Polymeric plasticizer for PVC

There are three major measurements used in judging TPU as a polymeric plasticizer for PVC the glass transition temperature (Tg), the compatibility with PVC, and the degree of crystallinity. 

Ethylene-vinylacetate blends with PVC have been widely used in Europe as permanent polymeric plasticizers for PVC. Low cost and good weatherability of these blends permitted their use in window profiles, cable jacketing and other outdoor applications. Ethylene vinylacetate copolymer with 65-75% vinyl acetate content is quite miscible with PVC exhibiting a single T for the blend [Hammer, 1971 Ranby, 1975 Rellick and Runt, 1985]. Two phases are apparent when the vinylacetate is < 45%. Vinylchloride grafted ethylene-vinyl acetate copolymers have also been used for blending with PVC. 

Braun D., Bergmann M., Polyesters with l,4 3,6-dianhydrosorbitol as polymeric plasticizers for PVC, Angew. Makromol. Cftem.,199,1993, 191-205. 

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

Azolides used as promotors in the anionic polymerization of lactams,1231,1241 and as plasticizers for PVC 1251... 

The volume leaders among fire retardants with 35 million pounds were the three phosphate plasticizers for PVC tricresyl phosphate, cresyl diphenyl phosphate and triphenyl phosphate. The remaining 6 million pounds were made up of octyl diphenyl phosphate, tributyl phosphate, tri(dibromopropyl) phosphate, tri(dichloropropyl) phosphate and tri-(chloroethyl) phosphate. Polymeric phosphorus and phosphorus halogen-containing additives are used in concentrations of 3-25 p.p.h. in polyesters, flexible and rigid polyurethane foam, and phenolics. 

The heading production of chemical products includes the conversion of allyl alcohol to glycerine with hydrogen peroxide, the production of epoxy-compounds such as epoxy soya oil (plasticizer for PVC) and organic peroxides (e.g. methyl-ethyl-ketone-peroxide, dibenzoylperoxide), which are used as free radical initiators in polymerization processes. The production of amine oxides such as lauryl-dimethyl-amine-oxide with hydrogen peroxide (used as a rinsing agent in dishwashers) is also included. 

The effect of the presence of compatibilized incompatible components is apparent in PVC plastisols. Monomeric and polymeric esters are good plasticizers for PVC because they have suitable solubility parameters. A good plasticizer is one which, in sufficient quantity, would almost be a solvent for the polymer. However, a good plasticizer, i.e. solvent, in a plastisol results in a high viscosity composition. This may be unsuitable for slush molding or other applications when low viscosity is desirable. The latter is obtained by adding a secondary plasticizer such as a hydrocarbon oil. In reality, the latter is not a plasticizer but actually a non-solvent which converts the good solvent plasticizer to a poor solvent mixture with resultant decrease in plastisol vis-... 

Ethylene-vinyl acetate (EVA) polymers (containing 65%-70% by weight of vinyl acetate) are of industrial interest as high-molecular weight plasticizers for PVC, mainly because of their low cost. A polymeric plasticizer PB-3041 available from Du Pont allows the preparation of a highly permanent plasticized PVC formulation. It is believed to be a terpolymer of ethylene, vinyl, acetate, and carbon monoxide. Also, butylene terephthalate-tetrahydrofuran block copolymers, with the trade name of Hytrel (Du Pont), are used as excellent permanent plasticizers of PVC. 

Both monomeric and polymeric plasticizers are suitable for plasticization. Practically all monomeric plasticizers for PVC can be used. Suitable polymeric plasticizers include polyadipates, chlorinated paraffins, carbamide resins, and epoxides. Vinyl chloride copolymers are compatible with most conventional pigments and extenders. Despite their high intrinsic stability, paints based on vinyl chloride copolymers have to be stabilized against dehydrochlorination in the presence of heat and/or UV radiation for some applications. Epoxy compounds are often sufficient for thermal stabilization. 

Chem. Descrip. Low m.w. polymeric polyester Uses Plasticizer for PVC compositions, other polymers, metal coatings, plastisols... 

Uses Flame retardant, plasticizer for PVC, cellulose nitrate, CAB, ethyl cellulose, polymethyl methacrylate. PS. buna N rubber, in vinyl film and sheeting, textile coatings, plastisols. organosols, adhesives, pkg. materials plasticizer in food-contact coatings, dip. rotationally, extnid and inj. molded parts, mech. foam in food-pkg. adhesives in resin-ous/polymeric food-contact coatings Features Low-temp, plasticizer... 

DBP and BBP are fast-fusing plasticizers for PVC. They are mostly used in combination with DEHP. BBP is further present in cosmetics, such as hair sprays containing 0.1 to 1% BBP. Cl to C4 phthalates are mainly used as plasticizers for cellulose resins and some vinyl ester resins. C4 phthalates are also appropriate plasticizers for nitrocellulose lacquers. Further non-polymeric uses of phthalates are fixatives, detergents, lubricating oils and solvents in products such as cosmetics and wood finishes as well as additives in insect repellents. ... 

Oligomers are intermediates between the low-molecular materials and the high-polymers. Their degree of polymerization may be 2 (dimer), 3 (trimer), or more up to 100. Some of the plasticizers for PVC are also oligomers even though they are called polymeric plasticizers. 

However, more recently, the ethylene-vinyl acetate-carbon monoxide (E-VA-CO) terpolymers (Tg = —32 °C), offering a more complete miscibility with PVC, because of the polar keto groups in the terpolymer structure, have replaced the EVA copolymers for fiexibilizing the PVC. The E-VA-CO/PVC blends exhibit a single Tg behavior, indicating the complete miscibility (McConnell et al. 2004). Thus, the E-VA-CO terpolymer is more effective as a miscible, polymeric plasticizer for effectively lowering the Tg of PVC to make it more fiexible. 

In 1860, Hofman described the "metamorphosis" of vinyl bromide to pol3winyl bromide and Baumann repeated this "conversion" with vinyl chloride in 1872. However, polyvinyl chloride (PVC) was not patented until 1912, when Klatte used sunlight to initiate the polymerization of vinyl chloride. Klatte produced the monomer by the mercuric chloride catalyzed addition of HCl to acetylene. He also suggested the use of camphor and triphenyl phosphate as plasticizers for PVC. 

Impact modifiers typically added to PVC are generally comprised of emulsion polymerization of acrylates in the presence of rubber particles [103]. The acrylate composition is chosen to exhibit high grafting with the rubber phase and good compatibility (or miscibility) with PVC. Chlorinated polyethylene (CPE) can be miscible or immiscible with PVC, depending on the Cl content. With immiscible blends, chlorinated polyethylene can be used as an impact modifier, whereas in miscible blends, CPE acts as a permanent plasticizer for PVC. 

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. 

Another rubbery material, chlorinated polyethylene, can be made directly from branched polyethylene by postchlorination. A major use of this material is as a polymeric plasticizer for poly(vinyl chloride) (PVC). 

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics hexanol and 2-ethylhexanol are used as part of the catalyst system in the polymerization of acrylates, ethylene, and propylene (55) the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization initiator for vinyl chloride various trialkyl phosphites find usage as heat and light stabHizers for plastics organotin derivatives are used as heat stabHizers for PVC octanol improves the compatibHity of calcium carbonate filler in various plastics 2-ethylhexanol is used to make expanded polystyrene beads (56) and acrylate esters serve as pressure sensitive adhesives. 

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). 

Chlorinated paraffins are versatile materials and are used in widely differing appHcations. As cost-effective plasticizers, they are employed in plastics particularly PVC, mbbers, surface coatings, adhesives, and sealants. Where required they impart the additional features of fire retardance, and chemical and water resistance. In conjunction with antimony trioxide, they constitute one of the most cost-effective fire-retardant systems for polymeric materials, textiles, surface coatings, and paper products. Chlorinated paraffins are also employed as components in fat Hquors used in the leather industry, as extreme pressure additives in metal-working lubricants, and as solvents in carbonless copying paper. 

PVC, the polymerization product of chlorine-substituted ethylene derivatives, is probably the most widely used plastic for process plant construction. It is available in four different types rigid, high impact, high temperature and plasticized. 

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