Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-p...Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.展开更多
The plastification modification of poly (vinyl chloride) (PVC) with the long-chain linear polyester (LP) synthesized by linear dodecanedioic acid (DC12) or tetradecanedioic acid (DC14) with different diols i...The plastification modification of poly (vinyl chloride) (PVC) with the long-chain linear polyester (LP) synthesized by linear dodecanedioic acid (DC12) or tetradecanedioic acid (DC14) with different diols is investigated. The processing characteristics, mechanical properties and extraction property of the PVC/LP blends in different solvents (xylene, cyclohexane, ethanol) were also studied in detail. All results were compared with that of the PVC plasticized with dioctyl phthalate (DOP). The results show that the molecular weight, molecular structure and loading of LP greatly influence the mechanical properties of the PVC/LP blends. The processability and the mechanical properties of PVC plasticized by LP are comparable to those of the corresponding PVC/DOP blends. However, the PVC/LP blends posses much better migration resistance property than the corresponding PVC/DOP blends, which makes the long-chain linear polyester become a very good plasticizer candidate for PVC industry.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financial support of this work by National Key Research and Development Program of China(2017YFB0308600)National Natural Science Foundation of China(21878196)Fundamental Research Funds for the Central Universities,China(20826041C4159).
文摘Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.
基金the Engineering Developing Foundation of Tongji University
文摘The plastification modification of poly (vinyl chloride) (PVC) with the long-chain linear polyester (LP) synthesized by linear dodecanedioic acid (DC12) or tetradecanedioic acid (DC14) with different diols is investigated. The processing characteristics, mechanical properties and extraction property of the PVC/LP blends in different solvents (xylene, cyclohexane, ethanol) were also studied in detail. All results were compared with that of the PVC plasticized with dioctyl phthalate (DOP). The results show that the molecular weight, molecular structure and loading of LP greatly influence the mechanical properties of the PVC/LP blends. The processability and the mechanical properties of PVC plasticized by LP are comparable to those of the corresponding PVC/DOP blends. However, the PVC/LP blends posses much better migration resistance property than the corresponding PVC/DOP blends, which makes the long-chain linear polyester become a very good plasticizer candidate for PVC industry.
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.