/PVC films was better than those of c/PVC and DOP/PVC.The volatility losses of a,b and c were lower than that of the DOP.Bio-base plasticizers a and c exhibited excellent migration resistance in different solutions(distilled water,50%ethanol(w/w)).The FT-IR of PVC films showed that the downfield shifts of the—CH—Cl groups of the PVC plasticized with a and c were greater than that of b/PVC.The bio-base plasticizers b had a better plasticizing effect at low temperature.展开更多
基金Funding Statement:The authors express their gratitude for the financial support from the National Natural Science Foundation of China(32101475)the Yuemu Technology Plan Project(YMKJ202201).
文摘In this study,as the plasticizer,Camellia oleifera seed-oil-based cyclohexyl ester(COSOCE)was prepared by the reaction of cyclohexene oxide and refined C.oleifera seed oil(RCOSO)obtained by acidification hydrolysis after saponification.In addition,the structure of the target product was confirmed by Fourier transform infrared(FTIR)spectroscopy,nuclear magnetic resonance(NMR)spectroscopy,and Raman spectroscopy.COSOCE was used as plasticizer-modified polyvinyl chloride(PVC)membranes.The structure of the COSOCE-modified PVC membranes were characterized by Raman spectroscopy and scanning electron microscopy(SEM).The properties of the COSOCE-modified PVC membrane were characterized by contact angle measurements,universal testing machine,thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).The results revealed that(1)The COSOCE-modified PVC membranes exhibit a good microscopic morphology.Combined with energy-dispersive X-ray spectroscopy(EDS)and contact angle measurement results,the COSOCE-modified PVC membranes are confirmed to be a hydrophilic material.(2)The modified PVC membrane with 60%COSOCE exhibited the best mechanical properties.The tensile strength reached 23.56±2.94 MPa.(3)COSOCE-modified PVC material exhibited better thermal stability,with a loss rate of less than 75%at the end of the first decomposition stage.Compared with that of the dioctyl-phthalate(DOP)-modified PVC membrane,the initial decomposition temperature of PVC was increased by 1.17°C–8.17°C,and the residual rate was increased by 0.67%–5.75%.The carbon–carbon double bond in the COSOCE molecular structure can remove the free radicals generated during the degradation of PVC material and slow down the decomposition rate of PVC.In addition,the double bond can be cross-linked partially with the PVC molecular chain containing the conjugated polyene structure,thereby increasing the movement resistance of the PVC molecular chain segment.Hence,COSOCE can replace DOP as a PVC plasticizer.
基金Sukanya Satapathy wishes to acknowledge Department of Science and Technology,Government of India,Women Scientists Scheme[Grant No.SR/WOS-A/CS-36/2016(G)]corresponding author Aruna Palanisamy wishes to acknowledge Ministry of environment,forests and climate change(Grant No.F.No.1-2/2013-CT)the funding(manuscript communication number:IICT/Pubs/2019/065).
文摘An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.
文摘In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.
文摘Plasticizers in plasticized polyvinyl chloride (PVC) are generally physically added into PVC by compounding so that they can be rapidly leached from PVC articles during service. This results in their migration into the human environment with potentially serious consequences and lower effectiveness of the additives in PVC. Potentially the chemical modification of PVC during processing via reactive processing procedure is one of the most attractive solutions to these problems. In this paper, we will report our work in exploring an environmentally friendly and cost-effective reactive processing approach for chemically binding plasticizer into PVC chains. Our research results indicate that it is possible to reduce the plasticizer migration from a plasticized PVC by chemically binding of a certain plasticizer into PVC chains via reactive processing. Thus, high levels of binding of DBM,a maleate plasticizer, to PVC may be reached in less than 10 min under prevailing reactive processing conditions. The extent of binding of DBM as a function of the loading shows two peaks: one at a relatively low loading (less than 0.12 mol·kg^-1 PVC) tends to 100%, the other in the high loading region (more than 1.5 mol·kg^-1 PVC) approaches around 50%. The DBM modified PVC polymer exhibits behaviours as a plasticized PVC but its bound plasticising groups would not be leached by solvent extraction.
文摘This aim of this work is to study the partial replacement of the plasticizer ordinarily used di-octyl phtalate (DOP) by the permanent plasticizers ethylene-vinyl-acetate (EVA) and acrylonytrile-bu- tadiene-styrene (ABS) in order to reduce migration of additives initially contents in polyvinyl chloride (PVC) stabilized with expoxidized sunflower oil (ESO). Migration tests with agitation to 40°C in sunflower oil and ethanol at 15% were made. Migration phenomenon was studied on the basis of the PVC samples mass variations, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) analysis. The results showed the effectiveness of the approach consisting in the partial substitution of DOP by plasticizers of polymeric nature. The following order concerning the migration of additives was found: DOP (40) > DOP:EVA > (30/10) DOP:ABS (30/10). Furthermore, all the measured values of overall migrations were lower than the maximum allowable overall migration: 10 mg-dm-2.
基金funded by the Scarce and Quality Economic Forest Engineering Technology Research Center(2022GCZX002)the Key Lab.of Biomass Energy and Material,Jiangsu Province(Grant No.JSBEM-S-202305).
文摘Plasticizers are essential additives in the processing of polyvinyl chloride(PVC),with phthalate plasticizers being widely used.However,these conventional plasticizers have been shown to be harmful to human health and environmentally unfriendly,necessitating the exploration of eco-friendly bio-based alternatives.In this study,Camellia oleifera seed oil,a specialty resource in China,was utilized as a raw material and reacted with 4,4′-Methylenebis(N,N-diglycidylaniline)(AG-80)to synthesize Phenyl Camellia seed Oil Ester(PCSOE).PCSOE was employed as a plasticizer to prepare modified PVC films with varying concentrations,with the conventional plasticizer dioctyl phthalate(DOP)serving as a control.Experimental results demonstrate that PSCOE-plasticized PVC films exhibit enhanced hydrophilicity,tensile strength,and thermal stability compared to DOP-modified PVC films.The contact angle of PSCOE-plasticized PVC films ranges from 66.26°to 78.48°,which is generally lower than the contact angle of DOP-modified PVC films at 78.40°,indicating improved hydrophilicity due to the modification with PCSOE.The tensile strength of PSCOE-plasticized PVC films ranges from 17.73 to 20.17 MPa,all surpassing the value of 16.41 MPa for DOP-modified PVC films.Moreover,the temperatures corresponding to 5%,10%,and 50%weight loss for PVC samples modified with PCSOE are higher than those for DOP.Hence,PCSOE presents a viable alternative to DOP as a plasticizer for PVC materials.
基金The authors are grateful to the financial support of National Key Research and Development Program,No.2016YFC1103205.
文摘Systemic toxicity caused by repeated exposure to both polar and nonpolar leachables of di(2-ethylhexyl)-1,2-cyclohexane plasticized polyvinyl chloride(PVC)was evaluated with dual routes of parenteral administration method on rats in the study.Experimental group and control group were designed by researchers.Tail intravenous injection with 0.9%sodium chloride injection extracts and intraperitoneal injection with corn oil extracts were conducted to the experimental rats while tail intravenous injection with 0.9%sodium chloride Injection and intraperitoneal injection with corn oil were conducted to the control rats.After 14 days,blood specimens were collected for clinical pathology(hematology and clinical chemistry)analysis.Selected organs were weighed and a histopathological examination was conducted.As a result,compared with the control animals,there were no toxicity-related changes on the parameters above.The results show that the rats do not show obvious systemic toxicity reaction caused by repeated exposure with dual routes of parenteral administration method on rats after administration with both polar and nonpolar exacts of di(2-ethylhexyl)-1,2-cyclohexane plasticized PVC simultaneously up for 14 days.
基金the financial support from National Key R&D Program of China(No.2018YFD-0600402)National Natural Science Foundation of China(No.31700503,3167030790,31470613)Natural Science Foundation of Jiangsu Province,China(No.BK20170160).
文摘Waste cooking oil was modified to prepare bio-base plasticizers(a,b and c)with terephthalic acid,adipic acid and benzoic acid by transesterification,epoxidation and ring opening reactions,respectively.The polyvinyl chloride(PVC)films(a/PVC,b/PVC and c/PVC)were prepared using a,b and c as bio-base plasticizers.The epoxidation and ring opening reactions were mainly investigated through GC-MS analysis.The structures of bio-base plasticizers(a,b and c)were confirmed by Fourier transform infrared spectroscopy(FT-IR),^(1)H NMR and ^(13)C NMR.The mechanical properties of a/PVC were as good as those of PVC films with the dioctyl phthalate(DOP)plasticizer.Meanwhile,the elongation at break of c/PVC reached 422%.The glass transition temperature(Tg)from dynamic mechanical analysis(DMA)was reduced to 30.6℃,45.3℃,23.6℃and 40.6℃,respectively when 40 phr of a,b,c and DOP plasticizer were added.Results of thermogravimetric analysis(TGA)illustrated that the thermal degradation stabilitiy of a/PVC films was better than those of c/PVC and DOP/PVC.The volatility losses of a,b and c were lower than that of the DOP.Bio-base plasticizers a and c exhibited excellent migration resistance in different solutions(distilled water,50%ethanol(w/w)).The FT-IR of PVC films showed that the downfield shifts of the—CH—Cl groups of the PVC plasticized with a and c were greater than that of b/PVC.The bio-base plasticizers b had a better plasticizing effect at low temperature.
