Studies in Estolides,Part III : Plasticizer for Polyvinyl Chloride

Acetoxy butyl esters prepared from estolides (derived from castor oil fatty acids) were evaluated as plasticizers for poly (vinyl chloride) (PVC) resin. They showed limited compatibility. They were useful as secondary plasticizers for PVC along with dioctyl phthalate plasticizer. The properties of the plasticized stocks were generally comparable to the ones obtained by incorporating 12-acetoxy butyl oleate, the commercial secondary plasticizer. Among the estolides derivatives tried, the acetoxy butyl ester obtained from estolides of acid value 83 showed better performance. 1For parts I and II in the series ,see Refference 3 and 4     

Benzyl ester of dehydrated castor oil fatty acid as plasticizer for poly(vinyl chloride)

The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio‐based non‐toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio‐based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, ¹H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co‐plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick‐up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP‐plasticized sheets and thus we can conclude that BE can be used as a co‐plasticizer in PVC. © 2013 Society of Chemical Industry     

Esters of hydroxystearic acids as primary low-temperature plasticizers for a vinyl chloride—Vinyl acetate copolymer

Summary Thirty-one acyloxy or aryloxy esters prepared from hydroxystearic acids have been evaluated as plasticizers for a vinyl chloride-vinyl acetate copolymer (95∶5). Many of them were found to be primary plasticizers, having outstanding low-temperature performance when employed at the 35% level. Formulations with these compounds compared quite favorably in tensile properties with those containing the di-2-ethylhexyl esters of phthalic, sebacic, azelaic, and adipic acids. Volatility losses were similar to those of the four di-2-ethylhexyl esters. The loss of plasticizer through migration was equal to or less than that from compositions containing the esters of sebacic, azelaic, and adipic acids but was greater than that of the phthalate ester. A mechanistic scheme of plasticizer-polymer interaction has been presented, proposing that the rate of diffusion of plasticizer through the polymer mass is a controlling factor in both good low-temperature performance and the resulting high migration losses. Methyl esters, some aromatic esters, and esters containing three or more polar centers have improved permanence but show a more rapid change in torsional modulus as the temperature is lowered during the determination of the Clash-Berg stiffening temperature. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Rheometric study of the gelation and fusion processes of poly(vinyl chloride‐co‐vinyl acetate) plastisols with different commercial plasticizers

Evolution of the complex viscosity of pastes of PVC‐VA (vinyl chloride‐vinyl acetate copolymer) plasticized with different commercial plasticizers has been studied. Knowledge of the rheological behavior of the formulations allows for better understanding of the gelation and fusion processes. Twenty commercial plasticizers of different types and with different functional groups have been studied and are grouped into five families: phthalate esters with linear chains, phthalate esters with branched chains, adipates (normal and polymeric), citrates, and rest of the plasticizers (carboxylates, alkylsulfonates, and pentaerythritol ester derivatives). Interesting relationships among the observed rheologies and the nature and molecular weight of the plasticizer have been observed. The evolution of the complex viscosity with temperature—at the temperatures where the blowing agents normally used in PVC plastisol foaming processes generate the main amount of gas—has been newly discussed with regard to the chemical structure and molecular weight of all of the plasticizers used. It was found that several different dynamic processes must be synchronized in order to understand the relationships among the chemical structure, plasticization, plasticizer compatibility, rheological properties, and foaming process of such materials. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

Phthalate esters received a considerable attention owing to its various applications and the harmful health effects resulting from phthalate exposure; thus, finding an alternative to phthalate derivatives became a necessity. Phthalate esters are commonly used as plasticizer in polymer formulation; in particular for poly(vinyl chloride) (PVC) formulation. According to the researches in the last 18 years, epoxidized vegetable oils are one of the alternatives that are strongly encouraged to substitute phthalate esters since they were proven to be valid in various applications, eco‐friendly and sustainable resource. However, most of the production practices for epoxidized vegetable oil are via conventional epoxidation that concentrates on a catalyst that is homogeneous and non‐reusable. This type of catalyst, however, causes several problems later in the process. Therefore, the selective epoxidation of vegetable oils process requires new catalytic systems that are more aligned with the green chemistry principles. This article reviews the harmful health effects associated with the exposure to phthalate esters products, explains the usage of oleochemicals resources as a substitute to phthalate esters and describes different approaches for the epoxidation of vegetable oils. Finally, it draws attention to the usage of epoxy and bio‐based compounds as plasticizers in PVC manufacturing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46270.     

Di(2‐propylheptyl) phthalate: A new plasticizer choice for PVC compounders

Science and practice have proven that phthalic acid esters are among the most functional plasticizers for polyvinyl chloride (PVC). The performance properties of phthalic acid esters can be modified for an advantageous cost/benefit position by varying the alcohol moiety of the ester molecule in the practical range of C4–C13 and by specifying the linearity of the alcohol main chain. The C8, C9, and C10 alcohols produce esters of most value as PVC plasticizers. Most plasticizer alcohols are produced by the oxonation process from primary olefins, of which ethylene, propylene, and butene are the major refinery products available on a world scale at costs acceptable to the application. This article introduces a C10 phthalate produced from butene rather than by the current route from propylene. J. VINYL. ADDIT. TECHNOL. 11:155–159, 2005. © 2005 Society of Plastics Engineers     

Performance of Di-n-Hexyl phthalate in flexible vinyl formulations

Low-molecular-weight esters have been available to the PVC compounder for many years. They have found a significant niche in the performance vs. permanence compromise as a compound ingredient that provides manufacturing efficiency or some special property with adequate permanence for many vinyl applications. In many respects, low-molecular-weight esters are the processing aids of the plasticizer family. This group of plasticizers may be said to include C₄ to C₇ dialkyl phthalates, the benzyl phthalates and the benzoic acid esters. This paper will introduce and compare di-n-hexyl phthalate (DNHP) to other phthalates against which it will directly compete.     

Optimizing performance of benzoate and phthalate blends for vinyl applications

To achieve required performance, blends of plasticizers are commonly used in flexible vinyl applications. Typically, when fast fusion is required, high solvating phthalates have been utilized in plasticizer blends. Benzoate esters are high solvators and can also be used in these blends. However, even though benzoate plasticizers offer additional performance benefits that can complement general‐purpose phthalate performance, most of the literature does not include the use of benzoate plasticizers in blends with phthalates. The purpose of this article is to demonstrate the performance benefits of blending benzoate and phthalate plasticizers. The approach selected to accomplish this task was to develop performance data by utilizing a mixture design approach with DOE (design of experiments) software. A resilient flooring plastisol formulation was selected as the model. The following properties were obtained: degassing, low and high shear viscosity, viscosity stability of the plastisol, gel and fusion characteristics, tensile strength vs. temperature, vinyl heat stability, stain resistance, volatility, and UV stability. The data indicate how to utilize the advantage of benzoates as “process aids” to speed production rates and improve product quality. J. VINYL. ADDIT. TECHNOL. 11:150–154, 2005. © 2005 Society of Plastics Engineers     

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.     

Adhesion properties of eco-friendly PVAc emulsion adhesive using nonphthalate plasticizer

An eco-friendly poly (vinyl acetate) emulsion adhesive was synthesized without phthalate. Four types of eco-friendly plasticizers for use in these adhesives were selected to confirm their primary properties by injecting the eco-friendly plasticizer without any prior change to its processing or cost. The four types of eco-friendly plasticizers used were dibutyl phthalate DBP-based product, dialkyl ester, acetyl tributyl citrate, and pentandiol-di-isobutyrate. Their properties were determined by comparison with the existing (DBP)-based product. As a result, an emulsion adhesive was produced without addition of phthalate or need for additional additives, resulting in a significant decrease in cost. However, the low temperature characteristics of the eco-friendly plasticizers were slightly inferior to those of DBP. These adhesives containing eco-friendly plasticizer were studied and their characteristics for adhesion strength, water resistance, ability for low temperature film formation, excellent storage stability, and lack of volatile organic compounds productions (including phthalate) were confirmed.     

Properties of a PVAc emulsion adhesive using a nonphthalate plasticizer obtained by condensation of 2-methylpropanal

The requirement to search for new plasticizers and coalescents for making water-based dispersion adhesives from poly(vinyl acetate) is of particular importance, especially now, after banning all kinds of toxic phthalates and restricting the use of glycol derivatives classified as volatile organic compounds. The poly(vinyl acetate) adhesive was synthesized using the eco-safe plasticizer – 3-hydroxy-2,2,4,-tri-methyl pentyl isobutyrate. The plasticizer was obtained by aldol condensation of 2-methylpropanal, byproduct of oxy synthesis from propylene. Its desirable properties were confirmed by comparing the composition of the adhesive comprising poly(vinyl acetate) as the principal component and the plasticizer as the additive. 3-hydroxy-2,2,4,-tri-methyl pentyl isobutyrate and commonly known plasticizers, such as: diisobutyl phthalate and diethylene glycol n-butyl ether acetate were used as the plasticizers in the experiment. The adhesives were compared in respect of the following parameters: dry weight, pH, viscosity, minimum film forming temperature, penetrability, setting time and stability in time. The test results indicate that 3-hydroxy-2,2,4,-tri-methyl pentyl isobutyrate can be used successfully as a plasticizer for making wood adhesives in the range from 2.0 to 2.5% of the adhesive formulation and for making bookbinding adhesives in the range from 4.7 to 5.6% of the adhesive formulation. This enables an about twofold reduction of the amount of the plasticizer, in comparison with the adhesive based on diisobutyl phthalate. 3-hydroxy-2,2,4,-tri-methyl pentyl isobutyrate can be used in dispersion adhesive formulations, thus replacing the undesirable, toxic phthalate esters and polyglycol derivatives classified as volatile organic compounds.     

增塑剂的选择与邻苯二甲酸酯的替代品

在拟定一款软质聚氯乙烯（PVC）配方时,所开发的产品能否满足客户的性能指标和成本要求,在很大程度上取决于适当的增塑剂体系的选择。在所有原料组分中,增塑剂会对产品的最终性能造成最大的影响。本研究将论述在选择增塑剂时所涉及的程序,先从通用型增塑剂开始,然后考虑邻苯二甲酸酯的替代品及其他增塑剂。     

偕二硝基类含能增塑剂的合成及应用

从偕二硝基含能增塑剂的结构和合成特点出发,综述了偕二硝基缩醛类、酯类及醚类等含能增塑剂的合成、性能及应用研究现状.重点介绍缩醛类含能增塑剂BDNPF和BDNPA的制备技术,论述了其物理化学性能、能量特性和热性能,以及在炸药、推进剂配方中的应用,指出此类化合物的合成及应用,将是含能增塑剂研究的重点.附参考文献21篇.     

Epoxidation of alkyl esters of 12,13-epoxyoleic acids and evaluation of the diepoxides as plasticizers for poly(vinyl chloride)

Methyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl esters of 9,10:12,13-diepoxystearic acid were prepared by peracetic acid oxidation of the corresponding esters of 12,13-epoxyoleic acid. Using a 60 mole per cent excess of peracid at 30 C in chloroform as solvent, epoxidation was complete in 5 hr. A small aqueous phase was observed in the reaction mixture which decreases the amount of peracid available for reaction. This is due to the water and H₂O₂ present in the commercial peracetic acid used. Thin-layer and gas chromatographic analysis showed that the diepoxides formed as isomers. These did not react quantitatively with HBr by the Durbetaki method. Isomers of methyl and propyl diepoxy esters were separated by crystallization. The methyl (pure and mixed isomers), isobutyl, 2-ethylhexyl and octyl (all mixed isomers) diepoxy esters were evaluated as plasticizers of poly (vinyl chloride). Delta values showed that these esters have good compatibility. Results are compared with commercial epoxidized soybean oil control. These diepoxy esters show better low temperature properties and have higher migration and volatility values than the control. They are more efficient plasticizers than the control. The liquid isomer of the methyl ester, as well as the 2-ethylhexyl ester, should be useful as primary plasticizers and in combination with other plasticizers as plasticizer stabilizers. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Preparation and evaluation of acetylated mixture of citrate ester plasticizers for poly(vinyl chloride)

Tributyl citrate (TBC) and acetyl tributyl citrate (ATBC), as phthalate alternative plasticizers, show limited application due to low migration resistance, high volatilization rate and intense respiratory irritation. Meanwhile, the developed pure citrates, such as butyryl trihexyl citrate (BTHC) due to its high cost, and triisooctyl citrate (TOC) and acetyl triisooctyl citrate (ATOC) due to their low absorption property, are not attractive plasticizers to manufacture phthalate-free poly(vinyl chloride)s (PVCs). In this study, we developed an effective method to synthesize acetylated mixture of citrate esters (ATMC) composed of acetyl (dibutyl-monoisooctyl) citrate, acetyl (monobutyl-diisooctyl) citrate, and a small amount of ATBC and ATOC, as an alternative for phthalate plasticizers. ATMC combines the advantages of ATBC in being easily absorbed and ATOC in having good migration resistance. Characterization results showed that the dynamic viscosity, absorption property and plasticizing efficiency of ATMC11 (1:1 molar ratio of n-butyl alcohol to 2-ethylhexanol) were similar to those of di(2-ethylhexyl) phthalate (DEHP). The thermal volatilization and migration of ATMC11 were less than those of ATBC, and were comparable to those of DEHP, which could be attributed to the improved compatibility with PVC. The performance of ATMC11 was improved compared with that of the mixture of ATBC and ATOC. As an environmental bio-based plasticizer, ATMC11 was demonstrated as a biologically safe plasticizer by biological safety evaluation tests. Therefore, ATMC11 with excellent comprehensive performances and low cost can be candidate as an ideal phthalate alternative for soft PVC formulations.     

国内外邻苯二甲酸酯类增塑剂的现状和展望

对邻苯二甲酸酯类增塑剂的国内外现状作了评述,并对我国提高DOP和高分子量邻苯二甲酸酯类增塑剂的比例、降低DBP的比例、开发高性能的复合增塑剂提出了积极的建议。     

Some esters of mono-, di-, and tricarboxystearic acid as plasticizers: Preparation and evaluation

Methyl mono-, di-, and tricarboxystearates were prepared by either a two-step hydroformylation-oxidation reaction or direct hydrocarboxylation of unsaturated vegetable oil methyl esters. Procedures were developed for preparing alkyl dicarbomethoxy-, dicarboethoxy-, and dicarbobutoxystearates. These triesters, along with some di- and tetraesters from mono- and tricarboxystearic acids, were evaluated as primary plasticizers for polyvinyl chloride (PVC). Except for butyl carbobutoxystearate, the esters were compatible at the 32% level and had properties equal or superior to those of dioctyl phthalate. Methyl and butyl diesters of carboxystearic acid had undesirable migration and volatility properties. The migration and volatility properties of some tri- and tetraalkyl esters were equal to or better than the controls. Of the various esters tested, methyl dicarbomethoxystearate containing 13–49% methyl tricarbomethoxystearate was an efficient plasticizer for PVC at the 32% level.     

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.     

Some fatty esters as plasticizers and fungicides for natural rubber

The prepared n-fatty alcohols from petroleum sources are esterified with a dibasic acid series (malonic, succinic, glutaric and adipic) or phthalic anhydride, giving the corresponding C₁₂ fatty esters. The prepared C₁₂ fatty esters were formulated with natural rubber. The drying time, some mechanical properties and fungitoxicity of the prepared film samples were examined. The conventional dibutyl phthalate plasticizer was used for the purpose of comparison. The data obtained indicate that the prepared fatty esters can be used as plasticizers with antifungal activity for natural rubber. ©1997 SCI     

Synthesis and evaluation of some fatty esters as plasticizers and fungicides for poly(vinyl acetate) emulsion

n-Fatty alcohols (average molecular weight 187), prepared from n-paraffins, were treated with a series of dibasic acids such as malonic, succinic, glutaric, adipic and phthalic anhydride to give the corresponding fatty esters. The prepared fatty esters were formulated with poly(vinyl acetate) emulsion and used as films or textile coatings. Tests such as rate of drying, mechanical properties and resistance to micro-organisms were carried out. Samples of poly(vinyl acetate) plasticized with dibutyl phthalate were also prepared and evaluated for the purpose of comparison. The antifungal activity of these compounds was studied. The results obtained indicate that the prepared fatty esters can be used not only as plasticizers but also as fungicides and in some respects they are better than the conventional dibutyl phthalate plasticizer.