Branched plasticizer

Fig. 8 Water absorption, weight loss, contact angle, and carbonyl/chlorine ratio at the surface of films plasticized with 20 wt. % linear PBA- or BT-based branched plasticizers. Reprinted from [43] with permission of American Chemical Society. American Chemical Society (2007)...

Consequently, from the free volume theory, it can be stated that the plasticizers with lower Tg are more efficient in reducing the Tg of the plasticized system. For the same molecul weight, a branched plasticizer is more efficient than the linear one, since there is more free volume associated in the branched plasticizer. In respect to the molecular weight of the plasticizer, increasing the molecular size of the plasticizer increases the free volume introduced into polymer, thus the plasticizer efficiency. Nevertheless, on a weight basis. 

Plasticizer types and their different concentrations do not perform in the same manner. More volatile plasticizers give films with a shorter outdoor life expectancy. Clear films, containing UV absorber, plasticized at 50 phr were exposed in Florida. Four general purpose plasticizers were studied diisodecyl phthalate, DIDP, diisononyl phthalate, DINP, di-(2-ethylhexyl) phthalate, DOP, and heptyl nonyl undecyl phthalate, HNUP. Less branched and linear phthalate plasticizers (DOP and HNUO) performed very well for 36 months whereas two highly branched plasticizers (DIDP and DINP) were brown after 24 months of exposure. ... 

It is particularly useful in plastisol applications because it Imparts lower initial viscosity, and better viscosity stability than branched plasticizers. 

The stability of plastisol viscosities was measured at low shear rate after aging up to 7 days at 38 °C (100 °F). Viscosities of the 610P and 71 IP plastisols increased by about 2-3 times, whereas the viscosities of the branched plasticizer plastisols increased by about 1.5-2 times the 15 percent DINA in DIDP had no significant effect on viscosity stability. 

In contrast, for many products which do not have significant UV exposure, or, are highly filled or effectively pigmented, branched plasticizers like DIDP can be very satisfactory substitutes for linear plasticizers such as L9P or 71 IP. In fact there are end uses (such as geomembranes and pipe liners) in which branched plasticizers such as DIDP are preferred over their linear counterparts because of relatively lower plasticizer biodegradability and mobility. However, in virtually all other end uses for which outdoor weatherability is a consideration, those flexible PVC formulas which have effective UV blockers, UV absorbers and/or antioxidants can still perform well when made with branched dialkyl phthalate plasticizers. 

Most higher alcohols of commercial importance are primary alcohols secondary alcohols have more limited specialty uses. Detergent range alcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer range alcohols are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fats and oils are always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussed in Synthetic processes. 

Plasticizer Range Alcohols. Commercial products from the family of 6—11 carbon alcohols that make up the plasticizer range are available both as commercially pure single carbon chain materials and as complex isomeric mixtures. Commercial descriptions of plasticizer range alcohols are rather confusing, but in general a commercially pure material is called "-anol," and the mixtures are called "-yl alcohol" or "iso...yl alcohol." For example, 2-ethyIhexanol [104-76-7] and 4-methyl-2-pentanol [108-11-2] are single materials whereas isooctyl alcohol [68526-83-0] is a complex mixture of branched hexanols and heptanols. Another commercial product contains linear alcohols of mixed 6-, 8-, and 10-carbon chains. 

The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties of several commercial plasticizer range alcohols are presented in Table 8. Because in most cases these ate mixtures of isomers or alcohols with several carbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chain alcohols are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9. 

Polygas Olefins. Refinery propylene and butenes are polymerized with a phosphoric acid catalyst at 200°C and 3040—6080 kPa (30—60 atm) to give a mixture of branched olefins up to used primarily in producing plasticizer alcohols (isooctyl, isononyl, and isodecyl alcohol). Since the olefins are branched (75% have two or more CH groups) the alcohols are also branched. Exxon, BASE, Ruhrchemie (now Hoechst), ICl, Nissan, Getty Oil, U.S. Steel Chemicals (now Aristech), and others have all used this olefin source. 

Other Dimer Olefins. Olefins for plasticizer alcohols are also produced by the dimerization of isobutene [115-11-7] 4 8 codimerization of isobutene and / -butene [25167-67-3]. These highly branched octenes lead to a highly branched isononyl alcohol [68526-84-1] product. BASE, Ruhrchemie, ICl, Nippon Oxocol, and others have used this source. 

Polyethylene (PE) is a genetic name for a large family of semicrystalline polymers used mostiy as commodity plastics. PE resins are linear polymers with ethylene molecules as the main building block they are produced either in radical polymerization reactions at high pressures or in catalytic polymerization reactions. Most PE molecules contain branches in thek chains. In very general terms, PE stmcture can be represented by the following formula ... 

Physical Properties. LLDPE is a sernicrystaUine plastic whose chains contain long blocks of ethylene units that crystallize in the same fashion as paraffin waxes or HDPE. The degree of LLDPE crystallinity depends primarily on the a-olefin content in the copolymer (the branching degree of a resin) and is usually below 40—45%. The principal crystalline form of LLDPE is orthorhombic (the same as in HDPE) the cell parameters of nonbranched PE are a = 0.740 nm, b = 0.493 nm, and c (the direction of polymer chains) = 0.2534 nm. Introduction of branching into PE molecules expands the cell slightly thus a increases to 0.77 nm and b to around 0.50 nm. 

The Cg—0 2 branched, odd and even, linear and internal olefins are used to produce improved flexible poly(vinyl chloride) plastics. Demand for these branched olefins, which are produced from propylene and butylene, is estimated to be increasing at a rate of 2% per year. However, the growth of the linear a-olefins is expected to slow down to a rate of 5% per year from 1992 to 1997 (3), as opposed to growth rates of 7—10% in the 1980s. 

The stringency of the conditions employed in the unmodified cobalt 0x0 process leads to formation of heavy trimer esters and acetals (2). Although largely supplanted by low pressure ligand-modified rhodium-catalyzed processes, the unmodified cobalt 0x0 process is stiU employed in some instances for propylene to give a low, eg, - 3.3-3.5 1 isomer ratio product mix, and for low reactivity mixed and/or branched-olefin feedstocks, eg, propylene trimers from the polygas reaction, to produce isodecanol plasticizer alcohol. 

Plasticizer Efficiency. This is a measure of the concentration of plasticizer required to impart a specified softness to PVC. Such a softness of material may be measured as a British Standard Softness (BSS) or a Shore hardness (Pig. 1). Por a given acid constituent of plasticizer ester, ie, phthalate, adipate, etc, plasticizer efficiency decreases as the carbon number of the alcohol chain increases, eg, for phthalate esters efficiency decreases in the order DBP > DIHP > DOP > DINP > DIDP > DTDP. An additional six parts per hundred in PVC of DIDP rather than DOP is required to give a hardness of Shore 80 when ah. other formulation ingredients remain constant. The consequence of this depends on the overall formulation and product costs. In addition to size of the carbon number of the alcohol chain, the amount of branching is also significant the more linear isomers are of greater efficiency. 

Polyester plasticizers give the best performance in this area, with performance increasing with molecular weight. Additionally, branched esters have somewhat higher volatUities than their linear equivalents. 

Plasticizer molecules can undergo thermal degradation at high temperatures. Esters based on the more branched alcohol isomers are more susceptible to such degradation. This can, however, be offset by the incorporation of an antioxidant, and plasticizer esters for cable appHcations frequently contain a small amount of an antioxidant such as bisphenol A. 

Mixtures of isomeric amyl alcohols (1-pentanol and 2-methyl-1-butanol) are often preferred because the different degree of branching imparts a more desirable combination of properties they are also less expensive to produce commercially. One such mixture is a commercial product sold under the name Primary Amyl Alcohol by Union Carbide Chemicals and Plastics Company Inc. 

Plasticizers. Plasticizers are materials that soften and flexibilize inherently rigid, and even britde polymers. Organic esters are widely used as plasticizers in polymers (97,98). These esters include the benzoats, phthalates, terephthalates, and trimeUitates, and aUphatic dibasic acid esters. Eor example, triethylene glycol bis(2-ethylbutyrate) [95-08-9] is a plasticizer for poly(vinyl butyral) [63148-65-2] which is used in laminated safety glass (see Vinyl POLYMERS, poly(vinyl acetals)). Di(2-ethyUiexyl)phthalate [117-81-7] (DOP) is a preeminent plasticizer. Variation of acid and/or alcohol component(s) modifies the efficacy of the resultant ester as a plasticizer. In phthalate plasticizers, molecular sizes of the alcohol moiety can be varied from methyl to tridecyl to control permanence, compatibiUty, and efficiency branched (eg, 2-ethylhexyl, isodecyl) for rapid absorption and fusion linear (C6—Cll) for low temperature flexibiUty and low volatility and aromatic (benzyl) for solvating. Terephthalates are recognized for their migration resistance, and trimeUitates for their low volatility in plasticizer appHcations. 

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