Dioctyl phthalates plasticizers

Addition of a dioctyl phthalate plasticizer (DOP) increases flammability and incompatability of PVC with flame retardants. 

Modulus-temperature behavior of amorphous polymers is also affected by admixture with plasticizers. These are the soluble diluents described briefly in Section 12.3.2. As shown in Fig. 11-11, the incorporation of a plasticizer reduces Tg and makes the polymer more flexible at any temperature above Tg. In polyfvinyl chloride), for example, T can be lowered from about 85°C for unplaslicized material to —30°C for blends of the polymer with 50 wt % of dioctyl phthalate plasticizer. A very wide range of mechanical properties can be achieved with this one polymer by variations in the type and concentration of plasticizers. 

PVC resin (medium mol. wt.) tetrahydrofuran methyl ethyl ketone organic tin stabilizer dioctyl phthalate (plasticizer) methyl isobutyl ketone... 

Figure 4.42. Determination of dioctyl phthalate plasticizer in polyvinyl chloride (100).

Chem. Descrip. 10,10 -Oxybisphenoxarsine in dioctyl phthalate plasticizer carrier... 

Butylene carbonate Dibutoxyethoxyethyl phthalate Ethylene carbonate N-(2-Hydroxypropyl) benzenesulfonamide plasticizer, PU foam Pentaerythrityl trioleate Tris (2,3-dichloropropyl) phosphate plasticizer, PU resins Triethylene glycol plasticizer, PU sealants Polypropylene glycol dibenzoate plasticizer, PU-based sealants Benzyl phthalate plasticizer, pulp/paper Oleyl alcohol Propylene glycol laurate plasticizer, PVA emulsion paints s-Dioctyl phthalate plasticizer, PVAc Butyl oleate Butyl ricinoleate Dibutoxyethoxyethyl adipate Dibutoxyethoxyethyl glutarate Dibutyl adipate... 

Today the installed hydroformylation capacity worldwide is more than 7.5 Mio tons per year (Baerns et al., 2006). The most important feedstock is propene, with the products n-butyraldehyde and iso-butyraldehyde (Scheme 6.14.3). The most important single product from propene hydroformylation is 2-ethyl-l-hexanol (>50% of the n-butyraldehyde production), the aldol condensation product obtained from n-butanal, which is an important plasticizer alcohol. After esterification with phthalic anhydride, dioctyl phthalates plasticizers are obtained that are used mainly in poly(vinyl chloride) plastics. 

Monomeric liquid plasticizers are closely analogous to monomeric solvents. If two polymers are immiscible, but are both miscible with the same plasticizer, adding this plasticizer to the polymer blend may improve its compatibility. For example, blends of CPE with polyvinyl chloride were compatibilized by addition of 50% of dioctyl phthalate plasticizer [67]. In commercial practice, polyvinyl chloride -I- polyurethane are sometimes compatibilized in a similar way. 

Zou J, Su L, You F, Chen G, Guo S. Dynamic rheological behavior and microcrystalline structure of dioctyl phthalate plasticized poly(vinyl chloride). J Appl Polym Sci 2011 121 1725-33. 

Dioctyl phthalate plasticizer is an ester that is usually synthesized by reacting an alcohol with an organic acid as shown in Figure 4.23. 

Synthesis of dioctyl phthalate plasticizer from reaction of alcohol and an organic acid... 

Superior bleed resistance in water, ethanol, diethylene glycol, xylol, toluol, butyl cellosolve, lacquer solvents, mineral spirits, paraffin, halogenated hydrocarbons, soap, or dioctyl phthalate (plasticizers). 

Nuisrn R., S. Omi, and S. Kiatkamjomwong, Synthesis and property behavior of dioctyl phthalate plasticized styrene-acrylate particles by Shirasu porous glass emulsification and subsequent suspension copolymerization./ourna/ of Applied Polymer Science, 2003.90 3037-3050. 

By far the largest volume synthetic alcohol is 2-ethylexanol [104-76-7] CgH gO, used mainly in production of the poly(vinyl chloride) plasticizer bis(2-ethylhexyl) phthalate [117-81-7], commonly called dioctyl phthalate [117-81-7] or DOP (see Plasticizers). A number of other plasticizer... 

Fig. 2. The effect of antimony oxide on the oxygen index of poly(vinyl chloride) plasticized with dioctyl phthalate (DOP), (—...

Raw Materials. PVC is inherently a hard and brittle material and very sensitive to heat it thus must be modified with a variety of plasticizers, stabilizers, and other processing aids to form heat-stable flexible or semiflexible products or with lesser amounts of these processing aids for the manufacture of rigid products (see Vinyl polymers, vinyl chloride polymers). Plasticizer levels used to produce the desired softness and flexibihty in a finished product vary between 25 parts per hundred (pph) parts of PVC for flooring products to about 80—100 pph for apparel products (245). Numerous plasticizers (qv) are commercially available for PVC, although dioctyl phthalate (DOP) is by far the most widely used in industrial appHcations due to its excellent properties and low cost. For example, phosphates provide improved flame resistance, adipate esters enhance low temperature flexibihty, polymeric plasticizers such as glycol adipates and azelates improve the migration resistance, and phthalate esters provide compatibiUty and flexibihty (245). 

Plasticizers. Monomeric (mol wt 250—450) plasticizers (qv) are predominantiy phthalate, adipate, sebacate, phosphate, or trimeUitate esters. Organic phthalate esters like dioctyl phthalate (DOP) are by far the most common plasticizers in flexible PVC. Phthalates are good general-purpose plasticizers which impart good physical and low temperature properties but lack permanence in hot or extractive service conditions and are therefore sometimes called migratory plasticizers. Polymeric plasticizers (mol wt up to 5000 or more) offer an improvement in nonmigratory permanence at a sacrifice in cost, low temperature properties, and processibiHty examples are ethylene vinyl acetate or nitrile polymers. 

Uses. Phthabc anhydride is used mainly in plasticizers, unsaturated polyesters, and alkyd resins (qv). PhthaUc plasticizers consume 54% of the phthahc anhydride in the United States (33). The plasticizers (qv) are used mainly with poly(vinyl chloride) to produce flexible sheet such as wallpaper and upholstery fabric from normally rigid polymers. The plasticizers are of two types diesters of the same monohydric alcohol such as dibutyl phthalate, or mixed esters of two monohydric alcohols. The largest-volume plasticizer is di(2-ethylhexyl) phthalate [117-81-7] which is known commercially as dioctyl phthalate (DOP) and is the base to which other plasticizers are compared. The important phthahc acid esters and thek physical properties are Hsted in Table 12. The demand for phthahc acid in plasticizers is naturally tied to the growth of the flexible poly(vinyl chloride) market which is large and has been growing steadily. 

Di-2-EthylhexylPhthalate. In Western Europe, di-2-ethylhexyl phthalate [117-81-7] (DEHP), also known as dioctyl phthalate (DOP), accounts for about 50% of all plasticizer usage and as such is generally considered as the industry standard. The reason for this is that it is in the mid-range of plasticizer properties. DEHP (or DOP) is the phthalate ester of 2-ethyIhexanol, which is normally manufactured by the dimerization of butyraldehyde (eq. 2), the butyraldehyde itself being synthesized from propylene (see Butyraldehydes). 

Fig. 4. SmaH-angle x-ray scattering pattern from PVC plasticized with 20 parts per hundred resin of dioctyl phthalate (18).

Vehicles are selected by two methods. In one a concentrate is designed directiy for a resin system, the resin itself, or a compatible resin. Thus when the concentrate is made there is a minimal effect on the properties of the final color. In PVC, often a plasticizer such as dioctyl phthalate (DOP) is used. In the other method, concentrates are made with a commercial universal concentrate vehicle. Concentrate manufacturers and some resin manufacturers have developed vehicles that can incorporate many types of colorants and can be used across many classes of polymers without adversely affecting final product performance. 

The polarity of the polyethers makes them incompatible with hydrocarbon-type plasticizers, which tend to bleed. Effective plasticizers are ethers such as di(butoxyethoxyethyl)formal [143-29-3] (Thiokors TP-90B), esters such as di(2-ethylhexyl) phthalate [117-81-7] dioctyl phthalate (DOP), polyesters such as Paraplex G50 (Rohm and Haas), and ether—esters such as di(butoxyethoxyethyl) adipate [114-17-3] (Thiokol s TP-95). The lower mol wt plasticizers, DOP, TP-90B, and TP-95 improve vulcanizate low temperature performance. The polymeric plasticizers maintain higher temperature and long-term aging properties. Epoxidized plasticizers should be avoided because they interfere with vulcanization. 

Produced from PVC compounds containing plasticizers such as dioctyl phthalate, this is a flexible sheeting suitable for lining tanks made from steel and concrete. The maximum temperature at which this lining can be used is 60°C. 

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