Dipropylene Glycol Dibenzoate Research Articles

Global Environmental and Toxicological Data of Emerging Plasticizers: Current Knowledge, Regrettable Substitution Dilemma, Green Solution and Future Perspectives.

The global plasticizer market is projected to increase from $17 billion in 2022 to $22.5 billion in 2027. Various emerging/alternative plasticizers entered the market following the ban on several phthalate plasticizers because of their harmful effects. However, there is limited data (especially peer-reviewed) on emerging plasticizers' toxicity and environmental impact. This review compiles available data on toxicity, exposure, environmental effects, and safe production of emerging plasticizers. It identifies gaps in scientific research and provides evidence that emerging plasticizers are potential cases of regrettable substitution. Several alternative plasticizers, such as acetyl tributyl citrate (ATBC), diisononyl cyclohexane-1,2 dicarboxylate (DINCH), tris-2-ethylhexyl phosphate (TEHP), tricresyl phosphate (TCP), tris-2-ethylhexyl phosphate (TPHP), bis-2-ethylhexyl terephthalate (DEHT), and tris-2-ethylhexyl trimellitate (TOTM), show potential as endocrine disrupting properties and other toxic characteristics. Some chemicals like bis-2-ethylhexyl adipate (DEHA), diisobutyl adipate (DIBA), ATBC, DINCH, bis-2-ethylhexyl sebacate (DOS), diethylene glycol dibenzoate (DEGDB), DEHT, and phosphate esters showed the potential to cause toxicity in aquatic species. Plus, there is great lack of information on compounds like diisononyl adipate (DINA), dibutyl adipate (DBA), diisodecyl adipate (DIDA), dipropylene glycol dibenzoate (DPGDB), dibutyl sebacate (DBS), alkylsulfonic phenyl ester (ASE), trimethyl pentanyl diisobutyrate (TXIB), DEGDB and bis-2-ethylhexyl sebacate (DOS). Some compounds like epoxidized soybean oil (ESBO), castor-oil-mono-hydrogenated acetate (COMGHA), and glycerin triacetate (GTA) are potentially safer or less toxic. Alternative plasticizers such as adipates (LogKow 4.3-10.1), cyclohexane dicarboxylic acids (LogKow 10), phosphate esters (LogKow 2.7-9.5), sebacates (LogKow 6.3-10.1), terephthalates (LogKow 8.4), and vegetable oil derivatives (LogKow 6.4-14.8) have logKow values that are comparable to phthalate plasticizers (LogKow 7.5-10.4), indicating potential bioaccumulation and health consequences. Field studies have demonstrated that phosphate esters can undergo bioaccumulation and biomagnification, but there is a lack of bioaccumulation studies for other compounds. We also discuss the metabolism of emerging plasticizers, though data is limited. Our article highlights that numerous alternative compounds display potential health and ecological risks, indicating they might not be suitable substitutes for legacy plasticizers. There is also a lack of scientific data on most emerging plasticizers. This way, we call for increased research and timely regulatory action to prevent global contamination and health risks. Finally, this study presents a scientifically robust protocol to avoid harmful substitutions and ensure the production of safer chemicals.

Are New Phthalate Ester Substitutes Safer than Traditional DBP and DiBP? Comparative Endocrine-Disrupting Analyses on Zebrafish Using In Vivo, Transcriptome, and In Silico Approaches.

Although previous studies have confirmed the association between phthalate esters (PAEs) exposure and endocrine disorders in humans, few studies to date have systematically assessed the threats of new PAE alternatives to endocrine disruptions. Herein, zebrafish embryos were continuously exposed to two PAEs [di-n-butyl phthalate (DBP) and diisobutyl phthalate (DiBP)], two structurally related alternatives [diiononyl phthalate (DINP) and diisononyl hexahydrophthalate (DINCH)], and two non-PAE substitutes [dipropylene glycol dibenzoate (DGD) and glyceryl triacetate (GTA)], and the endocrine-disrupting effects were investigated during the early stages (8-48 hpf). For five endogenous hormones, including progesterone, testosterone, 17β-estradiol, triiodothyronine (T3), and cortisol, the tested chemicals disturbed the contents of at least one hormone at environmentally relevant concentrations (≤3.9 μM), except DINCH and GTA. Then, the concentration-dependent reduced zebrafish transcriptome analysis was performed. Thyroid hormone (TH)- and androgen/estrogen-regulated adverse outcome pathways (AOPs) were the two types of biological pathways most sensitive to PAE exposure. Notably, six compounds disrupted four TH-mediated AOPs, from the inhibition of deiodinases (molecular initiating event, MIE), a decrease in T3 levels (key event, KE), to mortality (adverse outcome, AO) with the quantitatively linear relationships between MIE-KE (|r| = 0.96, p = 0.002), KE-AO (|r| = 0.88, p = 0.02), and MIE-AO (|r| = 0.89, p = 0.02). Multiple structural analyses showed that benzoic acid is the critical toxicogenic fragment. Our data will facilitate the screening and development of green alternatives.

Identification and semi-quantification of metabolites of new plasticizers in urine collected from flemish adults and children

A suspect screening workflow combined with a semi-quantification method was applied for the investigation of metabolites of the plasticizers di-propylene glycol dibenzoate (DiPGDB) and tri-n-butyl trimellitate (TBTM) in human urine collected from adults and children during winter (W) and summer (S) seasons. Liquid chromatography - quadrupole time of flight mass spectrometry (LC-QTOF-MS) was applied for the analyses. Two direct and one indirect metabolites of DiPGDB were identified: 3-(3-hydroxypropoxy) propyl benzoate (DiPGDB-M194), 3,4,5-trihydroxy-6-[3-(3-hydroxypropoxy) propoxy] oxane-2-carboxylic acid (DiPGDB-M310), hippuric acid (DiPGDB-M179) and one metabolite of TBTM: bis(butoxycarbonyl) benzoyloxy]-3,4,5-trihydroxyoxane-2-carboxylic acid (TBTM-M498). The identified metabolites were reported with levels of confidence (LoC) 2 and 3 and their concentrations were assessed using a semi-quantification approach. The respective concentration ranges for W and S samples were 0.20–42 ng/mL and 0.07–29 ng/mL for DiPGDB-M194, 2.5–1420 ng/mL and 5.0–2320 ng/mL for DiPGDB-M310, 230–10840 ng/mL and 320–8420 ng/mL for DiPGDB-M179, and 0.40–30 ng/mL and 0.65–30 ng/mL for TBTM-M498. The detection frequency order in urine samples was DiPGDB-M310 = DiPGDB-M179 (100%) >TBTM-M498 (44%) > DiPGDB-M194 (28%) for W and DiPGDB-M179 (99%)> DiPGDB-M310 (98%) > TBTM-M498 (57%) > DiPGDB-M194 (30%) for S. The identified metabolites DiPGDB-M310, DiPGDB-M194 and TBTM-M498 are potential biomarkers for the evaluation of human exposure to DiPGDB and TBTM. DiPGDB-M179 cannot be used for the same purpose due to its formation from compounds with multi-source origin. The application of the semi-quantification method could be useful for further studies where analytical standards are not available.

Occurrence of newly identified plasticizers in handwipes; development and validation of a novel analytical method and assessment of human exposure via dermal absorption

A novel analytical method for the monitoring of four newly identified plasticizers, namely di-propylene glycol dibenzoate (DiPGDB), tri-n-butyl trimellitate (TBTM), isooctyl 2-phenoxyethyl terephthalate (IOPhET) and bis 3,5,5-trimethylhexyl phosphate (TMHPh), in handwipes based on pulverization was developed and in-house validated. In total, 164 handwipe samples (paired with house dust and human urine) were collected during winter (n = 82) and summer (n = 82) 2019 from adults and toddlers living in Flanders, Belgium. Method LOQs ranged from 1 to 200 ng/g. The ranges of Σplasticizers were 70–5400 ng/g for winter and 70–3720 ng/g for summer. The detection frequencies were 39% for DiPGDB, 27% for TBTM and <5% for IOPhET and TMHPh in winter samples and 33% for DiPGDB, 21% for TBTM and <10% for IOPhET and TMHPh in summer ones. The dominant compound in handwipes was DiPGDB, with mean contributions of 74% and 83% for winter and summer, followed by TBTM (24% and 9.2%), TMHPh (1.8% and 8.1%) and IOPhET (<1% and <1%). Σplasticizers concentrations were positively correlated in summer with the use of sanitizer (r = 0.375, p < 0.05) and negatively correlated in winter with the use of personal care products (r = −0.349, p < 0.05). DiPGDB was found positively correlated with the age of the participants (r = 0.363, p < 0.05) and the time spent indoors (r = 0.359, p < 0.05), indicating indoor environment as a potential source. Levels of TBTM in handwipes were positively correlated with dust samples collected from the same households (r = 0.597, p < 0.05), and those detected in toddler handwipes were significantly higher compared to adults (p < 0.05). Human daily exposure via dermal absorption was evaluated using the dermal derived no effects level values (DNEL), available in the database of the European Chemicals Agency (ECHA) and estimated using the theoretical bio-accessible fractions per compound. Toddler exposure to TBTM was significantly higher compared to adults (T-test, p < 0.05). No risk for adverse human health effects was derived from the comparison with DNELs for all compounds.

In vitro Phase I metabolism of newly identified plasticizers using human liver microsomes combined with high resolution mass spectrometry and based on non-targeted and suspect screening workflows

Three plasticizers, namely bis (3,5,5-trimethylhexyl) phosphate (TMHPh), di(propylene glycol) dibenzoate (DiPGDB), and tri-n-butyl trimellitate (TBTM), were recently identified and reported in high concentrations in indoor dust from Belgian homes. In this study, their behavior within the human body was investigated by generating Phase I biotransformation products for the first time. Human liver microsomes (HLMs) were used following an in vitro assay and liquid chromatography time of flight mass spectrometry (LC-QTOF-MS) was employed for the analysis. Biotransformation products were identified for TMHPh as products of hydroxylation reactions that took place in one or two positions in the structure of the substrate. For DiPGDB, biotransformation products were formed after hydrolysis of carboxylic esters and oxidative-O-dealkylation. For TBTM, biotransformation products were formed through hydrolysis of the different carboxylic esters of the molecule, in agreement with studies on structurally similar compounds. The generated results can contribute to biomonitoring studies creating new knowledge on human exposure to emerging compounds and on the metabolism of xenobiotics.

EVALI Vaping Liquids Part 2: Mass Spectrometric Identification of Diluents and Additives.

The vaping liquid additive vitamin E acetate (VEA) was strongly linked to the 2019 United States nationwide outbreak of pulmonary lung illness (EVALI) associated with e-cigarettes or vaping liquids. Our laboratory received over 1,000 vaping liquid products for identification of the vaping liquid additives, including hundreds of vaping products from EVALI patients. In this work, we present results obtained for the GC-MS identification of numerous vaping liquid additives in a large subset of ca. 300 Cannabis vaping liquids, including vitamin E acetate, medium chain triglycerides oil (MCT oil), polyethylene glycols, squalane, triethyl citrate, dipropylene glycol dibenzoate (DPG dibenzoate), pine rosin acids, pine rosin methyl esters, and sucrose acetate isobutyrate (SAIB). Confirmation of DPG dibenzoate and SAIB using LC-HRMS is also presented. GC-MS analysis for additives identified as the parent compounds was conducted after separation on a commercial 5% phenyl phase. GC-MS analysis for additives identified as the trimethylsilyl derivatives was conducted after separation on a commercial 35% silphenylene phase. LC-HRMS analysis was conducted using gradient elution with either C18 or phenyl-hexyl phases and determination of exact masses for the target compounds. In addition to providing rapid methods for the identification of vaping liquid additives, this work highlights the variety of Cannabis vaping liquid additives in current use.

From suspect screening to target analysis: Occurrence of six newly identified compounds in indoor dust from Belgium

Six newly identified compounds, dimethyl azelate (DMA), dimethyl sebacate (DMS), di-propylene glycol dibenzoate (DiPGDB), tri-n-butyl trimellitate (TBTM), isooctyl 2-phenoxyethyl terephthalate (IOPhET) and bis-3,5,5-trimethylhexyl phosphate (TMHPh), were quantified in residential dust using a modified and in-house validated method. The method was based on vortex and ultrasonic extraction, Florisil fractionation and liquid chromatography with tandem mass spectrometry (LC-MS/MS) analysis. Fifty paired dust samples were collected from homes located in the Flemish region of Belgium, during winter (n = 25) and summer (n = 25) of 2019. Method LOQs ranged between 3.8 and 94 ng/g. The ranges of total concentrations of targeted compounds were 0.6–89 μg/g for winter and 0.8–130 μg/g for summer samples. DiPGDB was the dominant compound, with 88% and 92% contribution in dust samples per season, followed by TBTM > TMHPh > DMA (less than 10% contribution in both seasons) and DMS, detected only in the summer samples. Human exposure was evaluated for inadvertent dust ingestion using the oral derived no effects level values (DNEL) where available in ECHA, for (I) the hypothesis, where the total concentration of the chemical is considered bio-accessible, (II) the hypothesis where the bio-accessible fraction is defined by the theoretical bio-accessibility, calculated based on logKow values. In both scenarios, DiPGDB, TBTM and TMHPh had the most important contribution to human exposure, with toddlers being more exposed than adults. No risk for adverse human health effects was derived from the comparison with DNELs.

Plasticizing effect of biodegradable dipropylene glycol bibenzoate and epoxidized linseed oil on diglycidyl ether of bisphenol A based epoxy resin

AbstractMajor limitation for use of epoxy thermosets in engineering applications is its sudden brittle failure. In the present study dipropylene glycol dibenzoate (DPGDB) based plasticizer is used to modify diglycidyl ether of bisphenol A (DEGEBA) based epoxy resin system via simple blending technique. Bio‐based epoxidized linseed oil was also used to modify epoxy resin system and compared with DPGDB modified resin. For DPGDB modified resin storage modulus and loss modulus of the epoxy system modified with 10% plasticizer increased by 7.54% and 12.24%, respectively. The primary mechanism responsible for such behavior is improved crosslinking density. With 5% plasticizer loading, flexural strength increased by 21%. There was an improvement of 312.74% in strain at failure for 10% plasticizer loading, while preserving its mechanical strength. It was found that DPGDB based modification was better than epoxidized linseed oil modification.

Suspect screening analysis in house dust from Belgium using high resolution mass spectrometry; prioritization list and newly identified chemicals

In recent years, several changes have been made to the composition of various products which are used indoors. Plenty of new chemical additives have been incorporated to materials to comply with current legislation and safety rules. Consequently, the emission profiles of contaminants detected indoors may change over time, requiring continuous monitoring. In this study, dust samples were collected from 25 homes located in the Flemish region of Belgium during different seasons (winter and summer). Our aim was the development of a suspect screening workflow for the identification of new chemicals which might have been applied to indoor goods, released into the indoor environment, and accumulated in dust. An in-house suspect list was curated including selected groups of compounds, namely “phthalates”, “phosphates”, “terephthalates”, “citrates”, “trimellitates”, (di-, tri-, tetra-) “carboxylic acids”, “adipates”, “azelates”, “sebacates”, (di-)“benzoates”, and “succinates”. 63 chemicals were prioritized based on their level of identification and detection frequency in samples. Seasonal comparison was tested, indicating that higher temperatures of summer might facilitate the release of few chemicals from the products into the indoor environment. Seven chemicals, to the best of our knowledge not previously reported, were selected out of the 63 listed and identified for structure confirmation using high-resolution mass spectrometry. Tributyl trimellitate (TBTM), bis (3,5,5-trimethylhexyl) phosphate (Bis-3,5,5-TMHPh), iso-octyl 2-phenoxy ethyl terephthalate (IOPhET), dimethyl azelate (DMA), dimethyl sebacate (DMS), dipropylene glycol dibenzoate (DiPGDB) and 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) were detected at frequencies ranging from 8 to 52% in winter and 4–56% in summer dust.

The effect of Styrene Maleic Anhydride on the microstructure evolution of PSF-based membrane prepared by thermal-induced phase separation method

Polysulfone (PSF) and Styrene Maleic Anhydride (SMA) were blended by thermally induced phase separation method in the preparation of membranes for water treatment. Dipropylene Glycol Dibenzoate (DPGDB) was used as a diluent which was extracted using ethanol. The increase in SMA concentration was positively confirmed by monitoring the intensity of the peak at 1779 cm−1 characteristic to CO in the Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) spectra. This observation was validated by elemental quantification using X-Ray Photoelectron Spectroscopy (XPS). Scanning Electron Microscopy (SEM) showed that the surface and cross-section morphology changed with an increase in SMA concentration. The average membrane pore size increased from 38.25 nm to 61.30 nm. In the same regard, average porosity increased from 16% to 57%. These observations were attributed to the effect of SMA molecules on the liquid-solid phase separation. The effect of SMA on wettability of the membrane was investigated by contact angle measurements where it was found that the hydrophilicity decrease with an increase in SMA content. The hydrophilicity had positive influence in membrane fouling resistance. The antifouling propensity reached up to 91% when the SMA content was 2% wt/wt compared to the base membrane which was 86%. The maximum pure water flux was found to be 147 Lm−2 h−1 when the SMA content was 2%. It decreases to 33 Lm−2 h−1 when SMA increases to 10% wt/wt. On the other hand, Bovine Serum Albumin (BSA) rejection increased with an increase in SMA concentration. The highest rejection was 92 ± 3%.

Fabrication of polysulfone membrane via thermally induced phase separation process

Polysulfone (PSF) membranes were successfully prepared by thermally induced phase separation (TIPS) using dipropylene glycol dibenzoate (DPGDB) as the diluent for the first time. Interestingly, the typically liquid-liquid (L-L) phase separation with coarsening process was not observed and the gelation occurred for the system during the cooling process. Moreover, the cross-section morphologies of all the membranes showed the network structure for the PSF concentration is in the range of 17wt%–21wt%. The membrane formation mechanism concerning the phase separation-gelation was proposed. The rejection of bovine serum albumin (BSA) of the membrane increased from 83.5% to 95.9% with the increase of PSF concentration. Additionally, the maximum break strength the membrane was as high as 7.3MPa. The present study may open a new method to fabricate PSF membrane and control membrane structure.

Does Plasticizer Penetrate Tightly Bound Polymer in Adsorbed Poly(vinyl acetate) on Silica?

When only tightly bound poly(vinyl acetate) (PVAc) was adsorbed on silica, the plasticizer, di(propylene glycol) dibenzoate (DPGDB), was not effective in lowering its glass transition. To determine why the plasticizer was not effective, we probed the behavior of the deuterated plasticizer di(propylene glycol) dibenzoate (DPGDB-d10)/PVAc/silica system using deuterium (2H) solid state NMR and temperature-modulated differential scanning calorimetry (TMDSC). PVAc with 37% (w/w) of plasticizer/polymer was adsorbed on silica in adsorbed amounts of 2.60 and 0.76 mg PVAc/m2 silica. The dynamics of the plasticizer in the adsorbed PVAc was found to be more motionally heterogeneous than that observed in bulk samples. The NMR results provided firm evidence that when there is only a small amount of adsorbed polymer (e.g., only tightly bound polymer at less than 0.8 mg/m2), the plasticizer was effectively excluded from the polymer chains at the silica–polymer–air interface. When excluded from the tightly bound polymer,...

Plasticizing effect of glyceryl tribenzoate, dipropylene glycol dibenzoate, and glyceryl triacetate on poly(lactic acid)

The aim of this article is to compare the plasticizing effect of different plasticizers on poly(lactic acid) (PLA) including glyceryl tribenzoate (GTB), dipropylene glycol dibenzoate (DPGDB), and glyceryl triacetate (GTA). The chemical structures of plasticizers are characterized by 1H‐nuclear magnetic resonance. PLA is blended with GTA, DPGDB, and GTB at various contents by using a twin screw extruder. Plasticizing effect of three plasticizers are evaluated by comparison of thermal property, storage stability, melt plasticizing coefficient, thermal degradation, and water vapor permeability. This study reveals that PLA/DPGDB exhibits better physical properties than the others do. DPGDB containing ether and ester groups may therefore render good compatibility with PLA. POLYM. ENG. SCI., 56:1399–1406, 2016. © 2016 Society of Plastics Engineers

Nonisothermal Crystallization Kinetics of Poly(Vinylidene Fluoride) in a Poly(Vinylidene Fluoride)/Poly(Methyl Methacrylate)/Dipropylene Glycol Dibenzoate System via Thermally Induced Phase Separation

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/polymethyl methacrylate (PMMA)/dipropylene glycol dibenzoate (DPGDB) blends, where DPGDB served as a diluent, via solid–liquid (S-L) phase separation during a thermally induced phase separation process was investigated through differential scanning calorimetry (DSC) measurements. It was found that the Ozawa model could only describe the nonisothermal crystallization behavior of PVDF/PMMA/DPGDB system to some extent. The influence of the cooling rate and PMMA/PVDF weight ratio in the PVDF/PMMA/DPGDB system on the crystallization mechanism was also examined based on the Avrami–Jeziorny method and Mo method. Primary crystallization and secondary crystallization were observed in the Avrami–Jeziorny analysis. The analysis by the Avrami–Jeziorny and Mo models indicated that the increase of PMMA/PVDF weight ratio decreased the crystallization rate during the primary crystallization stage. The results showed that the Mo method could well explain the kinetics of the primary PVDF crystallization. The Avrami–Jeziorny method, however, could not well describe the nonisothermal crystallization process of PVDF in the primary crystallization stage. The activation energy, determined by the Kissinger method, was not suitable to reflect the PVDF crystallization process in the PVDF/PMMA/DPGDB system.

Preparation, characterization, and properties of silicate/polyurethaneurea composites based on dipropylene glycol dibenzoate

The silicate/polyurethaneurea composites based on dipropylene glycol dibenzoate were prepared via a room‐temperature‐cured process. Characterization of the composites was accomplished using scanning electron microscope, X‐ray diffraction, Fourier transformation infrared spectrum, and Raman spectroscopy, and the mechanism, mechanical properties and stability were discussed in detail. The obtained results indicated that a durable silicate/polyurethaneurea composite with inorganic‐organic network structure had been successfully prepared. The composites were thermally stable below 210°C and the compressive and flexural strength of the material could reach 42.6 and 29.2 MPa after curing for 6 h, respectively. POLYM. COMPOS., 37–43, 2016. © 2014 Society of Plastics Engineers

Biodegradation kinetics of dibenzoate plasticizers and their metabolites

The kinetics of the biodegradation of two commercial plasticizers, diethylene glycol dibenzoate (D(EG)DB) and dipropylene glycol dibenzoate (D(PG)DB), as well as two alternative plasticizers, 1,3-propanediol dibenzoate and 2,2-methyl-propyl-1,3-propanediol dibenzoate, were investigated in an aerated bioreactor. The experiments were conducted with resting cells of Rhodococcus rhodochrous, which had been grown with hexadecane as the substrate. The first step in the biodegradation was always the hydrolysis of an ester bond, releasing the corresponding monobenzoate and benzoic acid. Biodegradation of plasticizers and their associated metabolites were modeled using a Monod-type kinetic model. Significant differences between the biodegradation of commercial and alternative plasticizers were observed both in the biodegradation pathway and the biodegradation rates of monobenzoate metabolites. At a selected concentration of 0.4g/L, the monobenzoates released from the biodegradation of 1,3-propanediol dibenzoate and 2,2-methyl-propyl-1,3-propanediol dibenzoate were degraded approximately 13 and 4 times more quickly, respectively, than the monobenzoate released from the biodegradation of D(PG)DB. The rapid biodegradation of monobenzoates released from microbial hydrolysis of alternative dibenzoate plasticizers was attributed to the lack of an ether bond in these compounds.

Plasticization of Adsorbed Poly(vinyl acetate) on Silica by Deuterium Solid-State NMR

Deuterium nuclear magnetic resonance spectroscopy and temperature modulated differential scanning calorimetry (TMDSC) were used to probe the segmental dynamics of methyl-labeled poly(vinyl acetate)-d3 (PVAc-d3) adsorbed on Cab-O-Sil silica in the presence and absence of a plasticizer, dipropyleneglycol dibenzoate. Unlike the effect of this plasticizer on the bulk polymer, where the reduction in the glass transition temperature (Tg), was proportional to the amount of plasticizer added, the effectiveness of the plasticizer on the adsorbed polymer depended on the amount of polymer adsorbed. For samples with very small amounts of adsorbed polymer (i.e., 0.81 mg/m2), there was little or no effect of plasticizer on the dynamics of the adsorbed polymer. For samples with more adsorbed polymer (i.e., 1.42 or 1.81 mg/m2), the efficiency of the plasticizer was easily measurable on a fraction of the adsorbed polymer that can be considered loosely bound. The 2H NMR line shape changes obtained from the adsorbed samples were fitted to a small jump model (based on the vertices of a “soccer-ball” shaped polyhedron) to obtain the distributions of jump rates contributing to the spectra. The same samples were also studied using TMDSC, and the results were consistent with the NMR results in terms of the effects of the plasticizer on the amount of polymer adsorbed. On the basis of the TMDSC experiments, the plasticizer tends to have a greater effect on the more loosely-bound polymer and lesser effect on a fraction that is more-tightly bound. Compared to the bulk polymer, where the glass transition range was on the order of 10 K, the range for the adsorbed polymer was more around 60 K.

Mechanisms of biodegradation of dibenzoate plasticizers

Biodegradation mechanisms were elucidated for three dibenzoate plasticizers: diethylene glycol dibenzoate (D(EG)DB), dipropylene glycol dibenzoate (D(PG)DB), both of which are commercially available, and 1,6-hexanediol dibenzoate, a potential green plasticizer. Degradation studies were done using Rhodococcus rhodochrous in the presence of pure alkanes as a co-substrate. As expected, the first degradation step for all of these systems was the hydrolysis of one ester bond with the release of benzoic acid and a monoester. Subsequent biodegradation of the monobenzoates of diethylene glycol (D(EG)MB) and dipropylene glycol (D(PG)MB) was very slow, leading to significant accumulation of these monoesters. In contrast, 1,6-hexanediol monobenzoate was quickly degraded and characterization of the metabolites indicated that the biodegradation proceeded by way of the oxidation of the alcohol group to generate 6-(benzoyloxy) hexanoic acid followed by β-oxidation steps. This pathway was blocked for D(EG)MB and D(PG)MB by the presence of an ether function. The use of a pure hydrocarbon as a co-substrate resulted in the formation of another class of metabolites; namely the esters of the alcohols formed by the oxidation of the alkanes and the benzoic acid released by hydrolysis of the original diesters. These metabolites were biodegraded without the accumulation of any intermediates.

Characterization of 1,5‐pentanediol dibenzoate as a potential “green” plasticizer for poly(vinyl chloride)

Abstract1,5‐Pentanediol dibenzoate (PDDB) was evaluated as a potential “green” plasticizer for poly(vinyl chloride) (PVC) at concentrations ranging between 20 and 80 parts by weight per hundred parts of resin. The results of glass transition temperature (Tg) and tensile tests of PDDB blends with PVC were compared with those for blends of the commercial plasticizers di(2‐ethylhexyl) phthalate (DEHP), di(ethylene glycol) dibenzoate (DEGDB), and di(propylene glycol) dibenzoate (DPGDB) in PVC. The depression in Tg and the tensile properties were comparable for a PDDB/PVC blend at a fixed composition to those of blends with DEHP, DEGDB, and DPGDB. The PDDB was subjected to biodegradation using co‐metabolism by the common soil bacterium Rhodococcus rhodochrous (ATCC 13808). After 16 days of growth, nearly all of the PDDB was degraded, and only small amounts of transient, unidentified metabolites were observed in the growth medium during the experiment. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers

Biodegradation of plasticizers by Rhodotorula rubra

The degradation of plasticizers by the yeast Rhodotorula rubra J-96-1 (American Type Culture Collection 9449) in the presence of glucose was studied. The plasticizers included the commonly used bis-2-ethylhexyl adipate (B(EH)A), dioctyl phthalate (DOP), and dioctyl terephthalate (DOTP), and the less commonly used dipropylene glycol dibenzoate (D(PG)DB) and diethylene glycol dibenzoate (D(EG)DB). The proposal had been made that the latter two plasticizers be used as alternatives to the first three, which have been associated with negative environmental impacts. The degradation of D(PG)DB or D(EG)DB led to a significant increase in solution toxicity, which was associated with the production of metabolites resulting from the incomplete breakdown of the plasticizers. The toxic metabolites in the D(PG)DB system were identified as isomers of dipropylene glycol monobenzoate. A pathway for the formation of this metabolite was proposed. The metabolite observed when D(EG)DB was being degraded was tentatively identified as diethylene glycol monobenzoate by analogy to the D(PG)DB system. In contrast, no metabolites were observable and toxicity did not increase in the media during the degradation of B(EH)A, DOP, or DOTP by R. rubra. Collectively, these results do not support the use of D(PG)DB and D(EG)DB as environmentally safe alternatives to B(EH)A, DOP, or DOTP.