GREEN CHEMISTRY
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2019
·Vol. 21
·期 23
·6430-6440
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IF 9.405
Siyu Pan,Delong Hou,Jinming Chang,Zhou Xu,Songhang Wang,Sunxian Yan,Qi Zeng,Zhonghui Wang,Yi Chen
The safety of flexible polyvinyl chloride (PVC) materials is now being questioned, partially due to allegations that di-(2-ethylhexyl) phthalate (DEHP), the dominant PVC plasticizer, is an endocrine disruptor and a probable carcinogen. As sustainable alternatives, aliphatic ester-derived plasticizers feature low cytotoxicity, biodegradability, and renewability, but they can only partially replace DEHP in PVC formulations because they have a strong tendency to migrate. Here, using epoxidized fatty acid methyl esters and aliphatic diesters as representatives, we demonstrate that covalently attaching one short ester at each α-position of aliphatic esters via Claisen condensation with judiciously selected dialkyl carbonate significantly suppresses their migration from the PVC matrix. In certain scenarios, the engineered plasticizers even migrate at a rate comparable to, or improved beyond that of DEHP. This approach harnesses the α-proton, a structural feature shared by all aliphatic esters, and dialkyl carbonate, an established “green chemical”, thus providing a potentially general and green route towards DEHP alternatives with unprecedented performance that may contribute to sustainability of the old and oft-maligned PVC industry.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Polymers
·
2020
·Vol. 12
·期 4
·913
·
IF 3.426
Qiaoguang Li,Xugang Shu,Puyou Jia,Yonghong Zhou
The aim of this study was to develop a facile one-pot reaction for the synthesis of biomass-based hyperbranched poly(ether)s end-capped as acetate esters (BHE) for use as a sustainable, safe and feasible plasticizer for flexible poly(vinyl chloride) (PVC) materials. BHE is completely miscible with PVC but shows weaker plasticizing effect than dioctyl phthalate (DOP) (EΔTgvalue of BHE reaches 64.8%). PVC plasticized with BHE displays greater thermal stability than that of PVC or PVC plasticized with DOP materials. BHE improves the thermal stability and flexibility of PVC materials. As a plasticizer, BHE displays lower solvent extractability and greater volatilization resistance than DOP. Acute oral toxicity indicates that BHE has toxic doses of 5 g/kg, suggesting that BHE is non-toxic.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
DOI
高影响因子
Journal of CO2 Utilization
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2024
·
IF 7.2
Sifan Chen,Tingting Zhao,Peiyuan Li,Shuanjin Wang,Dongmei Han,Sheng Huang,Wei Liu,Zhiheng Huang,Min Xiao,Yuezhong Meng
A completely new poly(carbonate-ester) macrodiol (PPCP-mDL), derived from direct copolymerization of carbon dioxide (CO 2 ), propylene oxide (PO), phthalic anhydride (PA) and 1, 4-butanediol (BDO) catalyzed by metal-free triethylborine (TEB)/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) pairs has been developed. The molecular weight of PPCP-mDL produced varying from 1.1–2.3 kg mol −1 can be easily controlled through the regulation of reaction conditions. For the formulation of non-toxic, phthalate-free flexible PVC, novel and biodegradable ec-PPCP-mDL with high molecular weight may be obtained through end-capping the PPCP-mDL using benzoyl chloride. The ec-PPCP-mDL/PVC blends display better comprehensive plasticization performance than do comparable blends with commercial DEHP plasticizers. These blends exhibit high thermal stability, mechanical properies, plasticizer migration resistance and transmittance. The interaction between ec-PPCP-mDL and PVC has been characterized using FTIR spectroscopy. A possible mode of plasticization has been suggested. The rich ester groups in the structure of ec-PPCP-mDLs interact well with PVC via hydrogen bonding, resulting in excellent compatiblity with PVC. Overall, the novel ec-PPCP-mDL material, respects an attractive alternative to plasticizers as a green, non-toxic, biodegradable, partially sustainable for the preparation of flexible PVC formulations.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF VINYL & ADDITIVE TECHNOLOGY
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2019
·Vol. 26
·期 1
·35-42
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IF 1.292
Yanke Li,Erlei Yu,Xiangming Yang,Zhong Wei
A series of multiarm structure hyperbranched polyester-b-poly( ε -caprolactone) (HEPCLs) with different lengths of poly( ε -caprolactone) (PCL) segments ( s = 3, 6, 7, 8) were synthesized. Hyperbranched polyester (HE) was synthesized from glycidol and succinic anhydride and used as a macromolecular polymerization initiator for ε -caprolactone. The HEPCLs were used as polyvinyl chloride (PVC) plasticizers and the mechanical properties, thermal properties, morphology, and migration stabilities of PVC films were explored. The plasticizing efficiency increased with the increase in PCL segments, and the plasticizing efficiency of HEPCL 8 exceeded that of dioctyl phthalate. Scanning electron microscopy and solid-state 1 H NMR showed that the HEPCLs possess better compatibility with PVC than HE. Moreover, HEPCLs exhibited excellent migration stability even at very harsh condition, indicating that HEPCLs can be used as no-migration PVC plasticizers in medical products, children's toys, and food packaging. J. VINYL ADDIT. TECHNOL., 26:35–42, 2020. © 2019 Society of Plastics Engineers
研究领域:
材料科学
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高分子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMERS AND THE ENVIRONMENT
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2020
·Vol. 28
·期 8
·2101-2107
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IF 2.572
Ma Yufeng,Song Fei,Kong Qinying,Li Qiaoguang,Jia Puyou,Zhou Yonghong
Dioctyl phthalate (DEHP), as the most used commercial plasticizer, has been restricted in many polymer products due to its reproductive toxicity to human body. In this study, castor oil based polyol ester(CPE) was synthesized via a simple and efficient way and used as a sustainable plasticizer in poly(vinyl chloride) (PVC) films to replace toxic DEHP. The chemical structure of the obtained bio-based plasticizer was characterized. The oral toxicity test indicated that CPE had toxic doses of over 3000 mg/kg. Tg of PVC films decreased from 87.4 to 19.1 °C, which is lower than PVC-DEHP systems. The tensile strength and elongation at break of PVC films plasticized with 50 phr CPE is 12.10 MPa and 450.15% respectively, which shows more flexible than PVC/50 prh DEHP samples.The DMA and tensile tests results indicated that the plasctizing effect of CPE was more excellent than DEHP. DEHP can be completely replaced with CPE in flexible PVC products.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2019
·
IF 6.97
Yechang Feng,Zhuangzhuang Chu,Limin Man,Yang Hu,Chaoqun Zhang,Teng Yuan,Zhuohong Yang
Herein, fishbone-like poly(methyl eleostearate) (PME) plasticizer with high biobased content of near 90% was developed for the production of flexible poly(vinyl chloride) (PVC) by the green cationic polymerization of biobased monomer methyl eleostearate (ME) using renewable coconut oil as solvent, rather than the traditional alkyl halides with toxicity and volatility. The microstructure of PME was investigated by multiple technologies, and the results show that the favored microstructure of PME is the 9,10-unit because of the lower surface electrostatic potential and average local ionization energy near the double bond at C9 and C10. The acute toxicity test of PME shows that it is biologically safe and nontoxic. The effect of content of PME and the commercial plasticizer bis(2-ethylhexyl) phthalate (DOP) on the performance of plasticized PVC was investigated. When the weight ratio of PME and DOP is fixed at 1:1, PVC film presents higher stretchability (604.7% vs 309.1%) and enhanced strength (21.0 MPa vs 11.0 MPa) compared with PVC plasticized with DOP. A possible mechanism related to chain entanglements and dipole–dipole interaction is proposed. Further, as DOP is substituted with PME, PVC films show improved migration resistance with the weight loss being more than 75% lower after leaching in petroleum ether and olive oil.
研究领域:
材料科学
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聚合物化学
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环境科学
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生物技术
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产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2020
·Vol. 45
·期 1
·123-130
·
IF 3.288
Wei Gao,Pingping Jiang,Qian Gu,Hong Zhang,Pingbo Zhang,Agus Haryono
A novel green plasticizer, acetylated lactic acid 1,6-hexane diester (ALHD), was successfully synthesized based on L-lactic acid, a renewable organic acid from corn starch. Its chemical structure was characterized using FTIR, 1H NMR and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). The plasticizing effects of ALHD as an alternative substitute for commercial plasticizer acetyl tributyl citrate (ATBC) in poly(vinyl chloride) (PVC) were investigated in detail. The results show that the PVC films plasticized using ALHD have better organic solvent resistance and food mimic migration stability than ATBC. After 24 hours of extraction in cyclohexane and petroleum ether, the weight loss of PVC sample S5 plasticized using pure ALHD was reduced by 83.6% and 77.5%, respectively, compared to that of PVC sample S1 plasticized with pure ATBC. Furthermore, after 72 hours of migration in activated carbon, the weight loss of PVC sample S5 decreased by 44.0% compared to that of PVC sample S1, which indicated that ALHD had excellent volatility and migration stability. The elongation at break of the PVC pieces increased from 644.65% to 802.15% as the content of ALHD improved, showing an increase of 24.4%. The mechanical property analysis showed that, with the replacement of ALHD in the place of ATBC, the PVC blends exhibited better flexibility and elasticity.
研究领域:
材料科学
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化学
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环境科学
·
高分子科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）