Phthalate alternatives

A review of phthalate alternatives, taking account of the history of phthalates and cost performance, has been presented (89). 

The CHAP also recommends the appropriate U.S. agencies to investigate exposure and hazard data to estimate total exposure to the phthalate alternatives and assess the potential health risks for these products. 

CHAP, 2014. Report to the U.S. Consumer Product Safety Commission by the Chronic Hazard Advisory Panel On Phthalates And Phthalate Alternatives. Available from http //www. cpsc.gov/PageFiles/169902/CHAP-REPORT-With-Appendices.pdf (accessed 10.11.14). 

Because of the lower volatility of DIDP and DPHP relative to other GP plasticizers, these two plasticizers are also sometimes considered low-volatility plasticizers. For automotive interior products the plasticizers DEHP, DINP, DEHTP, DC9CH, citrates, benzoates, as well as many of the phthalate alternatives would fail many interior emission or fogging requirements while DIDP and DPHP, along with trimellitate esters and the linear phthalates L9P and L91P, would pass. 

Citrates are fast-fusing plasticizers, especially when compared to many of the phthalate alternatives. Unfortunately citrates are not as permanent because of high volatility losses, and the finished PVC products do not remain as flexible for as long as those prepared from more permanent plasticizers. Citrates are often used in blends with the harder-to-process terephthalate or cyclohexanoate plasticizers, but in these applications, because of costs, dibenzoate plasticizers may be preferred. Citrate esters also find uses with other plastics such as acrylics, cellulosic polymers, and vinyl acetate. Acetylated tributyl citrate (ATBC) does have a number of food contact and medical approvals and is commonly found in toys, often in combination with DEHTP or DC9CH. 

In the mid-1970s, Hercules Chemical Company introduced two polyol ester plasticizers, Hercoflex 600 and Hercoflex 707. These plasticizers were prepared by the esterification of pentaerythritol and dipentaerythritol with a mixture of short-chain acids, predominately C6 acid. Although a few PVC applications and patents were developed, because of high costs, they have met with limited commercial success in PVC, although the products continue to be sold into the elastomer market in both North America and in Europe. A PVC plasticizer based on the pentaerythritol ester prepared with predominately C5 acids plus lesser amounts of C7 and C9 acids was patented in 1995 [41] as a low smoke plasticizer. The pentaerythritol ester prepared from C5 acids [42] is now being promoted by the Perstorp Group as a new phthalate alternative under the product brand Pevalen. 

DIDP is used as one of the phthalate alternatives for DOR DIDP, with its higher molecular weight, imparts greater permanence to rubber compounds. However, San Francisco in 2006 became the first jurisdiction to prohibit DIDP (and other phthalate esters) in toys. 

Alkyl Sulfonic Acid Esters of Phenol There are two esters in this category, differing in average chain length of the alkyl group. The esters are reported to be used for GP applications in Europe and are often promoted as a phthalate alternative. They are also used in polyurethane sealants. Plasticizing efficiency (SF) is similar to that of... 

Triglyceride Plasticizers. Glycerol Di-2-ethylhexanoic Acid/Benzoic Acid Ester and Glycerol Acetylated Esters Two differing types of glycerol esters have been recently introduced as phthalate alternatives. In one form, the performance... 

Benzoate esters. As a class, these specialty plasticizers are known as high sol-vators for vinyl compositions. Within this class of plasticizers, the applications range from viscosity reducers for plastisols to bleed-resistant plastisols for screen ink. They arc considered as phthalate alternates for applications requiring phthalate-free compositions. 

Rubbers. Plasticizers have been used in mbber processing and formulations for many years (8), although phthaHc and adipic esters have found Htde use since cheaper alternatives, eg, heavy petroleum oils, coal tars, and other predominandy hydrocarbon products, are available for many types of mbber. Esters, eg, DOA, DOP, and DOS, can be used with latex mbber to produce large reductions in T. It has been noted (9) that the more polar elastomers such as nitrile mbber and chloroprene are insufficiendy compatible with hydrocarbons and requite a more specialized type of plasticizer, eg, a phthalate or adipate ester. Approximately 50% of nitrile mbber used in Western Europe is plasticized at 10—15 phr (a total of 5000—6000 t/yr), and 25% of chloroprene at ca 10 phr (ca 2000 t/yr) is plasticized. Usage in other elastomers is very low although may increase due to toxicological concerns over polynuclear aromatic compounds (9). 

FauserP, Vikelspe J, Sorensen PB, Carlsen L (2003) Phthalates, nonylphenols and LAS in an alternately operated wastewater treatment plant - fate modeling based on measured concentrations in wastewater and sludge. Water Res 37 1288-1295... 

An alternative means of detection involves UV spectrophotometry, the mobile phase containing the strongly absorbing phthalate ion which gives a constant high absorbance baseline signal that displays negative peaks as the sample components elute from the separator column. No suppressor column is therefore needed and the sensitivity is comparable to conductometric detection. 

Alternative to m-chloroperbenzoic acid.1 This oxidant has been introduced as a suitable replacement for m-chloroperbenzoic acid, which is no longer available from commercial sources because of hazards in the manufacture. Actually MMPP is a safer reagent than MCPBA, which is shock-sensitive and potentially explosive. MMPP is soluble in water and in low-molecular-weight alcohols. The by-product, magnesium phthalate, is water-soluble and easily removed. It is generally more stable than other percarboxylic acids. It can replace MCPBA for the usual classic oxidations epoxidation, Baeyer-Villiger reactions, and oxidation of amines to N-oxides. 

Diallyl isophthalate (DAIP), 2 258, 261 physical properties of, 2 258t thermoset molding properties of, 2 262t Diallyl phthalates (DAP), 2 258-263 20 110 copolymerization, 2 259-260 Diallyl terephthalate (DATP), 2 259 DIALOG file, 18 246 DIALOG OneSearch, 18 244 -dial suffix, 2 58 Dialysate, 26 814, 815 composition of, 26 817 Dialysis. See also Hemodialysis alternative modes of, 26 832-833 requirements for adequate, 26 821-822 treatment time and frequency of, 26 833-834... 

The rapid movement in the global phthalates market away from using plasticisers 2-ethylhexanol (2-EH) and diethylhexyl phthalate (DEHP) in favour of alternative products was underscored recently when BASF revealed plans to close its 2-EH and DEHP plants in Germany. The restructuring in Europe will have no effect on BASF s plasticiser portfolio in Nafta and Asia, however, where the company will continue to offer 2-EH and DEHP. About 70% of the plasticiser maiket volume is phthalates, and plasticisers make up about 60% of the plastic additives maiket. PVC accounts for 80-90% of global plasticiser consumption. In October 2003, California added DEHP to the state s list of more than 750 chemicals known to cause birth defects or reproductive harm. Previous studies had shown that the chemical can leach from plastic bags that contain intravenous fluids, blood, tube feedings or other medical treatment, and thereby enter the bodies of patients. 

PVC INDUSTRY WELCOMES ALTERNATIVE TO PHTHALATES IN TOYS, MEDICAL ITEMS... 

For some time now plasticisers, especially phthalates, have been under pressure from environmentalists and regulatory bodies. In the regulatory arena there is the RCRAand CERCL A requirements of the EPA, Proposition 65 in California and the EU labelling requirements of chemicals. Taking this into account, as well as customer demand for alternative plasticisers, BASF has undertaken a project to develop a plasticiser suitable in a wide range of applications and which would meet the following... 

In April, an EC scientific committee concluded that there was reason for concern about estimated exposures of the phthalate DINP to toddlers chewing soft P VC toys. A study commissioned by the Dutch Health Ministry also failed to provide a robust defence of the plasticisers. Elsewhere, the Canadian Health Ministry has advised retailers to withdraw PVC teethers and find alternatives to soft PVC in other toddlers toys. Toys R Us has announced a worldwide withdrawal of teethers and other direct-to-mouth products containing phthalates. 

In SL-PC, a catalyst is supported on a solid matrix in the form of the film of a nonvolatile liquid phase adsorbed on the solid. The catalytic film can be, for example, a molten salt or a molten oxide (e.g., Deacon s catalyst (CUCI2/KCI) used to oxidize HCl with oxygen for the chlorination of ethylene in the synthesis of vinyl chloride. Figure 6.1 V2O5 for the oxidation of sulphurous to sulphuric anhydride). Alternately, it can be a liquid phase (e.g., ethylene glycol, PPh3, butyl benzyl phthalate, etc.) that contains a soluble catalytic species such as a metal complex. 

There are several large impediments to achieving the goal of more accurate risk assessments. First, it often requires a considerable investment in the research necessary to uncover the types of information needed to replace default assumptions in specific cases. If one hypothesizes that di-(2-ethylhexyl)phthalate (DEHP, a real and important chemical) produces liver tumors in rodents by mechanisms that either do not apply to humans at all, or that do not operate at low (human) doses, or both, then there arises the question of what type of research information is necessary to test the validity of such hypotheses If such research is actually carried out, then what type of results from that research would allow conclusions to be drawn about the validity of the hypotheses In many specific cases creative and knowledgeable scientists can hypothesize alternatives to the usual defaults and ways to test their validity. But it often turns out to be difficult to arrive at... 

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