Adipic polymeric plasticizer

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. 

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. 

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

Castle, L., Mercer, A.J., Gilbert, J., 1988, Migration from plasticized films into foods. 4. Use of polymeric plasticizers and lower levels of di-(2-ethylhexyl)adipate plasticizer in PVC films to reduce migration into foods. Food Additives and Contaminants 5 (3) 277-282. 

ADIPATE BASED POLYMERIC PLASTICIZER WITH IMPROVED LOW TEMPERATURE PROPERTIES... 

Other plasticizers include adipates, azelates, sebacates and various polymeric plasticizers made from glycols and aliphatic dicarboxylic acids. 

Plasthall [Hall]. TM for a broad range of monomeric and polymeric plasticizers used in polymers and elastomers. Types include adipates, gluta-rates, trimellitates, azelates, sebacates, and tallates. 

Chem. Descrip. Med.-low m.w. polymeric adipate Uses Plasticizer for medical applies., hospital sheeting, beverage tubing, food equip, coatings, polymers in contact with food Features Nonextractable by lipids in medical applies. washable permanent... 

Studies of hydrolytic stabihty of polymeric plasticizers, such as poly(propylene adipate) and poly(butylene adipate) were conducted in simulated body fluids such as saliva, gastric and intestinal fluids. It was found that no hydrolysis occurred under saliva and gastric conditions but plasticizers were hydrolyzed to a large extent in simulated intestinal fluid. Enzymes selectively catalyzed the primary alcohol ester linkage. It is expected that other polymeric ester plasticizers will behave in a similar manner. ... 

Polypropylene adipate (polypropylene glycol adipate) n. A polymeric plasticizer for vinyl chloride polymers and co-polymers formed by reacting propylene glycol and adipic acid. 

Oligomeric and polymeric plasticizers (usually polyesters, based on adipic acid) extend the life of PVC end-products considerably. They reduce migration, extraction, and volatility. They are suitable for pastes (oligomeric) and extrusion/calendering compounds (polymeric). They are non-migratory, scarcely volatile, and have low dependency on temperature. Some types resist extraction by aliphatic hydrocarbons, mineral oils, or fats some are difficult to incorporate or are compatible with PVC only in mixes. 

Additives used in final products Plasticizers acetyl tri-n-butyl citrate, epoxidized soybean oil, polymeric condensation product of azelic acid and 1,3-butane-diol, polymeric plasticizer of adipic acid and propylene glycol. Antistatics ionic polymer, imidazoline/metal salt ... 

Other plasticizers are used in various applications where a specific property or properties are required of the end product. These include phosphate esters used in fire retardant applications such as cables and spread contract flooring polymeric plasticizers (usually a polymeric adipate, used in low migration food contact applications) benzoates (fast fusion), and sebacates and azelates (which are similar to adipates but give enhanced properties). For further information the reader is directed to the recent definitive text by A.S. Wilson. 

Keywords glass transition temperature, PVC, phthalates, adipates, trimellitates, polymeric plasticizers. 

Butylene Glycol Adipate Polyester n (Santicizer 334F) A polymeric plasticizer for PVC. 

The largest class of polymeric plasticizers is polyesters, which are prepared by the reaction of differing diols, dibasic acids (such as adipic acid or phthalic anhydride), and an aliphatic primary alcohol or an aliphatic acid acting as a chain stopper to help control the molecular weight. These products typically range from high viscosity liquids to gels or semisolids at room temperature. Polymeric plasticizers offer improved performance in resistance of plasticizer extraction by solvents or oils, resistance to... 

Adipic acid is directly used in the production of DBEEA, a polymeric plasticizer for specialty elastomers. In addition, adipic acid is a very important feedstock in the production of nylon-6,6 fiber, which is used to make nylon tire cord. 

Cylcohexane is a feedstock for adipic acid, which is needed to produce DOA plasticizer (for low-temperature applications in rubber) and DBEEA polymeric plasticizer for rubber. 

Polymeric plasticizers, such as poly(propylene adipate) and poly(propylene sebacate), are non-volatile, non-migratory and resistant to hydrocarbon extraction. However, they are expensive and the compounds are difficult to manufacture. Extender plasticizers are not compatible with PVC but are miscible with plasticized PVC. A processor can use them to replace a part of the more expensive plasticizer content. Examples include chlorinated paraffin waxes, paraffin liquids or oil extracts. 

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