Vernolic acid esters as plasticizers for polyvinyl chloride

The methyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, and 2-ethylhexyl esters of vernolic (epoxyoleic) acid, a naturally-occurring epoxy acid, were prepared and evaluated as plasticizers of polyvinyl chloride. All the esters showed good compatibility. The data indicated that they are excellent low temperature plasticizers having T_f temperatures below −50C. They also have the added advantage of greatly increasing the heat stability of the polyvinyl chloride and improving the light stability. The results are compared with DOP and other epoxy-containing plasticizers now being used commercially. These esters should not only be useful as primary plasticizers but also in combination with other plasticizers as plasticizer-stabilizers. Presented at the AOCS Meeting. Cineinnati, October 1965 E. Utiliz. Res. Dev. Div., ARS, USDA.     

Ethylene and dimethyl acetals from hydroformylated linseed,soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Dimethyl and ethylene acetals of polyformylated unsaturated fatty esters were prepared, characterized, and evaluated as polyvinyl chloride plasticizers. Dimethyl acetals were prepared with trimethyl orthoformate as a water scavenger in the acid catalyzed acetalation reaction. With ethylene acetals, water was removed azeotropically. Although the acetals prepared were mixtures, molecular distillation gave diacetal esters of 80–90% purity and triacetal esters of 80–95% purity. The samples were characterized by gas liquid chromatography and by IR and NMR spectra. Compared to di-2-ethylhexyl phthalate as a plasticizer for polyvinyl chloride, the triacetal esters (both dimethyl and ethylene acetals) gave less migration and at least equivalent volatility characteristics; the triacetals also gave equivalent compatibility and strength, but somewhat less desirable low temperature and heat stability properties. The diacetal esters also had good compatibility, equivalent strength, somewhat better low temperature, but less desirable migration and volatility properties. Presented at the AOCS Meeting, Chicago, Illinois, September 1973. ARS, USDA.     

Synthesis of difuran diesters from furfural,and their evaluation as plasticizers for polyvinyl chloride

The compounds 1,1-bis[5-(2-ethylhexyl, 2-octyl, hexyl, and butyl)carboxylate-2-furyl)ethane, and 5,5′-dihexylcarboxylate-2,2′ bifuran were synthesized from furfural and characterized for their plasticizing abilities toward polyvinyl chloride (PVC) by dynamic mechanical thermal analyses (DMTA) with di-(2-ethylhexyl)phthalate (DOP)as the standard of reference. DMTA gave values for the depression of the glass-transition temperature (T_g) per mass fraction of plasticizer, and it also yielded a set of parameters, relative to those of DOP, which describe the compatability of the furan diesters with PVC. These values are compared to those of DOP and furan diesters incorporating only one furan ring in the molecular structure, which have previously been tested by this method. The difuran plasticizers are less efficient in lowering T_g than the monofuran plasticizers or DOP, with 1,1-bis[5-(2-octyl)carboxylate-2-furyl]ethane the least efficient and 1,1-bis(5-hexylcarboxylate-2-furyl)ethane the most efficient. On average the compatability toward PVC is better than that of DOP, and similar to that of analogous monofuran structures. © 1995 John Wiley & Sons, Inc.     

Epoxidized esters of fatty acids as internal and external plasticizers for polyvinyl acetate

Summary Fatty acid esters modified with epoxy or acetoxy groups were found to be compatible with polyvinyl acetate. These esters are good plasticizers for polyvinyl acetate compositions and may be used for plasticizing polyvinyl acetate in latex form. The use of a good swelling agent, such as toluene, was found desirable for permitting plasticization of these emulsions. The epoxidized oils may also assist in reducing container corrosion and in stabilizing the emulsions by reacting with the acetic acid formed by the hydrolysis of residual vinyl acetate. Emulsions of copolymers of vinyl acetate and vinyl epoxystearate were prepared, yielding clear, hard films which were internally plasticized. The epoxy group in these interpolymers is a potential source for cross-linking vinyl acetate polymer films. The epoxy group of the co-polymers (internal-phase stabilization) and the epoxidized oils (external-phase stabilization) were found to be virtually equivalent for removal of acetic acid from polyvinyl acetate emulsions. Presented at the Fall Meeting, American Oil Chemists' Society, Philadelphia, Pa., October 11, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

New benzoate plasticizers for polyvinyl chloride: Introduction and performance example

Two new unique benzoate ester plasticizers that will offer the vinyl formulator improved performance have been developed. One is an excellent solvator that will yield lower plastisol viscosities than existing plasticizers. The other will provide an excellent alternate with low volatility. The new products provide expanded performance utility over existing benzoates and phthalates on a global basis. Basic plastisol performance data and an example of use in a specific application, vinyl leathercloth, are presented. The data demonstrates that these blends are compatible, effective high solvating plasticizers and are performance alternates for plastisols and other polyvinyl chloride applications.     

Low‐molecular‐weight glycerol esters as plasticizers for poly(vinyl chloride)

Phthalates are the most important plasticizers used in the polymer industry. However, their fossil origin and the results of recent tests showing their potential negative effect on human health have encouraged the polymer industry to turn toward non‐phthalate plasticizers. At the same time, the biodiesel industry produces a surplus of glycerol, thus leading the scientific community to seek new applications for this substance. This paper presents the performance of eight esters derived from glycerol as plasticizers for poly(vinyl chloride), including tests to evaluate their compatibility. Results show that glycerol esters obtained from propanoic, butanoic, isobutanoic, isopentanoic, and benzoic acids, while volatile, can be used as poly(vinyl chloride) plasticizers in certain applications. J. VINYL ADDIT. TECHNOL., 20:65–71, 2014. © 2014 Society of Plastics Engineers     

Oligomeric isosorbide esters as alternative renewable resource plasticizers for PVC

Oligo(isosorbide adipate) (OSA), oligo(isosorbide suberate) (OSS), and isosorbide dihexanoate (SDH) were synthesized and evaluated as renewable resource alternatives to traditional phthalate plasticizers. The structure of the synthesized oligomers was confirmed by nuclear magnetic resonance spectroscopy (¹H‐ and ¹³C‐NMR), and molecular weight was determined by size exclusion chromatograph. The plasticizers were blended with poly(vinyl chloride) (PVC), and the miscibility and properties of the blends were evaluated by differential scanning calorimetry, fourier transform infrared spectroscopy, tensile testing, and thermogravimetry. Especially the blends plasticized with SDH had almost identical properties with PVC/diisooctyl phthalate (DIOP) blends. The blends containing OSA and OSS plasticizers, based on dicarboxylic acids, had somewhat lower strain at break but higher stress at break and better thermal stability compared to the PVC/DIOP or PVC/SDH blends. All the synthesized isosorbide plasticizers showed potential as alternative PVC plasticizers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Citrate esters as plasticizers for poly(lactic acid)

Citrate esters were used as plasticizers with poly(lactic acid) (PLA). Films were extruded using a single-screw extruder with plasticizer contents of 10, 20, and 30% by weight. All of the citrate esters investigated were found to be effective in reducing the glass transition temperature and improving the elongation at break. It was observed that the plasticizing efficiency was higher for the intermediate-molecular-weight plasticizers. Hydrolytic and enzymatic degradation tests were conducted on these films. It was found that the lower-molecular-weight citrates increased the enzymatic degradation rate of PLA and the higher-molecular-weight citrates decreased the degradation rate as compared with that of unplasticized PLA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1507–1513, 1997     

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     

合成柠檬酸酯类增塑剂催化剂及柠檬酸酯类增塑剂的应用

介绍柠檬酸酯类增塑剂的最新发展概况,重点阐述合成柠檬酸酯类增塑剂催化剂的研究进展及柠檬酸酯类增塑剂的应用。合成柠檬酸酯的催化剂有磺酸、固体超强酸、杂多酸、离子液体和无机盐,柠檬酸酯类增塑剂应用于食品包装、儿童玩具和医疗器具。展望柠檬酸酯类增塑剂的发展前景。     

丙烯酸酯单体对聚氯乙烯密封胶粘剂的改性作用

丙烯酸酯有较大的反应活性，能与聚氯乙烯发生接技共聚反应。本文中，我们着重研究不同结构丙烯酸酯单体对聚乙烯基密封胶粘剂的改性作用。以PVC为100份，分别加入甲基丙烯酸一缩二乙二醇双脂（DEGDMA），甲基丙烯酸乙二醇双酯（EGDMA）和丙烯酸一缩二乙二醇双酯（DEGDA）各为10份、20份、30份的试验结果看出，随着丙烯酸酯单体添加量的增加，PVC片基的硬度增大，拉伸强度提高，而伸长率降低。不同的单体其影响也不同。就硬度和拉伸强度有EGDMA＞DEGDA＞DEGDMA的规律伸长率的降低则为DEGDMA＞DEGDA＞EGDMA。就丙烯酸…     

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.     

Euphorbia andVernonia seed oil products as plasticizer-Stabilizers for polyvinyl chloride

Seed oils ofEuphorbia lagascae Spreng. andVernonia anthelmintica (L.) Willd. were prepared, refined and epoxidized; trivernolin was prepared fromV. anthelmintica and also epoxidized. These products were each comparatively evaluated as plasticizer-stabilizers for polyvinyl chloride against commercial controls. EpoxidizedEuphorbia andVernonia oils and epoxidized trivernolin have potential value as primary plasticizers with the added advantage of increased heat and light stability; they could also be used in combination with other plasticizers utilizing the latter properties. Crude and refinedEuphorbia andVernonia oils are not considered suitable primary plasticizers because of poor compatibility and permanence; at low levels they probably could be used as stabilizers. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Feasibility study of water as thinner for polyvinyl chloride plastisol

In the traditional formula of polyvinyl chloride (PVC) gloves, the diluent of PVC plastisol is usually organic solvent, which causes serious environmental pollution during the molding process. The aim of this study was to develop a low viscosity PVC plastisol emulsion (PDE) using water as a thinner by blending PVC emulsion (PVCE) with diisononyl phthalate (DINP) emulsion. DINP emulsion (DINPE) was prepared by a compound emulsifier of polyoxyethylene octyl phenol ether-10 and sorbitan monooleate. The effects of compound emulsifier concentration on the stability and microstructure of DINPE were investigated. The results showed that the optimal compound emulsifier concentration of DINPE was 10 wt%. In addition, the PDE obtained by blending exhibited a relatively uniform unimodal droplet size distribution. The steady state data revealed that the emulsions were shear-thinning pseudoplastic liquid. The effect of solid content and temperature on the apparent viscosity of PDE were also evaluated. The mechanical spectra obtained suggested the presence of weak gel structure in the PDE. The mechanical test results showed that the tensile strength and elongation at break of PVC film obtained by PDE were 12.62 MPa and 310.31%, respectively. This study demonstrated that water was effective in reducing the viscosity of PVC plastisol, which would promote the application of water thinner in glove production.     

Azelaaldehydic acid ester-acetal derivatives as plasticizers for poly(vinyl chloride)

Certain ester-acetal derivatives of azelaaldehydic acid have been evaluated as a new type of plasticizer of PVC. In gerneral, these compouonds have high compatibility and impart excellent low-temperature, mechanical, heat- and light -stability properties to the plasticized PVC. The 2-ethylihexyl ester bis (2-methoxyethyl) acetal, in particular, appeared to have the best combination of properties for a useful plasticizer. The results indicate that a unique and useful type of plasticizer-stabilizer can be obtained from derivatives of azelaaldehydic acid.     

Carbon material from polyvinyl chloride as an adsorbent of 2,4-dichlorophenoxyacetic acid

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) as a typical herbicide from aqueous solutions on activated carbons prepared based on polyvinyl chloride by its alkaline dehydrochlorination and the subsequent heat treatment was studied. The structure of the activated carbon surface and the presence of functional groups on it were established. The kinetics of the process of adsorption was studied. The influence of activated carbon preparation conditions on the properties of the adsorbents was demonstrated.     

Thermoplastic elastomers from NBR and polyvinyl chloride

This paper will discuss recently developed technology that demonstrates the effectiveness of a thermoplastic polyvinyl chloride/nitrile rubber alloy versus commercially available thermoplastic elastomers and conventionally cured rubbers. Compounding variations, mixing and processing of thermoplastic elastomers such as low temperature properties, compression set, heat resistance, flex properties, and oil and fuel resistance will be examined. Compounding variations of the PVC/NBR allows will be explored to show how recipe changes can affect these important properties.