Styrene-acrylonitrile copolymer grafting

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. 

Styrene-acrylonitrile copolymer/grafted acrylic ester elastomer, SAN/acrylic elastomer... 

Acrylonitrile-butadiene-styrene copolymers (ABS) are random styrene-acrylonitrile copolymers grafted to butadiene, which are amorphous, opaque, and process easily. The properties depend on the ratios of the comonomers used. ABS is used in cosmetics packaging, and has been used in margarine tubs. 

ABS comprises the dispersed phase of styrene/acrylonitrile copolymer grafted on polybutadiene rubber and the continuous phase of styrene/acry-lonitrile copolymer. The use of SAN grafted on polybutadiene rubber provides high impact strength, processability, chemical resistance, staining property, etc., as the characteristics peculiar to ABS resins. 

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). 

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. 

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. 

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). 

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. 

Sonic Modulus. If crack or craze branching is the operative mech-nism in toughening, toughness should be directly related to the difference in sonic speeds in matrix and dispersed phases. Experiments to confirm this effect were undertaken using three commercial ABS resins. These were selected to represent the three main rubber types encountered commercially an acrylonitrile/butadiene copolymer rubber, a butadiene rubber with grafted styrene/acrylonitrile copolymer, and a block polymer of... 

Table II. Weight Percent of Grafted Styrene—Acrylonitrile Copolymer ...

Acrylonitrile-Butadiene-Styrene (ABS) Copolymers. This basic three-monomer system can be tailored to yield resins with a variety of properties. Acrylonitrile contributes heat resistance, high strength, and chemical resistance. Butadiene contributes impact strength, toughness, and retention of low-temperature properties. Styrene contributes gloss, processibility, and rigidity. ABS polymers are composed of discrete polybutadiene particles grafted with the styrene-acrylonitrile copolymer these are dispersed in the continuous matrix of the copolymer. 

Various patents on the homopolymerization of BD in the presence of styrene are available [581-590]. According to these patents, St is used as a solvent in which BD is selectively polymerized by the application of NdV/DIBAH/EASC. At the end of the polymerization a solution of BR in St is obtained. In subsequent reaction steps the unreacted styrene monomer is either polymerized radically, or acrylonitrile is added prior to radical initiation. During the subsequent radical polymerization styrene or styrene/acrylonitrile, respectively, are polymerized and ris-l,4-BR is grafted and partially crosslinked. In this way BR modified (or impact modified) thermoplast blends are obtained. In these blends BR particles are dispersed either in poly(styrene) (yielding HIPS = high impact poly(styrene) or in styrene-acrylonitrile-copolymers (yielding ABS = acrylonitrile/butadiene/ styrene-terpolymers). In comparison with the classical bulk processes for HIPS and ABS, this new technology allows for considerable cost reductions... 

The styrene-acrylonitrile copolymers were prepared in the form of a thin film. The graft polybutadiene solution was coated on a glass slide. But, for the graft polymer containing acrylonitrile, it was undesirable to use the glass slide because of the induced orientation, therefore, we used a Mylar film to support a thick smooth film of the graft rubber. 

Copolymers of styrene include a large group of random, graft, and block copolymers. Those with a high proportion of acrylonitrile used in barrier films as well as others such as methacrylic-butadiene-styrene copolymer (MBS) plastic is used as modifiers in PVC, SAN, ABS, ASA, etc. The styrene-acrylonitrile copolymer (SAN) is the most important when considering volume and number of applications. 

Acrylonitrile-Ethylene/Propylene-Styrene Copolymer AES is a terpolymer obtained by grafting styrene-acrylonitrile copolymer to ethylene-propylene or ethylene-propylene-diene monomer rubber. Similar to ABS except with improved weathering resistance. 

Impact Properties. Chemical Nature of the Rubber. If the rubber is too compatible with the matrix, it will dissolve in the rigid material and disperse on a molecular scale. Little or no reinforcement will occur since the rubber particles become smaller than the radius of the tip of a stress-induced propagating crack. However if it is highly incompatible, good adhesion between rubber and matrix cannot be obtained. For example polybutadiene rubber adheres poorly to a styrene/acrylonitrile copolymer, but a nitrile rubber adheres well to the SAN copolymer. If grafting techniques are used however, compatibility is less of a problem since the rubber is chemically bonded to the matrix. 

Like HIPS, acrylonitrile-styrene-butadiene (ABS) polymers have polybutadiene rubber incorporated into styrene-acrylonitrile copolymer (SAN), giving a resin consisting of a two-phase system with inclusions of rubber in a continuous glassy matrix. Again, development of the best properties requires grafting between the glassy and rubbery phases. 

Selected blends of styrene-acrylonitrile copolymer (30 to 55%), a styrene-butadiene copolymer grafted with styrene and acrylonitrile (45 to 70%), and a coal-tar pitch (0 to 25%), were prepared. Physical properties of the experimental blends were determined and statistical techniques were used to develop empirical equations relating these properties to blend composition. Scheff canonical polynominal models and response surfaces provided a thorough understanding of the mixture system. These models were used to determine the amount of coal-tar pitch that could be incorporated into ABS compounds that would still meet ASTM requirements for various pipe-material designations. ... 

There is an increasing market for higher resilience foams using the so-called polymer polyols. Amongst the earliest to become established were suspensions of styrene-acrylonitrile copolymer in the polyol. A variation involved some grafting of SAN, either instead of or in addition to the use of a suspension. 

An ABS sample prepared in our laboratory was used to develop the separation technique. Its composition was (wt %) butadiene, 20 acrylonitrile, 21 and styrene, 59. The ABS powder was dispersed in methyl ethyl ketone (MEK) at 1 wt % concentration. MEK was chosen because it is a good solvent for styrene/acrylonitrile copolymers, it is a poor solvent for polybutadiene, and its density is lower than that of polybutadiene and therefore lower than the density of the graft copolymer. 

Styrene-acrylonitrile copolymer (SAN) and its impact modified versions, viz., ABS (polybutadiene rubber grafted SAN), ASA (acrylate rubber grafted SAN), AES (EPDM rubber grafted SAN)... 

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