Study On The Synthesis And Properties Of Bio-based Epoxide Plasticizers

With the increasing requirements of health, environment friendly and high-performance of plastics, it is a tendency in the plasticizer industry that to produce and use more safety and multi-functional products. Furthernore, using bio-based plasticizer as a traditional petroleum-based phthalate substitute has become an industry hot topic. Therefore, the aim of this study is to develop oil based plasticizers from the abundantly and cheaply woody oil resources and cardanol. By using unsaturated double bonds, phenolic hydroxyl and other active groups of these natural resources, a series of reactions such as transesterification, Diels-Alder reaction, Williamson ether synthesis and epoxidation reaction were used to design and preparate oil base epoxy plasticizer products. These products were expected to have high plasticizing efficiency and low cost, and can impart excellent mechanical properties, thermal properties, processability, heat resistance and durability of the plasticized polyvinyl chloride products. The effects of the obtained plasticizers replacing the phthalate plasticizers were studied to reduce the dependence on petrochemicals in the plastic additive industry. This work also offered theoretical references and basis for the diversification and environmentally friendly of bio-based plasticizer, as well as a new approach for utilization of natural oil resources. The specific research work includes the following six parts:1. In this work, some kinds of peroxophosphatotungstate phase transfer catalysts were prepared. The chemical structural of catalysts were confirmed by FT-IR. The epoxidation of the fatty acid methyl ester(FAME) from Styrax tonkinensis seeds oil was selected as probe reaction, in order to build catalytic system without carboxylic acid for epoxidation of the long chain unsaturated compounds. The effects of reaction papameters on epoxidation were determined by orthogonal test. The epoxy value of the FAME was 4.71 %, under the optimum reactive conditions of catalyzed by(C21H38N)3{PO4[WO(O2)2]4}, hydrogen peroxide of 5.67 g, dropping of hydrogen peroxide by 150 ml / h, reaction time of 0.5 h, ethyl acetate solvent of 20 ml. The adaptability of the catalyst was studied. The kinetics of the epoxidation by phase transfer catalyst was investigated. And the dynamic model described the kinetics of the epoxidation was studied. The activation energy for the epoxidation was calculate which can provide a theoretical basis for the further study of the epoxidation of long chain unsaturated compounds.2. Based on part 1, rubber seed oil based epoxy fatty acid methyl ester plasticizer(EFAME) was synthesized with peroxophosphatotungstate catalyst. The structure of intermediates and final product were confirmed by GC-MS and 1 H NMR. EFAME was blended with PVC to inspect the plasticizing performance in soft PVC and its effects on replacing of DOTP. The mechanical properties, thermal properties, processability, heat resistance and durability of the plasticized systems were measured by tensile testing, Shore hardness, DSC, TGA, dynamic mechanical thermal analyzer and thermal aging oven. The results showed that the EFAME can significantly reduce Tg of PVC blends, and improve the flexibility, abrasion resistance, heat resistance, chemical resistance and processability of the plastic products.3. Dimer fatty acid methyl ester plasticizer(EDAF) was synthesized by dimerization reaction and epoxidation, using the intermediate rubber seed oil-based fatty acid methyl ester in Part 2 as a raw material. The structure and composition of products were analyzed by FT-IR and GPC respectively. The properties of mechanical, transition temperature, thermal stability, heat resistance and durability of the PVC blends were investigated and compared with DOP. The results show that when the amount of EDAF from 0 to 10 %, the elongation at break increased from 233.56 % to 270.12 %, the glass transition temperature decreased from 0.55 ℃ to-5.32 ℃and thermal degradation temperature increased from 238.0 °C to 255.4 °C. Furthermore, the thermal aging time extended from 16 min to 38 min and the organic solvent resistance has also been improved. It can be concluded that the EDAF is an effective plasticizer for PVC, and have the potential to be used as a durable plasticizer.4. In this work, two natural plasticizers, cardanol acetate(CA) and epoxidated cardanol acetate(ECA) were prepared by esterification and epoxidation from cardanol. 1H NMR and 13 C NMR analyses were used to characterize the structure of the product. The plasticizing effects of the obtained plasticizers on semi-rigid poly(vinyl chloride) formulations were also investigated. Two commercial phthalate ester plasticizers bis(2-ethylhexyl) benzene-1, 4-dicarboxylate(DOTP) and diisononyl phthalate(DINP) were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by means of DMA, mechanical analysis, TGA, SEM, and dynamic stability analysis, respectively. Results indicated that natural plasticizer ECA had overall superior flexibility, compatibility, thermal stability and workability comparable to both controls. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanical analysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These cardanol derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.5. A novel plasticizer derived from cardanol, epoxied cardanol glycidyl ether(ECGE), was synthesized by Williamson etherification and epoxidation reaction, and characterized by 1H NMR and 13 C NMR. Effects of ECGE combined with the commercial plasticizer dioctyl phthalate(DOP), in softPVC films, were studied. DMA was utilized to investigate the thermal properties of the plasticized PVC films and indicated a decrease in loss factor(tan δ) values and an increase in damping capability with the addition of small amounts of ECGE. Mechanical properties of PVC films showed both tensile strength and percent elongation increases with increasing ECGE content. TGA was performed to characterize the thermal stabilities of the plasticized samples and showed the stability of films increased with increasing the content of ECGE. The properties of volatility, extraction, and exudation resistance of plasticizers were tested and analysis by means of solubility parameters as reported in the literature suggests the ECGE has similar or higher stability in those properties than that of DOP. FTIR analysis for films also revealed that ECGE interacted with PVC. Due to its inherent chemical backbone and the modified epoxy groups, ECGE properly balanced the properties and improved the performance of PVC films compared with the neat DOP plasticizer.6. In this work, epoxied cardanol ethyl phosphate(ECDCP) was obtained through the modification of phenolic hydroxyl group and side-chain. The product was expected to work as a multifunctional plasticizer with great thermal stability and plasticizing effect. The product was characterization by FT-IR, 1H NMR and 13 C NMR, and subsequently use in PVC blends. The plasticizing effect of ECDCP on PVC and the thermal stability of the plasticized product were evaluated by DMA, TGA and thermal degradation kinetics analysis, and the performance analysis method of stretching before and after thermal aging. The results show that when the amount of EDAF increased from zero to 30% of the total mass of the plasticizer, Tg decreased from 41.07 °C to 36.43 °C, T10 and T50 increased from 26.85 °C to 43.51 °C. Furthermore, Ea of the thermal degradation reactions improved with the increase of ECDCP, indicating a higher thermal stability. The results of the tensile properties before and after heat aging showed that the flexibility of the samples containing ECDCP was significantly improved, and the mechanical properties differences before and after heat aging were less than that of DOP. When ECDCP replace 20 % of the DOP, PVC sample exhibits a low glass transition temperature, the optimal mechanical properties and good thermal stability.