Phthalate Derivatives Research Articles

Synthesis and characterization of biobased polyester PVC plasticizers to industrial manufacturing of tubes

AbstractThe search for the substitution of phthalate derivatives in the process of polyvinyl chloride (PVC) plasticization is a matter of intensive research, due to the increasing proofs about phthalate toxicity. With this objective, a series of novel saturated polyesters (SPs) were synthesized by polycondensation from different biobased acids and diols, and end‐capped with 2‐tetradecyloctadecan‐1‐ol (TDOD). After characterization, the SPs were incorporated in an industrial formulation for flexible PVC and the mechanical properties of the films analyzed by tensile tests, DMTA, and DSC. The tensile tests revealed a similar ultimate tensile strength and a higher elongation at break for the PVC with SP as plasticizers compared with DEHTP (di[2‐ethylhexyl] terephthalate). The SP showing the most promising results was chosen to carry on an industrial manufacturing of a transparent tube. The migration tests of the tube show a much less leaching properties compared with tube prepared using the plasticizer DEHTP. All the results indicate that SPs can be an industrially viable and excellent alternative to DEHTP.

Phthalimide Residue in Coffee: Does It Solely Derive from Folpet?

Folpet, a fungicide used on several crops, easily degrades into phthalimide (PAI) at high temperatures and basic pH. The maximum admitted limit for Folpet in foodstuffs as coffee is defined by the sum of its amount and that of PAI. Noteworthy, PAI can also arise from the reaction between ubiquitous phthalate derivatives and NH3. This work aims to demonstrate that the detection of PAI in roasted coffee is not necessarily diagnostic for Folpet as it can also originate from the reaction between phthalic anhydride (PAA), derived from phthalates, and amino acids (AAs), as a NH3 source. Thermal treatment of AAs with PAA confirmed that PAI generation follows a temperature-dependent path. Experiments with diethyl phthalate (DEP) and AAs have shown that maximum PAI generation via heating occurs at 200 °C for 60 min. PAI generation has also been proven for Folpet-free green coffee beans that were heated under laboratory and industrial roasting conditions.

In vitro evaluation of cytotoxic effects of di (2-ethylhexyl) phthalate (DEHP) produced by Bacillus velezensis strain RP137 isolated from Persian Gulf

Phthalates are widely used in polymer science and have potential toxicity related to their chemical structures. However, lots of evidence indicate that phthalate derivatives are undoubtedly produced as secondary metabolites by organisms, including plants, animals, and microorganisms. In the present study, Bacillus velezensis strain RP137 was cultured under optimized conditions. Its biomass was extracted with ethyl acetate with one fraction showing cytotoxic properties. A pure compound was isolated from the active fraction using combined silica gel and LH20 size exclusion column chromatography. Structural evaluation including FT-IR, 1H NMR, 13C NMR, HR-MS and CHN analysis identified the purified compound as di(2-ethylhexyl)phthalate (DEHP) with the formula C24H38O4 and the molecular weight of 389.29Da. The microorganism-derived (stereospecific) DEHP was strongly reduced the proliferation and induced cytotoxic effects on various eukaryotic cell lines in compare to the synthetic racemic mixture of the compound when assessed by MTT assay. Furthermore, crystal violet assay and morphological changes confirmed the cytotoxic effect of DEHP. Interestingly, non-malignant SV40-immortalized fibroblast cells were less affected by the purified DEHP. Further evaluation on the antibacterial activity of DEHP documented no effect toward Gram-positive (S. aureus) and Gram-negative (E. coli and P. aeruginosa) pathogens even at a high concentration of 100μM. In conclusion, existence of DEHP as byproduct of microorganism's metabolism can seriously be considered as a warning to human health.

Bio-oil production from fast pyrolysis of furniture processing residue

The pyrolysis characteristic of furniture processing residue (FPR), which was analyzed by thermogravimetric analysis (TGA) under nitrogen atmosphere, mainly decomposed between 230 °C and 500 °C. The FPR was submitted to fast pyrolysis in a bubbling fluidized-bed reactor (BFR) for converting into bio-oil, bio-char. The product distribution and characteristics of bio-oil depend on the operating conditions (temperature, fluidizing flow rate, particle size of sample). The bio-oil yield showed the highest value (50.68 wt%) at the pyrolysis temperature of 450 °C with a biomass particle size of 1.0 mm and a fluidization velocity of 2.0×Umf. The bio-oil had high selectivity for dioctyl phthalate, levoglucosan, and phenolic derivatives. The carbon number proportions in bio-oils of FPR were 32.74 wt% for C5–C11 fraction, 47.60 wt% for C12–C18 fraction and 19.38 wt% of C25–C38 fraction, respectively. The gas product included CO, CO2, H2, and hydrocarbons (C1–C4), and the selectivity of CO2 was the highest. The high heating value (HHV) of gas products was between 4.60 and 12.90 MJ/m3. The bio-char shows high HHV (23.87 MJ/kg) and high C content (62.47 wt%) that can be applied as a solid fuel.

Towards bio-based plasticizers with reduced toxicity: Synthesis and performance testing of a 3-methylphthalate

As a very durable material, soft polyvinyl chloride (PVC) is used for many applications in the field of consumer products. To enable the desired properties, for example for medical devices, the addition of plasticizers is required. For this purpose, mostly dialkyl phthalates are used being produced on a multi-million tons scale annually. Since some of these are associated with human health effects, there is an increasing demand for the search of alternatives. Besides reduced toxicity while maintaining excellent performance features, an economic access as well as biorenewable starting materials are further criteria, which should be ideally fulfilled by such a new plasticizer generation. Targeting these demands and in contrast to most available substitutes being based on petrochemical feedstock, we developed a synthetic route starting from bio-renewable platform chemicals. In detail, a Diels-Alder reaction of 2-methylfuran and maleic anhydride and subsequent dehydration leads to three phthalate derivatives with different alcohol components bearing a methyl group at the aromatic ring. As a representative substance, di(2-ethylhexyl) 3-methylphthalate was chosen for performance tests, and this new bio-based alternative offers properties similar to known plasticizers in such initial studies. • Potential new plasticizers based on biorenewables were prepared starting from 2-methylfuran and maleic anhydride. • By means of different alcohol components, three dialkyl 3-methylphthalates were synthesized. • Initial performance tests with di(2-ethylhexyl) 3-methylphthalate showed several promising plasticizer properties.

A Modified 3D-QSAR Model Based on Ideal Point Method and Its Application in the Molecular Modification of Plasticizers with Flame Retardancy and Eco-Friendliness.

The addition of plasticizers makes plastics flammable, and thus, poses a potential risk to the environment. In previous researches, plasticizers with flame retardancy had been synthesized, but their eco-friendliness had not been tested or described. Thus, in this paper, eco-friendliness plasticizers with flame retardancy were designed based on phthalic acid esters (PAEs), which are known as common plasticizers and major plastic additives. For a comprehensive analysis, such as flammability, biotoxicity, and enrichment effects, 17 PAEs’ comprehensive evaluation values were calculated based on the ideal point method. Further, a multi-effect three-dimensional quantitative structure-activity relationship (3D-QSAR) model of PAEs’ flammability, biotoxicity and enrichment effects was constructed. Thus, 18 dimethyl phthalate (DMP) derivatives and 20 diallyl phthalate (DAP) derivatives were designed based on three-dimensional contour maps. Through evaluation of eco-friendliness and flammability, six eco-friendly PAE derivatives with flame retardancy were screened out. Based on contour maps analysis, it was confirmed that the introduction of large groups and hydrophobic groups was beneficial to the simultaneous improvement of PAEs’ comprehensive effects, and multiple effects. In addition, the group properties were correlated significantly with improved degrees of the comprehensive effects of corresponding PAE derivatives, confirming the feasibility of the comprehensive evaluation method and modified scheme.

Enhanced Biodegradation of Phthalic Acid Esters' Derivatives by Plasticizer-Degrading Bacteria (Burkholderia cepacia, Archaeoglobus fulgidus, Pseudomonas aeruginosa) Using a Correction 3D-QSAR Model.

A phthalic acid ester’s (PAEs) comprehensive biodegradability three-dimensional structure-activity relationship (3D-QSAR) model was established, to design environmentally friendly PAE derivatives, which could be simultaneously degraded by plasticizer-degrading bacteria, such as Burkholderia cepacia, Archaeoglobus fulgidus, and Pseudomonas aeruginosa. Only three derivatives of diethyl phthalate (DEP (DEP-27, DEP-28 and DEP-29)) were suited for their functionality and environmental friendliness, which had an improved stability in the environment and improved the characteristics (bio-toxicity, bioaccumulation, persistence, and long-range migration) of the persistent organic pollutants (POPs). The simulation inference of the microbial degradation path before and after DEP modification and the calculation of the reaction energy barrier exhibited the energy barrier for degradation being reduced after DEP modification and was consistent with the increased ratio of comprehensive biodegradability. This confirmed the effectiveness of the comparative molecular similarity index analysis (CoMSIA) model of the PAE’s comprehensive biodegradability. In addition, a molecular dynamics simulation revealed that the binding of the DEP-29 derivative with the three plasticizer-degradation enzymes increased significantly. DEP-29 could be used as a methyl phthalate derivative that synergistically degrades with microplastics, providing directional selection and theoretical designing for plasticizer replacement.

Sixth-generation of ziegler-natta catalyst for homopolymer polypropylene polymerization: Effect to product properties and regulation

The development of catalysts for polypropylene (PP) polymerization has begun since Ziegler-Natta (Z-N) discovered the catalyst for polyethylene polymerization. However, the first-generation catalyst which was a combination of TiCl3-AlEt2Cl (catalyst-co-catalyst) has low productivity and isotacticity. The modifications continue to be made to increase the productivity and isotacticity by combining the Z-N catalyst with MgCl2, internal donors, and external donors. The fourth-generation Z-N catalyst, TiCl4/Phthalate/MgCl2-AlEt3/Silane, has given satisfactory results with high productivity and isotacticity. Another concern arose when phthalate derivatives turned out to be able to initiate cancer formation. This problem has led catalyst development to the sixth-generation Z-N catalyst with a phthalate-free internal donor. This research intends to study the effects of sixth-generation catalysts to polypropylene properties when compared to the fourth-generation catalysts. We produced homopolymer polypropylene (HPP) by fourth- and sixth-generation of Z-N catalyst with the same polymerization technology. Then, the effects on product properties, namely melt flow rate (MFR), xylene soluble, residual catalyst, physical properties, optical properties, and rheological properties were observed. Sixth-generation catalyst exhibited a better stereoregularity and it made a better flexural modulus. The rheological properties showed the sixth-generation catalyst products have lower molecular weight and it generates fewer gels and lower impact strength. Sixth-generation catalyst also exhibited lower catalyst residue which allows lower dosage of an acid scavenger with comparable color performance. With increasingly strict restrictions on the use of phthalates, the sixth-generation catalyst is more convenient to use. In terms of the effect on the polypropylene properties, fourth-and sixth-generation catalysts have their respective advantages.

Cytotoxic effects of new bioactive compounds isolated from a Nigerian anticancer plant Melastomastrum capitatum Fern. leaf extract

Abstract The use of medicinal plants in human's health care delivery system in Nigeria exist for decades. Medicinal plants have been used to treat diseases such as malaria fever, cancers, hypertension, microbial infections, among others in Africa of which Melastomastrum capitatum is one of such plant. The plant has been used to cure many diseases notably cancer of the ovary in women by Fulani herdsmen. Hence, this study was carried out in order to isolate major bioactive compounds from the leaf of M. capitatum, and evaluate their cytotoxic effects on cancer cell lines. Methanol extracted was partitioned successively with solvents of varying polarities in ascending order, bio-monitored by anticancer activities. Fractions with the most anticancer activity after 24 hours’ incubation were purified in a silica gel column chromatography. Isolated bioactive compounds from ethyl acetate leaf extract of M. capitatum were then characterized using GC–MS, while in vitro anticancer activity was determined by MTT bio-assay on MCF-7, HMVII and OV-7 cell lines. Five compounds which are mainly saturated fatty acid esters and phthalate acid derivatives were isolated. They include di-benzofuran, 3-nitro (Z, 211.0; RT, 14.08 min), di‑butyl phthalate (Z, 278; RT,14.09 min), 2,4,7-trioxabicydo (4.4.0)9-decene, 8(4-(4-pentylcyclohexyl) cyclohexyloxy)-3-phenyl (Z, 467; RT, 14.31 min), 9- octadecenoic acid E, oleic acid (Z, 294.45; RT, 15.94 min) and phthalic acid-di(2-propylpentyl) ester (Z, 390.56; RT, 19.44 min). The compounds were cytotoxic against breast cancer cell line MCF-7, woman vagina melanoma cell line HMVII and ovarian cancer cell line OV-7. Two of the compounds showed high selective indices on breast and ovarian cancer cell lines. Oleic acid, Di-benzofuran-3-nitro, 2,4,7-Trio-B (4.4.0)-9D..... and DiBP ester showed IC50 values of 2.12 ± 0.01 μg/mL, 24.13 ± 6.12 μg/mL, 6.03 ± 0.21 μg/mL and 31.01 ± 5.04 μg/mL respectively on OV-7 cell line which were better than the values shown on MCF-7 and HMVII cell lines in vitro. The results showed that M. capitatum leaf extract possessed compounds which are cytotoxic on cancer cells. The plant's leaf might be a source for the discovery of new anticancer drug.

Biopolyurethane/Diethylhexyl Phthalate Hybrid Plasticizer for Flexible Polyvinyl Chloride

Worldwide concerns on the endocrine disruption of phthalate derivatives have sparked extensive research on its alternatives. One of the most prominent use of phthalate derivatives are on the plasticization of polyvinyl chloride (PVC). Therefore, numerous carboxyl acids and their derivates have been studied as candidates for PVC plasticizer. Elastomeric polyurethanes have been extensively studied as solid-state plasticizer to induce flexibility to otherwise rigid PVC. In this research, bio-based polyurethane (BPU) elastomers and phthalate hybrid plasticizer was used for the fabrication of flexible PVC. Even though half the amount of phthalate plasticizer was replaced with BPU the PVC with the hybrid plasticizer showed strain at break of 320.5 %. The of BPU reduced phthalate use by increasing the flexibility of PVC and reduced the migration of phthalate plasticizer.

Phthalate acid esters corrected with the summation of relative difference method in the construction of multispectral activity pharmacophore models and its application in molecular modifications

The phthalate acid esters were modified by multispectral activity pharmacophore model corrected with the summation of relative difference method to obtain phthalate derivatives with environmentally friendly and took into account Raman, infrared and ultraviolet multispectral activity. The multispectral enhancement mechanism of phthalate derivatives was studied by three-dimensional imaging showing the enhancement of the multispectral activity of the derivatives is related to the spatial overlap between the pharmacophore models. The findings provide a new theoretical calculation method for the joint evaluation of compounds multi-activity and provide theoretical support for the development of technology to enhance spectrum detection for phthalate acid esters.

Molecular Design of Environment-Friendly PAE Derivatives Based on 3D-QSAR Assisted with a Comprehensive Evaluation Method Combining Toxicity and Estrogen Activities

In this paper, a phthalic acid ester (PAE) three-dimensional quantitative structure-activity relationship (3D-QSAR) model with a double activity (toxicity and estrogenic activities) combination was established using a comprehensive evaluation method, in which the database of the combined activities consisted of 17 and 13 employed in the training sets and test sets, respectively. Ditridecyl phthalate (DTDP) derivatives with low-toxicity and estrogen combined activities were designed with DTDP as the target molecule. Four environmentally friendly DTDP derivatives were screened out by evaluating their environmental friendliness (expressed by persistence, bioaccumulation and migration) and practicability (expressed by insulation). Through the toxicity and estrogen single-activity model validation and contour map analyses, the results showed that the 3D-QSAR model for PAE toxicity and estrogen combined activities was feasible and the weight setting was reasonable. In addition, the mechanism analysis showed that the toxicity and estrogen combined activities of the four DTDP derivatives (2-CH3-DTDP, 2-OCHO-DTDP, 2-CH2COOH-DTDP, 2-CH2OH-DTDP) decreased in turn and were consistent with the single-activity model prediction. Meanwhile, it was speculated that the binding effect of the DTDP derivative molecules and estrogen-related proteins might be related to their hydrophobic interaction.

Investigation of the Potential Environmental Risks of Phthalate Derivatives Designed To Be Environmentally Friendly.

Phthalate derivatives with low estrogenic activity, high infrared spectrum signals, high Raman characteristic vibration spectrum, high fluorescence intensity, and high ultraviolet sensitivity were selected as precursors from our previous studies, so that the changes in their toxicity and estrogenic activity during biological metabolism, ozone oxidation, photocatalytic degradation, photodegradation, and microbial degradation could be studied.The transformation pathways of these derivatives were simulated, and the reaction energy barriers were calculated. To determine the potential environmental risks of these phthalate derivatives, the pharmacophore models of biotoxicity and estrogen activity of phthalates were used to predict the biotoxicity and estrogen activity of the transformed products. The results showed an increase in the biotoxicity and estrogen activity of the biometabolites, ozonation products, photocatalytic degradation products, and microbial degradation products; the only products that did not follow this trend were the photodegradation products. Notably, the pathways that produced more potentially toxic compounds were the less favorable paths. Our results indicate that the transformation products of the designed environmentally friendly phthalate derivatives potentially pose environmental risks. To avoid such risks, the environmental transformation pathway of these derivatives should be simulated to screen for environmentally friendly phthalate molecules. Environ Toxicol Chem 2020;39:1138-1148. © 2020 SETAC.

Electrochromism of substituted phthalate derivatives and outstanding performance of corresponding multicolor electrochromic devices

Abstract A new series of phthalate-based electrochromic materials were prepared and investigated. The introduced functional substituents on phthalate π-framework have a significant influence on the optical and electrochemical behaviors. Electrochromic devices of these phthalates exhibit a praiseworthy electrochromism, to be specific, with vivid colors, high optical contrast, fast response and excellent durability. To our surprise, one phthalate with the methoxyl substituent reveals an unanticipated photoluminescent nature, which renders the compound multifunction. In summary, outstanding electrochromic performances indicate that these phthalate derivatives are promising for applications in displays.

Palladium-Catalyzed Carboxylate-Assisted Ethoxycarboxylation of Aromatic Acids To Synthesize Monoethyl Phthalate Derivatives with Ethyl Bromodifluoroacetate.

A novel and efficient approach for direct carbonation of aromatic acids with ethyl bromodifluoroacetate as the carbonyl source is reported. A broad range of substrates bearing various functional groups were tolerated, leading to monoalkyl phthalate derivatives in moderate to good yields.

Phthalate derivatives from marine Penicillium decumbens and its synergetic effect against sepsis bacteria

Septicemia is a serious bloodstream bacterial infection resulting in blood poisoning and rapidly become human threats. The excessive usage of antibiotics against septicemic diseases developed the pan-drug resistant bacteria. Out of 15 marine fungal isolates, Penicillium decumbens was isolated from El-Shatby, Alexandria, Egypt, and identified as the potent isolate produced bioactive material(s) against some virulent septicemic pathogens. Diisooctyl phthalate (DIOP) in the butanol crude extract was determined by gas chromatography/mass spectrum. Antimicrobial activities were tested in comparison with some known antibiotics used for sepsis treatment. Five antibiotics were, in vitro, tested against septicemic resistant bacteria, either individually or in combination with butanol extract (BE) showed minimum inhibitory concentrations (MIC) 14.7 and 7.3 µg/ml against G+ve and G-ve tested strains, respectively. Combination of BE with azithromycin (AZM) reduced the MIC value by 73% for G+ve bacteria with the synergistic effect (fractional inhibitory concentration index) FICI = 0.39. Moreover, combination of BE with azithromycin (AZM), also, reduced the MIC value by 92% for Gve bacteria with the synergistic effect FICI = 0.37. The highest antiheamolytic activity reduction percentage was detected at 88% when the combined BE-AZM interact with the supernatant of K. pneumonia, whereas, the lowest antiheamolytic reduction percentage of 57% against E. coli. The findings suggest the use of Diisooctyl phthalate as improving agent in combination with antibiotics in pharmaceutical preparations.

Electrocarboxylation of halobenzonitriles: An environmentally friendly synthesis of phthalate derivatives

Abstract This manuscript presents an efficient approach for producing high valuable compounds using CO2 as building block. The methodology employed is based on electrochemical techniques, which allow performing eco-friendly chemistry solutions and maintaining the aim of offering a potential long-term strategy for reducing the CO2 emissions in the atmosphere, while obtaining useful compounds, such as aromatic acids and phthalate derivatives. This work describes the electrochemical reduction behavior of 4-halobenzonitrile compounds using Glassy Carbon and Silver as cathodes under inert and carbon dioxide atmosphere. Controlled potential electrolysis of 4-halobenzonitriles under CO2 allows obtaining, in very good yields, the corresponding mono- and di-carboxylated organic compounds in CO2-saturated solutions of dimethylformamide containing 0.1 M of tetrabutylammonium tetrafluoroborate. Electro-catalytic effects are seen when Ag is used a cathode, which give very high yields, especially as regards di-carboxylated products. The methodology offers a new “green” route for the synthesis of different phthalate derivatives, which can be potentially used for making plastic polymers in a more environmentally friendly way.

Electrocatalytic Processes for the Valorization of CO2: Synthesis of Cyanobenzoic Acid Using Eco-Friendly Strategies

Carbon dioxide (CO2) is a known greenhouse gas, and is the most important contributor to global warming. Therefore, one of the main challenges is to either eliminate or reuse it through the synthesis of value-added products, such as carboxylated derivatives. One of the most promising approaches for activating, capturing, and valorizing CO2 is the use of electrochemical techniques. In the current manuscript, we described an electrocarboxylation route for synthesizing 4-cyanobenzoic acid by valorizing CO2 through the synergistic use of electrochemical techniques (“green technology”) and ionic liquids (ILs) (“green solvents”)—two of the major entries in the general green chemistry tool kit. Moreover, the use of silver cathodes and ILs enabled the electrochemical potential applied to be reduced by more than 0.4 V. The “green” synthesis of those derivatives would provide a suitable environmentally friendly process for the design of plasticizers based on phthalate derivatives.

Triacetin as a Secondary PVC Plasticizer

The use of biobased plasticizers with low toxicity and good compatibility with polyvinyl chloride (PVC) has become more attractive in the recent years in contrast with phthalate derivatives. In this study, a glycerol derivative plasticizer (triacetin—TAG) was tested as a secondary plasticizer for PVC. TAG was added to PVC formulations from 10 up to 20 phr. The increase of the plasticizer content had a great influence on the properties of PVC samples. The good miscibility and therefore the efficient plasticization action of the TAG were supported by DMA results, since narrow peaks of tan (δ) curves and reduction of the Tg values for the samples were observed. The ensuing PVC demonstrated good rheological properties and thermal stability up to 200 °C. Finally, the presence of TAG reduces the hardness of materials and does not increase their density.

In Silico Screening of Green Plasticizers for Poly(vinyl chloride)

Phthalate derivative plasticizers used in poly(vinyl chloride) (PVC) processing have been a subject of concern because of their possible toxicity. Hence, there is a growing interest toward new, non...