Highly stable and highly stretchable poly(vinyl chloride)‐based plastics prepared by adding novel green oligomeric lactate plasticizers

Abstract

Poly(vinyl chloride) (PVC) is one of the most widely applied plastics in the world, with inherent mechanical brittleness and inflexibility in room temperature. With the growing concern for health and safety, especially in some fields (children's toys, food packaging, medical supplies) that require high‐safety plastics, there is an urgent need to develop phthalate‐free high‐performance green PVC products. Herein, by blending novel green oligomeric lactate plasticizers 1, 4‐cyclohexane dimethanol oligomeric lactate‐levulinate (CDOL‐L) and 1,4‐cyclohexane dimethanol oligomeric lactate‐levulinic acid ketal ester (CDOL‐LKE), highly stretchable and highly stable PVC‐based plastics were prepared successfully. CDOL‐L and CDOL‐LKE were synthesized by a green route of esterification and ketalization using biomass as the main raw material, and their structures were jointly confirmed by Fourier transform infrared spectroscopy, 1H NMR and TOF‐MS. Through performance testing, CDOL‐L or CDOL‐LKE plasticized PVC material were determined to have triple high stability (thermal, mechanical and migration stability) superior to DOP, DOTP and ATBC plasticized PVC. The PVC plasticized by CDOL‐L exhibited break at elongation as high as 833.0% at 50 phr addition and 877.1% at 60 phr addition. Moreover, PVC plasticized by 50 phr CDOL‐LKE exhibited relatively better thermal stability (Ti,CDOL‐LKE = 271.4°C) for the special ketal structure on the plasticizer. In conclusion, CDOL‐L and CDOL‐LKE showed potential to substitute traditional plasticizers and pointed a new direction for the preparation of high‐performance PVC‐based plastics.

Flame-Retardant Plasticizer Derived from Renewable Acids for Poly(Vinyl Chloride) Improved Toughness and Flame Retardancy

“…According to the spectra, the chemical shifts for each proton in CL, RCL, LRCL, and PLRCL were as expected. As shown in the CL curves, the signals at 1.37 and 5.13 ppm corresponded to lactate groups (peaks 1 and 2), and the signals at 1.19–2.12 ppm (peaks 4–6) and 4.26 ppm (peak 3) belonged to the hexatomic ring of cyclohexanol, proving that CL was successfully synthesized by the esterification of cyclohexanol and l -lactic acid . As shown in Figure b, compared to the CL curves, the appearance of signals at 2.16–2.51 ppm (peaks 7, 9, and 11), 1.65–2.10 ppm (peaks 8, 12, and 13), 5.50 ppm (peak 10), and 0.85 ppm (peak 14) on the RCL curve belonged to the protons of RA, indicating that RA was successfully capped via CL.…”

“…As shown in the CL curves, the signals at 1.37 and 5.13 ppm corresponded to lactate groups (peaks 1 and 2), and the signals at 1.19−2.12 ppm (peaks 4−6) and 4.26 ppm (peak 3) belonged to the hexatomic ring of cyclohexanol, proving that CL was successfully synthesized by the esterification of cyclohexanol and L-lactic acid. 19 As shown in Figure 2b, compared to the CL curves, the appearance of signals at 2.16−2.51 ppm (peaks 7, 9, and 11), 1.65−2.10 ppm (peaks 8, 12, and 13), 5.50 ppm (peak 10), and 0.85 ppm (peak 14) on the RCL curve belonged to the protons of RA, 20 indicating that RA was successfully capped via CL. In the third reaction (see Figure 2c), the occurrence of the signals at 2.65−2.81 ppm (peaks 15 and 16) and 0.85 ppm (peak 14) belonged to levulinic acid, 21 proving the successful esterification of RCL and levulinic acid.…”

Synthesis and application of environmental plasticizers based on benzene polyacid ester

“…TEE, TMEE, TPE, and TMPE are compounds belonging to the benzene polyacid ester. They exhibit the following structural characteristics that contribute to their excellent thermal stability, enhancing the overall thermal stability and service life of PVC materials: The hexyl and heptyl ester chains in TEE, TMEE, TPE, and TMPE are longer, reducing molecular volatility and flammability, thereby improving material thermal stability 23 The benzene ring structure in TEE, TMEE, TPE, and TMPE provides resonance stability, dispersing and stabilizing electron density.…”

“…The hexyl and heptyl ester chains in TEE, TMEE, TPE, and TMPE are longer, reducing molecular volatility and flammability, thereby improving material thermal stability. 23 2. The benzene ring structure in TEE, TMEE, TPE, and TMPE provides resonance stability, dispersing and stabilizing electron density.…”