Synthesis and study of properties of new oligoesters based on soybean oil as potential poly(vinyl chloride) plasticizers

New compounds as potential poly(vinyl chloride) plasticizers based on soybean oil and oligoesters of adipic acid and different glycols by one-pot transesterification are synthesized. In the first step of the plasticizer synthesis oligoesters of adipic acid and diethylene glycol, triethylene glycol, or dipropylene glycol are synthesized, and then in situ in the second step, a defined amount of soybean oil is introduced. By degradation of soybean oil with oligoesters, and transesterification reaction, different compounds are obtained. Their physicochemical properties are determined by NMR, SEC, DSC, TGA, and volatility analyses. The properties of synthesized plasticizers are compared with commercial products: monomeric (DEHP) and aliphatic oligoster of adipic acid and 1,3-butanediol (H-1).     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

Bis(2‐ethylhexyl) succinate in mixtures with epoxidized soybean oil as bio‐based plasticizers for poly(vinylchloride)

Mixtures of bis(2‐ethylhexyl) succinate and epoxidized soybean oil (ESO) have been evaluated as bio‐based plasticizers for poly(vinylchloride). The rate of absorption of the bioplasticizers and their mixtures in the polymer was fast and, unlike that of petroleum‐derived plasticizers, did not vary significantly with molecular weight. These bio‐derived plasticizers and their mixtures were compatible with the polymer even at high loadings. The succinate was the most volatile and efficient plasticizer, but on heat aging of the polymer compositions, it also had the greatest deleterious effects. Diffusion coefficients and apparent activation energies of formulations containing bioplasticizer mixtures were controlled by the more volatile succinate. Mixtures comprising up to 50 wt% of the succinate yielded acceptably high‐tensile properties after thermal aging as well as better plasticization efficiency than the epoxy bioplasticizer. Although the succinate resulted in inferior volume resistivity of the polymer compositions, improvements were obtained with increasing proportions of the epoxidized derivative in plasticizer mixtures. Melt state viscosity‐shear rate curves of compositions containing dioctyl succinate (DOS) were similar to those made with two of the petroleum‐derived plasticizers, but a DOS/ESO mixture yielded extended non‐Newtonian behavior at low‐shear rates. POLYM. ENG. SCI., 55:634–640, 2015. © 2014 Society of Plastics Engineers     

Thermomechanical film properties and aging of blends of poly(lactic acid) and malonate oligomers

Malonate oligomers were synthesized as plasticizers for poly(lactic acid) (PLA). Esterification reactions were performed between diethyl bishydroxymethyl malonate (DBM) and either adipoyl dichloride or succinyl dichloride. Two molar masses were obtained within each series. Blending was carried out with PLA and the four oligomers as well as the monomeric unit from the syntheses (DBM). Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the viscoelastic mechanical and thermal film properties of the blends. All the investigated plasticizers reduced the glass‐transition temperature of PLA, and the plasticization effect was better for the plasticizers of low molar mass. However, the amorphous domains of PLA became saturated with plasticizer at a certain concentration, and phase separation occurred. A higher molar mass of the plasticizer caused this saturation to occur at lower plasticizer concentrations. Subsequently, the aging of the blends at the ambient temperature for 4 months induced phase separation in the blends containing DBM, whereas those with an oligomeric plasticizer were stable and remained compatible with PLA within the aging period. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2140–2149, 2004     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

The effects of plasticizers on the properties of poly(vinyl chloride) foams

The effects of plasticizers on poly(vinyl chloride) (PVC) plastisol mixtures were investigated. The investigations were carried out by determining the density of the PVC foam obtained by gelling the plastisol, as well as its elasticity and degree of expansion. Two series of experiments using different types of PVC were performed, using eight plasticizers, individually or as mixtures. Two-component plasticizer mixtures showed better properties than single-component plasticizers, and mixtures of di-iso-heptyl phthalate (DiHP) and butyl benzyl phthalate (BBP) proved to be the most appropriate. The effect of plasticizer amount also was investigated, and of the three parameters studied, the foam density, which steadily increased with plasticizer amount, was the critical one. It was also shown that in order to obtain consistent results, the foam expansion had to be precisely timed and the temperature carefully chosen.     

Effect of poly(vinyl chloride) resin type in the preparation process of slush powder

During the preparation of the poly(vinyl chloride) (PVC) slush powder, we found that PVC resins obtained by different polymerization methods affected many properties of slush powder and its products. Two types of commercial PVC resins were used for slush powder preparation: mass poly(vinyl chloride) (M‐PVC) and suspension poly(vinyl chloride) (S‐PVC). We used the Haake rheomix test to characterize the absorption of plasticizers into PVC resins, and the results showed that M‐PVC absorbed the plasticizers more quickly than S‐PVC. The fusion behavior of the two slush powders was studied by the thermal plate test and Haake rheomix test, and the results showed that the slush powder of M‐PVC was easier to fuse than that of S‐PVC. The different properties of the two resins and slush powder could be explained by the morphology, average size, and size distribution. Due to the “skin” of the particles' surfaces, the wider size distribution, and the large size of particles, S‐PVC absorbed the plasticizers more slowly and was more difficult to fuse. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3331–3335, 2002     

Emissivity values for poly(vinyl chloride) with varying plasticizer compositions

The emissivity of plasticized poly(vinly chloride) (PVC) containing varying compositions and amounts of plasticizer was investigated. The four plasticizers examined were dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) (Phthalic acid type), and dioctyl adipate (DOA) (adipic acid type). The emmissivity of plasticized PVC film increased almost equally with the difference in the compositions between DOP and DOA. It was also clear that the emissivity of the plasticized PVC film decreased gradually with the molecular sequence length of DBP, DOP, and DIDP.     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

Acetoxyglycerol acetal derivatives of mono- and polyformyloctadecanoate esters: Plasticizers for poly(vinyl chloride)

Methyl and butyl(acetoxyglycerol acetal) esters were prepared from 9(10)-formyloctadecanoate or its dimethyl acetal. Mixtures of acetoxy mono- and diglycerol acetals, plus acetoxy mono-, di-, and triglycerol acetals, were prepared respectively from hydroformylated safflower and linseed methyl esters. The glycerol acetals were characterized with respect to physical, thermal, chromatographic, and spectroscopic properties. Acetoxy-mixed glycerol acetals from safflower and linseed methyl esters were good primary plasticizers for poly(vinyl chloride) (PVC), whereas acetoxyglycerol acetals of hydroformylated methyl and butyl oleate were good secondary PVC plasticizers. As primary plasticizers, the poly(acetoxyglycerol acetal) esters showed less migration, better heat stability, and higher tensile strength than the generally used PVC plasticizer di(2-ethylhexyl) phthalate.     

Poly(vinyl chloride) films plasticized with novel poly‐nadic‐anhydride polyester plasticizers

In this work, several novel poly‐nadic‐anhydride polyester plasticizers were developed to be used in poly(vinyl chloride) (PVC) film fabrication for the first time. Mechanical properties of the films, the compatibility of plasticizers in PVC resin, as well as testing of migration of the plasticizers, were performed in order to evaluate the efficiency of plasticization. Scanning electron microscopy, Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry were used to characterize the unplasticized and plasticized polymer. The results demonstrated that the as‐prepared poly‐nadic‐anhydride plasticized PVC film significantly improved the plasticization efficiency of PVC film based on the increase in the break in elongation of the films. According to scanning electron microscopy analysis, the poly‐nadic‐anhydride polyester plasticizers presented good compatibility with PVC resin. In volatility and extraction tests, PVC films plasticized with the poly‐nadic‐anhydrides showed enhanced migration resistance. The plasticizing effects induced by the poly‐nadic‐anhydride polyester plasticizers were also confirmed by a glass transition temperature shift toward lower temperatures in the plasticized films. J. VINYL ADDIT. TECHNOL., 23:321–328, 2017. © 2015 Society of Plastics Engineers     

Effect of biobased plasticizers on thermal,mechanical, and permanence properties of poly(vinyl chloride)

Phthalates can be replaced by other harmless and environmentally friendly plasticizers, such as isosorbide diesters (ISB), and epoxidized sunflower oil (ESO), which has been proved an efficient stabilizer for poly (vinyl chloride) (PVC) in helping to prevent degradation during processing. Formulations based on PVC with different amounts of ISB, ESO, and di‐(2‐ethylhexyl) phthalate (DEHP) from 0 to 60 parts by weight per hundred parts of resin were realized. To make PVC flexible with partial amounts of the debated phthalates as plasticizers, we use a combination of DEHP, ISB, and ESO. Effects of these two biobased plasticizers, ISB and ESO, and their mixture with DEHP on thermal stability by measuring discoloration degrees and thermal gravimetric analysis, on mechanical properties such tensile strength, elongation at break, and hardness, were characterized. Plasticizer permanence properties of PVC compounds were studied. Studies showed that processibility and flexibility were improved by the addition of a plasticizer system (ISB, ESO, and DEHP). An increase in the content of ISB and/or ESO increased thermal and mechanical properties, whereas compositions with ternary compositions of ISB/ESO/DEHP (15/15/30) exhibited the best performance properties. J. VINYL ADDIT. TECHNOL., 20:260–267, 2014. © 2014 Society of Plastics Engineers     

Characterization of alternative plasticizers in poly(vinyl chloride) sheets for blood containers

This study aimed to optimize the ratio of dioctyl 4‐cyclohexene‐1,2‐dicarboxylate (DOTH) and di‐isononyl‐cyclohexane‐1,2‐dicarboxylate (DINCH^®) for use as plasticizers in poly(vinyl chloride) (PVC) sheets. We also evaluated the biological safety of DOTH for its potential to be part of a safe PVC‐based blood container. The suppression of hemolysis in mannitol‐adenine‐phosphate / red cell concentrates (MAP/RCC) with DOTH/(DINCH^®‐PVC) sheets and the elution of plasticizers from the sheets increased with higher DOTH compositions. The properties of the PVC sheet containing DOTH and DINCH^® in the ratio of 25:33 parts against PVC 100 parts as a weight were almost identical to the PVC sheet made of di(2‐ethylhexyl) phthalate. From a subchronic toxicity test, DOTH did not show any adverse effects on all organs, including the testes, epididymis, liver, and kidneys. The no‐observed‐adverse‐effect level was 300 mg/kg body weight/day in a rat. These results suggest that DOTH/DINCH^® (25:33) is a promising candidate for the replacement of di(2‐ethylhexyl) phthalate in blood containers. J. VINYL ADDIT. TECHNOL., 22:520–528, 2016. © 2015 Society of Plastics Engineers     

Effect of plasticizers on mechanical,electrical, permanence,and thermal properties of poly(vinyl chloride)

Effects of three different plasticizers and their blends with dioctyl phthalate (DOP) on thermal stability, flammability, mechanical, electrical, and permanence properties of poly(vinyl chloride) (PVC) compound were studied. Various plasticizers used were DOP, butyl benzyl phthalate (BBP), isodecyl diphenyl phosphate (IDDP), and polybutylene adipate (PBA) at concentrations of up to 40 phr level. Studies showed that processability and softness were improved by addition of BBP. An increase in the content of IDDP increased the electrical and flammability properties, whereas compositions with PBA exhibited the best permanence properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3278–3284, 2003     

Succinate-based plasticizers: Effect of plasticizer structure on the mechanical and thermal performance of poly(vinyl chloride) plastic formulations

A new family of succinate-based plasticizers, consisting of molecules with a linear alkyl chain capped with n-alkyl succinates on both ends, was evaluated as potential bio-based plasticizers for stiff polymers. The influence of the central and side alkyl chain lengths on the mechanical and thermal properties as well as the migration behavior of poly(vinyl chloride) (PVC)/plasticizer blends was evaluated. The central chain length had the greatest influence on plasticizer performance, with shorter chains leading to blends with higher stress at break and surface hardness, whereas long chains produced softer blends. An optimum chain central length of five carbon atoms was observed, with longer chains leading to reduced compatibility and exudation of the plasticizer at higher plasticizer concentrations. The entire family of plasticizers performed comparably or better than the commercial plasticizer di(2-ethylhexyl) phthalate (DEHP) when incorporated into the blend at concentrations of 20–60 parts per hundred resin (phr). Overall, the succinate-based plasticizers/PVC blends all exhibited equal or improved tensile properties (by up to 77%), surface hardness (reduced by up to 43%), glass transition temperature (reduced by up to 11°C), and migration into organic media (reduced by up to 38%) when compared with blends with DEHP at 40 phr.     

Blends of plasticized poly(vinyl chloride) and waste flexible poly(vinyl chloride) with waste nitrile rubber powder

Blends of poly(vinyl chloride) (PVC) with varying contents of plasticizer and finely ground powder of waste nitrile rubber rollers were prepared over a wide range of rubber contents through high‐temperature blending. The effects of rubber and plasticizer (dioctyl phthalate) content on the tensile strength, percentage elongation, impact properties, hardness, abrasion resistance, flexural crack resistance, limiting oxygen index (LOI), electrical properties, and breakdown voltage were studied. The percentage elongation, flexural crack resistance, and impact strength of blends increased considerably over those of PVC. The waste rubber had a plasticizing effect. Blends of waste plasticized PVC and waste nitrile rubber showed promising properties. The electrical properties and LOI decreased with increasing rubber and plasticizer content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1552–1558, 2004     

Dialkyl furan‐2,5‐dicarboxylates,epoxidized fatty acid esters and their mixtures as bio‐based plasticizers for poly(VInylchloride)

Dialkyl furan‐2,5‐dicarboxylates and epoxidized fatty acid esters (EFAE) of varying molecular weights and volatilities, as well as their mixtures, were investigated as alternative plasticizers for poly(vinylchloride) (PVC). The EFAE utilized were epoxidized soybean oil (ESO) and epoxidized fatty acid methyl ester (e‐FAME). All plasticizers were compatible with PVC, with plasticization efficiencies usually increasing with decreasing molecular weights of the plasticizers (except in the case of ESO, which was remarkably effective at plasticizing PVC, in spite of its relatively high molecular weight). In comparison with phthalate and trimellitate plasticizers, the alternatives generally yielded improved balance of flexibility and retention of mechanical properties after heat aging, with particularly outstanding results obtained using 30?50 wt % e‐FAME in mixtures with diisotridecyl 2,5‐furandicarboxylate. Although heat aging characteristics of the plasticized polymer were often related to plasticizer volatilities, e‐FAME performed better than bis(2‐ethylhexyl) 2,5‐furandicarboxylate, and bis(2‐ethylhexyl) phthalate of comparatively higher molecular weights. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42382.     

Synthesis of amphiphilic PVC‐b‐poly(hydroxypropyl acrylate) (PHPA)‐b‐PVC block copolymers with low PHPA contents and different molecular weights by (Single Electron Transfer)—(Degenerative Chain Transfer) living radical polymerization

The aim of this work was to synthesize new amphiphilic block copolymers, based on poly(vinyl chloride) (PVC) and containing poly(hydroxypropyl acrylate) (PHPA), by using the controlled/“living” radical polymerization (CLRP) method. Various block copolymers containing a small proportion of PHPA were prepared, each having a different molecular weight. The technique used was the same as that employed in the production of commercial PVC made by free‐radical polymerization. The materials were characterized in terms of their molecular structure, morphology, particle size, and surface and thermal properties. The CLRP preparation of block copolymers that are based on PVC and have low contents of other monomer units opens the possibility of synthesizing new materials whose properties are close to those of PVC but have new properties that may considerably enhance their performance. The incorporation of small amounts of PHPA into PVC block copolymers provided greater surface hydrophilicity and improved thermal stability while maintaining relevant processing properties, such as particle size and average molecular weight, so that they close to those of conventional PVC homopolymers. J. VINYL ADDIT. TECHNOL., 19:157‐167, 2013. © 2013 Society of Plastics Engineers     

Evaluation of the effects of biobased plasticizers on the thermal and mechanical properties of poly(vinyl chloride)

Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (T_g) were similar, with T_g close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006     

Recycling of Waste PET: Usage as Secondary Plasticizer for PVC

Postconsumer water bottle poly(ethylene terephthalate) (PET) flakes were depolymerized with ethylene glycol (EG) by the glycolysis reaction in the presence of zinc acetate as the catalyst. In the depolymerization reactions, different weight ratios of PET/EG were used. In order to obtain polyesters used as PVC plasticizers, these glycolysis products containing hydroxyl end groups were reacted with an adipic acid (AA)–containing diacid group at equivalent amounts. In order to obtain PVC plastisols, PVC was dispersed into a plasticizers' mixture composed of di-isooctyl phthalate (DOP) and polyester products by using a high-speed mixer (PVC/plasticizers, 65/35 w/w). For the preparation of plasticizer mixture polyester products were used at a weight ratio of 20%, 40%, 60% of DOP. Plasticized PVC sheets were prepared from plastisols and their glass transition temperatures (T_g), migration, and mechanical properties were determined. The results show that the polyester products obtained from glycolysis products of waste PET can be used as secondary plasticizers, with DOP for PVC.