Linear phthalate

As the seventies got underway, the premium price on the GP linear phthalates decreased to where these plasticizers also began to capture a share of the general purpose plasticizer market, particularly if improved low temperature flexibility was important. The phthalate of the Cn fraction of the linear C7-C9-C11 alcohols was introduced by Monsanto and found acceptance in high temperature wire and cable where it competes with branched chain DTDP. In Europe, linear alcohol phthalates based on alcohol blends made by oxonation of cracked wax olefins gained acceptance. These differed from the U.S. linear alcohol blends in having both odd and even carbon chain lengths. 

The Declining Market for Linear Phthalates in Automotive Upholstery. The major market for linear phthalates has historically been automotive upholstery. However, the U.S. built share of the automotive market has continued to decline, and the trend (now a landslide) to smaller cars has resulted in a sharp decrease in demand for domestic vinyl upholstery. Besides this, fashion trends have turned to increased use of non-vinyl upholstery. Finally, the use of softer vinyls with higher plasticizer levels means increased opportunities in the automotive upholstery market for diisodecyl phthalate (DIDP). DIDP meets the low temperature requirements of these new softer vinyls, and at the same time offers reduced windshield fogging and lower cost on a... 

However, during the period when DOP was in short supply many users converted to DINP, DIDP, and linear phthalates. They have found the better overall performance, and in many cases better compound economics of these plasticizers justifies continued use. Although DOP will regain some of its lost ground, it is not expected to dominate the U.S. market as in the past. 

Wilkinson and Lamb 1999). The use of DEHP in domestically produced teethers and rattles has been discontinued (Consumer Product Safety Commission 1999d). DEHP is also no longer used as a plasticizer in plastic food wrap products (Mannsville Chemical Products Corporation 1999). In addition, some applications, like automobile upholstery, might switch from DEHP to linear phthalates because of their superior performance and low toxicity, which will put further downward pressure on DEHP use (Mannsville Chemical Products Corporation 1999). Finally, in the future, polyolefin metallocene plastomers might replace flexible applications for PVC altogether because they provide flexibility without the need for plasticizers. 

C - C " 8 11 L911P, L810P Linear and semi-linear phthalates for low viscosity applications Low temperature... 

Linear phthalates Volatility less than 1% low-temperatme properties to 50°C good outdoor weathering low viscosity improved compatibility with PVC Costs more than DOP Wire and cable to 90°C automotive interiors roofing membranes... 

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. ... 

A few companies have reduced their commitment to polymer additives. The Swiss company Lonza places increasing emphasis on pharmaceutical intermediates in its European operations, but also makes oleochemicals for plastics. Other additive products include plasticisers, both general-pm tose types and linear phthalates, together with polymeries and trimellitates. It is a leading supplier in the US of polymer lubricants such as EBS (ethylene bis-stearamide) and other amide waxes. First half profits overall were down 16% in 2004. Research and development expenditure in 2003 amoimted to US 65 M. A new CEO, Stefan Borgas, has been appointed from BASF. 

In Europe, plasticised flexible PVC is the key material used in single ply membranes used to cover large flat roofs. For these applications, plasticiser systems used are mostly linear phthalates (mainly due to their low volatility and high photostability). 

The linear phthalates produced from these alcohols provide many advantages over their branched coimterparts. Among these are processability, efficiency, volatility, viscosity, thermal stability, light stability, low temperature, and long-term permanence. 

The family of adipic acid esters in PVC applications has improved low temperature performance relative to phthalates and lower plastisol viscosities, because of the lower inherent viscosities of the plasticizer. Adipates used are typically in the C7-C10 range. Incompatibility problems can be encoimtered at higher carbon numbers, especially at high addition levels. Adipates are more volatile and have higher migration rates than phthalates. Because they are a specialty for the PVC industry, they are higher priced. As a result, it is not imcommon to encounter adipates used in blends with phthalates to produce a compromise of properties. Because of these limitations, linear phthalates are often used in place of adipates wherever possible. 

Low volatility Polymeries, trimellitates, linear phthalates, epoxy plasticizers... 

Examples of some of the more common plasticizers and their classifications are listed in Table 24.2. Often a plasticizer can be placed in multiple classifications. For example, linear phthalates are recognized for both their low temperature performance and low volatility. In addition some specialty plasticizers could also fit in the fast fast-fusing plasticizers classification. 

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. 

Low-temperature plasticizers are used in applications where improvements in the low temperature flexibility limits are desired. Applications can include automotive interiors, weather stripping, outdoor cables, hoses, and vinyl roofing. Low-temperature plasticizers include the linear phthalate esters L9P, L911P, and LI IP or DUP. The dibasic acid esters such as DEHA (DOA), DINA, and DEHZ (di-2-ethylhexyl azelate) are also low-temperature plasticizers, but their higher volatility may Unfit their use in some applications. 

The addition of plasticizers to a PVC product extends the lower useful temperature limit of the finished product. Generally, the lower temperature performance is enhanced as the plasticizer concentration is increased. Some plasticizers are more efficient in providing low temperature flexibility than others. Aliphatic diesters of adipic, azelaic, and se-bacic acids are the preferred plasticizers for very low temperature requirements. In addition, the linear phthalates based on linear C9 alcohols, linear Cl 1 alcohols, and the linear C9/C11 blends offer enhanced low temperature performance over the corresponding branched esters. The low temperature flexibility as reported by the Clash-Berg (ASTM D1043) method for PVC plasticized with several esters is shown in Fig. 24.4. 

Historically, di(2-ethylhexyl) phthalate has constituted approximately 50% of all the phthalate ester plasticizers used. However, in recent years, the use of di(2-ethylhexyl) phthalate has diminished because of health concerns. It is no longer used in plastic food packaging or baby teethers and rattles. Many toy manufacturers have discontinued its use in toys, and it is being replaced by linear phthalates and other plasticizers (12). 

Formulations made from PX-111 have low volatility and excellent resistance to chemical breakdown at high temperatures and therefore, better retention of properties after oven aging. It can be blended with other linear phthalates. 

A low-molecular-weight linear phthalate designed to perform as a primary plasticizer and a PVC processing aid. It is designed to compete with the branched phthalates DHP and DIHP, BBP and benzoate plasticizers. 

PX-911 is a medium molecular weight linear phthalate. Physical Properties ... 

Palatinol 7P plasticizer is a linear phthalate ester based on a predominantly linear C7 alcohol. Palatinol 7P can be used as a primary plasticizer in flexible vinyl compounding or added with other phthalate plasticizers to enhance fast fusion applications. Palatinol 7P shortens both gelation and fusion times while enhancing plastisol viscosity when compared to equivalent branched alcohol chain phthalate plasticizers. Product Specifications ... 

Palatinol 11-9P-I High Molecular Weight Linear Phthalate Formula C28H4604 Molecular Weight 458... 

CAS Registry Numbers 85507-79-5/111381-91-0/68515-45-7 Palatinol 11-9P-1 plasticizer is a linear phthalate ester based on predominantly linear C9 and Cll alcohols. It exhibits extremely low volatility in vinyl for automotive applications that require low weight loss, long-term property retention and excellent low temperature performance properties. 

Palatinol IIP-E plasticizer is a linear phthalate ester based on a predominantly linear Cll alcohol. 

Palatinol 79P is a predominantly linear phthalate plasticizer based upon C7 and C9 alcohols. The ratio of these alcohols and their degree of linearity provide excellent processing characteristics, superior plastisol rheology and iiqiroved product flexibility under low temperature conditions when compared to OOP, DINP and DOTP in vinyl resins. 

With this fluxed polymCT blend, try to keep the plasticizer choice as simple and as basic as possible. Use a commodity phthalate (DOP, DINP, and DIDP) to keep the cost down. If better low-temperature flex is required use a 100% linear phthalate (810P) or DOA/DIDA for maximum low-temperature performance. Rarely does an NBR/PVC application call for the expensive low-temperature types DOZ, DOS, TOF. To improve extraction resistance and to control swell use a medium viscosity (4,000-15,000 cps) adipic or glutaric polymeric plasticizer for 20%—40% of the total plasticizer content. Poor low-temperature flex and softening efficiency are the weak points of all polymeries. Monoesters (oleates, stearates, tallates) and process oils are not recommended for NBR/PVC. 

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