Styrene-acrylonitrile -grafted

Not only ate ABS polymers useful engineering plastics, but some of the high mbber compositions are excellent impact modifiers for poly(vinyl chloride) (PVC). Styrene—acrylonitrile-grafted butadiene mbbers have been used as modifiers for PVC since 1957 (87). 

Ligno Styrene, acrylonitrile Grafting of styrene in methanolic solution [190,... 

Table 9. Styrene-acrylonitrile grafting onto isobutene copolymers ... 

Methylstyrene-styrene-acrylonitrile-grafted polybutadiene or with maleated styrene-methyl-methacrylate-butadiene (ABS-MA) processability, high impact strength, mechanical properties Dufour, 1988... 

Elastomeric silicones with methyl substituents Methylstyrene-styrene-acrylonitrile-grafted polybutadiene Thermoplastic copolymer from a-methyl styrene and acrylonitrile... 

Suprel Styrene-acrylonitrile grafted on PVC, SAN or ABS/PVC alloys Vista Chemical Co. 

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

In all manufacturing processes, grafting is achieved by the free-radical copolymerization of styrene and acrylonitrile monomers in the presence of an elastomer. Ungrafted styrene—acrylonitrile copolymer is formed during graft polymerization and/or added afterward. 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

At one time butadiene-acrylonitrile copolymers (nitrile rubbers) were the most important impact modifiers. Today they have been largely replaced by acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-buta-diene-styrene (MBS) terpolymers, chlorinated polyethylene, EVA-PVC graft polymers and some poly acrylates. 

To produce the Type 2 polymers, styrene and acrylonitrile are added to polybutadiene latex and the mixture warmed to about 50°C to allow absorption of the monomers. A water-soluble initiator such as potassium persulphate is then added to polymerise the styrene and acrylonitrile. The resultant materials will be a mixture of polybutadiene, polybutadiene grafted with acrylonitrile and styrene, and styrene-acrylonitrile copolymer. The presence of graft polymer is essential since straightforwsird mixtures of polybutadiene and styrene-acrylonitrile copolymers are weak. In addition to emulsion processes such as those described above, mass and mass/suspension processes are also of importance. 

Polypropylene block and graft copolymers are efficient blend compatibilizers. These materials allow the formation of alloys, for example, isotactic polypropylene with styrene-acrylonitrile polymer or polyamides, by enhancing the dispersion of incompatible polymers and improving their interfacial adhesion. Polyolefinic materials of such types afford property synergisms such as improved stiffness combined with greater toughness. 

The authors of [317] investigated compositions based on PS, PMMA and styrene-acrylonitrile copolymer grafted to various fillers and found that it was possible, in this manner, to obtain particles with a grafted polymeric coating of sufficiently homogeneous thickness. 

The electrophilic functions most commonly used in grafting onto processes are ester 141 144), benzylic halide 145,146) and oxirane, 47). Other functions such as nitrile or anhydride could be used as well. The backbone is a homopolymer (such as PMMA) or a copolymer containing both functionalized and unfunctionalized units. Such species can be obtained either by free radical copolymerization (e.g. styrene-acrylonitrile copolymer) or by partial chemical modification of a homopolymer (e.g. 

Second step polymerisation of styrene (to get HIPS) or styrene and acrylonitrile (to get ABS) with partial grafting of PS or SAN (styrene/ acrylonitrile) sequences onto the PB chains. 

Styrene-acrylonitrile (SAN) copolymers have a high natural affinity for PBT, giving blends with good mechanical properties. If the SAN copolymer is grafted... 

E4 polystyrene-Z)/ocA -[l,4-polybutadiene-grq/Z -poly(styrene-co-acrylonitrile)] (copolymer from styrene and acrylonitrile grafted to a 1,4-polybutadiene-polystyrene two-block copolymer at unspecified sites of some of the but-2-ene-... 

Although this method yields a mixture of homopolymer and graft copolymer, and probably also ungrafted backbone polymer, some of the systems have commercial utility. These are high-impact polystyrene (HIPS) [styrene polymerized in the presence of poly(l,3-buta-diene)], ABS and MBS [styrene-acrylonitrile and methyl methacrylate-styrene, respectively, copolymerized in the presence of either poly(l,3-butadiene) or SBR] (Sec. 6-8a). 

Metallation of a polymer by treatment with strong base, for example, t-butyllithium, yields polymeric anions that initiate the grafting of monomers such as styrene, acrylonitrile, and... 

Example 5-23) and of ABS-polymers (made from acrylonitrile, butadiene, and styrene), whereby grafting occurs in situ at the beginning of the polymerization process. The formed graft copolymers act in two ways As emulsifiers during the polymerization process and, secondly, in the solid end product as compatibilizer between the thermoplastic hard phase and the rubber-elastic dipersed phase (already in concentrations below 3%). 

The production of ABS and SAN resins consumes the second largest quantity of acrylonitrile. The ABS resins are produced by grafting acrylonitrile and styrene onto polybutadiene or a styrene-butadiene copolymer and contain about 25 wt% acrylonitrile. These products are used to make components for automotive and recreational vehicles, pipe fittings, and appliances. The SAN resins are styrene-acrylonitrile copolymers containing 25-30 wt% of acrylonitrile. The superior clarity of SAN resin allows it to be used in automobile instrument panels, for instrument lenses and for houseware items (Langvardt, 1985 Brazdil, 1991). 

Z. Zhou, N. Liu, and H. Huang, Reactivity of acrylonitrile-butadiene-styrene terpolymer grafted with long-chain unsaturated carboxylic acids, Polymer, 45(21) 7109-7116, September 2004. 

ASA structural latexes have been synthesized in a two stage seeded emulsion polymerization. In the first stage, partially crosslinked poly(n-butyl acrylate) and poly( -butyl acrylate-sfaf-2-ethylhexyl acrylate) rubber cores are synthesized. In the second stage, a hard styrene acrylonitrile copolymer (SAN) shell is grafted onto the rubber seeds (16). 

High impact strength thermoplastic resins can be prepared by mixing a styrene/acrylonitrile copolymer with rubber particles. In general, the styrene/acrylonitrile copolymer is prepared by the graft copolymerization of styrene and acrylonitrile in the presence of rubber itself (17). 

H.P. Siebel and H.-W. Otto, Styrene- acrylonitrile copolymers blended with graft copolymers of styrene onto butadiene-alkyl acrylate-vinyl alkyl ether terpolymers, US Patent 3280219, assigned to BASF AG, October 18,1966. 

A critical appreciation of this review shows that there has been a large interest on the subject in the last twenty years. Most of the papers and patents deal with immersion techniques. Irradiation with gamma-rays seems to be the field to which more attention has been given. Practically all common unsaturated monomers have been studied more or less extensively, in specially styrene, acrylonitrile, methyl methacrylate, and vinyl acetate, respectively. In more recent years, grafts have been attached to the backbone polymer through reactions of the branch polymer with active centers generated on the polyamide matrix. 

Already in 1955 Polymer Corporation (63) had applied for a patent on a process of treating naturally occurring polymeric substances or their derivatives with ozone containing inert gases and subsequently contacting the ozonized substrates with polymerizable monomers. In the presence of redox activators butadiene, acrylonitrile, and styrene were grafted onto cellulose, starch, casein, gelatin, and rubber. 

In the late fifties Regie Nationale des Usines Renault (86) described the preparation of allyl ethers through reaction of alkali cellulose with allyl halides in carbon tetrachloride or benzene. With products having degrees of substitution between 0.2 to 0.8 graft copolymerization could be achieved when activated by pretreatment with air or ozone or by initiation with peroxide catalysts with styrene, acrylonitrile, vinyl acetate, or acrylates. 

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