Acetate Containing Terpolymers

In addition to the terpolymers previously mentioned in Sec. 9.4.1, the vinyl acetate-MA monomer pair has also been copolymerized with diethyl fumarate, lauryl fumarate, allyl acetate,vinyl crotonate, and vinyl chloride. 

The incorporation of small amounts of MA or maleic acid into vinyl chloride-vinyl acetate copolymers substantially improves their stability and adhesion.The introduction of the anhydride group also significantly increases the viscosity of the copolymers. Terpolymers of this type, having a 

The vinyl chloride-vinyl acetate-MA terpolymers are conveniently made in acetone, with acetyl peroxide initiator.Suspension polymerization techniques are used to prepare the terpolymer as a fine powder. A recent 

Interpolymerizing vinyl acetate, acrylic acid, and a monoalkyl ester of maleic or fumaric acid, in which the alkyl group contains 1-8 carbon atoms, gives materials used for sizing spun polyester or polyester blends.The formulations contained about 2% by weight of the maleate. 

Vinyl acetate terpolymers prepared with lauryl fumarate are claimed useful as ashless detergency additives, viscosity index improvers, dispersants, etc., for lubricating and additives to improve jet fuel 

---

The hydroxyl containing terpolymers have solubilities similar to those of the medium-to-low molecular weight vinyl chloride-vinyl acetate copolymers. This resin solubility system is shown in Figure 18. The ketones evaluated were methyl n-butyl ketone and methyl n-propyl ketone. 

Many esters such as butyl acetate and ethyl acetate are used as solvents for vinyl polymers. Figure 19 shows the solubility properties of a carboxyl containing terpolymer in various acetate solvents. These esters can also be used as diluents or to alter evaporation rates in mixed solvent systems. If a primary solvent such as a ketone is present, very high solids can be obtained. 

Nitroparaffins are effective vinyl solvents. The solubility characteristics of 2-nitropropane are shown in Figures 20 and 21. Toluene and xylene are true solvents for only the most soluble copolymers and terpolymers. These polymers are represented by the carboxyl containing terpolymer (Figure 12), the high solubility copolymers (VC-TFCE copolymer) (Figure 14), and a non-vinyl acetate containing copolymer (Figure 13). Heat had to be applied to the last polymer to obtain complete solution. 

Solution polymerization is used almost exclusively for production of copolymers of vinyl chloride and vinyl acetate and terpolymers containing maleates. The vinyl acetate copolymers contain 10-25% acetate, are highly uniform with a narrow molecular weight range, and are valuable mainly because of their unique solubility and film-forming characteristics. They find use as... 

Originality While terpolymer-positive resists containing acetal components are... 

Copolymers of acrylonitrile and methyl acrylate and terpolymers of acrylonitrile, styrene, and methyl methacrylate are used as bamer polymers. Acrylonitrile copolymers and multipolymers containing butyl acrylate, ethyl aciylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methaciylate. vinyl acetate, vinyl ethers, and vinylidene chlonde are also used in bamer films, laminates, and coatings. Environmentally degradable polymers useful in packaging are prepared from polymerization of acrylonitrile with styrene and methyl vinyl ketone. 

The compatibility of blends of poly (vinyl chloride) (PVC) and a terpolymer (TP) of ethylene, vinyl acetate, and carbon monoxide was investigated by dynamic mechanical, dielectric, and calorimetric studies. Each technique showed a single glass transition and that transition temperature, as defined by the initial rise in E" at 110 Hz, c" at 100 Hz, and Cp at 20°C/min, agreed to within 5°C. PVC acted as a polymeric diluent which lowered the crystallization temperature, Tc, of the terpolymer such that Tc decreased with increasing PVC content while Tg increased. In this manner, terpolymer crystallization is inhibited in blends whose value of (Tc — Tg) was negative. Thus, all blends which contained 60% or more PVC showed little or no crystallinity unless solvent was added. 

Terpolymers of ethylene, vinyl acetate and N15AK ac e prepared by adding the lal er two inder constant ethylene pressure into an initiated emulsifier solution containing polyvinyl alcohol, controlling the amount of unpolymerised vinyl acetate at any one time to be under This method enables ethylene to be copolymv... 

Some other interesting copolymers having properties of PVC thermal stabUizers, like poly[Af-(a-benzothiazolonylmethyl)methacrylate-co-methyl methacrylate] [45], of flame retardants like a terpolymer of styrene, acrylonitrile and a polymerizable perbrominated phenol [76] or poly[4-methacryloyloxy-2,3,5,6-tetrabromobenzyldi-phenyl phosphonate-co-methyl methacrylate] [104] (93), bioddes, mostly copolymers of monomers containing tris(n-butyl tin) or triphenyl tin moieties and alkyl acrylates, methacrylates, vinyl acetate, acrylonitrile, styrene or A-vinylpyrrolidone [105], e.g. a terpolymer of styrene, MMA and tri(n-butyl tin) itaconate [106] (94),... 

Pentachlorophenyl acrylate, (1), was terpolymerized with methyl methacrylate (MMA) and n-butyl acrylate (nBA) (Scheme III) to give a latex containing 537 solids and a pll of 4.7 which was adjusted to 6.8 by adding aqueous NaOH. The latex was stable up to pH =10. A small aliquot vzas coagulated and the resulting polymer purified. Its intrinsic viscosity was 3.1 /g and analysis indicated 2 mole percent (1), 587 CIA and 40" nBA. Similar terpolyner latices were prepared from acrylates (2) and (3) (Scheme III). Another terpolymer latex made from (3), vinyl acetate, and 2-ethylhexyl acrylate contained 547 solids. Tliese latices and their compositions are summarized in the Table 1 and a sample experimental procedure is given in the experimental section. 

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. 

Ethylene Copolymers. Ethylene-vinyl acetate copolymers differ according to their vinyl acetate content and molecular mass. With increasing vinyl acetate content, compatibility with paraffin waxes decreases, but that with other binders increases. Low molecular mass types containing 25-40% vinyl acetate are readily or sufficiently soluble in solvents. With a 40% vinyl acetate content, they can be combined with polar resins and nitrocellulose. Terpolymers with free carboxyl groups exhibit improved adhesion. Ethylene-vinyl acetate copolymers are primarily added to waxes to improve their properties, but are also used to increase flexibility and adhesion in paints, printing inks and adhesives, and for hot melt coatings. Ethylene-vinyl acetate copolymers have low water vapor and gas permeabilities (barrier effect). 

A polymer consisting of a single kind of monomer is called a homopolymer. A polymer manufactured from more than one kind of monomers is a copolymer. The most frequent copolymerization processes use two monomers (e. g. copolymerization of vinyl chloride with vinyl acetate, styrene with butadiene, etc.). If a polymer contains three different monomers, it may be called a terpolymer. The most common terpolymer is ABS consisting of acrylonitrile, butadiene, and styrene. 

---