Styrene-butadiene rubber copolymer grafting

The MABS copolymers are prepared by dissolving or dispersing polybuiadiene rubber in a methyl methacrylate—acrylonitrile—styrene monomer mixture. MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene rubber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid polytvinyl chloride). 

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... 

Another widely used copolymer is high impact polystyrene (PS-HI), which is formed by grafting polystyrene to polybutadiene. Again, if styrene and butadiene are randomly copolymerized, the resulting material is an elastomer called styrene-butadiene-rubber (SBR). Another classic example of copolymerization is the terpolymer acrylonitrile-butadiene-styrene (ABS). Polymer blends belong to another family of polymeric materials which are made by mixing or blending two or more polymers to enhance the physical properties of each individual component. Common polymer blends include PP-PC, PVC-ABS, PE-PTFE and PC-ABS. 

The first patent on HIPS, a blend of synthetic rubber and transparent polystyrene, was granted in Great Britain as early as 1912. The first graft copolymerization of styrene in the presence of rubber was carried out by Ostromislensky [5]. The decline in the demand for styrene monomer and styrene-butadiene rubber and the simultaneous availability of natural rubber on the world market in the late 1940s drove the development of styrene copolymer processes. 

Graft copolymers are important as elastomeric (e.g., styrene-butadiene rubber (SBR)) and high-impact polymers (e.g., high-impact polystyrene and acrylonitrile-butadiene-styrene (ABS)). 

SMA copolymers and terpolymers have also been used for blending with PVC to improve the heat distortion temperature and processability of PVC. These blends also contain a rubbery component for impact modification that is usually a high rubber ABS or a polymethyl methacrylate grafted styrene-butadiene rubber (MBS). For improved weatherability, acrylic rubber modified PVC has been used for blending with SMA copolymers and terpolymers (Table 15.4). The market for SMA/PVC blends is still relatively low in volume with only a few applications such as in business machine housings as a low cost replacement for flame retarded ABS. 

Addition of rubbery materials, however, does improve the impact resistance of polystyrene. This is therefore done extensively. The most common rubbers used for this purpose are butadiene-styrene copolymers. Some butadiene homopolymers are also used, but to a lesser extent. The high-impact polystyrene is presently prepared by dissolving the rubber in a styrene monomer and then polymerizing the styrene. This polymerization is either done in bulk or in suspension. The product contains styrene-butadiene rubber, styrene homopolymer, and a considerable portion of styrene-graft copolymer that forms when polystyrene radicals attack the rubber molecules. The product has very enhanced impact resistance. 

Styrene and butadiene can be put together in various ways so as to produce a wide range of rubbers and plastics. A en each is polymerized on its own then homopolymers are produced, for example, polystyrene and polybutadiene. When styrene is polymerized onto polybutadiene then the graft copolymer, TPS may be produced. If the two monomers are polymerized together then the random copolymer known as styrene butadiene rubber (SBR) is obtained this contains approximately 75% styrene and 25% butadiene. 

Kalf et al. studied the effect of grafting cellulose acetate and methylmethacrylate as compatibilizers on acrylonitrile butadiene rubber (NBR) and styrene-butadiene rubber (SBR) blends. Morphology studies of the samples show an improvement in interfacial adhesion between the NBR and SBR phases in the presence of the prepared compatibilizing agents. The authors also reported the samples with grafted compatibilizers showed superior crosslink density and thermal stability, as compared to the blends without graft copolymers. ... 

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. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

Isocyanates can be added to solvent-borne CR adhesive solutions as a two-part adhesive system. This two-part adhesive system is less effective with rubber substrates containing high styrene resin and for butadiene-styrene block (thermoplastic rubber) copolymers. To improve the specific adhesion to those materials, addition of a poly-alpha-methylstyrene resin to solvent-borne CR adhesives is quite effective [76]. An alternative technique is to graft a methacrylate monomer into the polychloroprene [2]. 

Problem 31.7 1 Irradiation of poly(-l,3-butadiene), followed by addition of styrene, yields a graft copolymer that is used to make rubber soles for shoes. Draw the structure of a representative segment of this styrene-butadiene graft copolymer. 

Similar results were obtained by shear blending of two synthetic elastomers (45). The formation of a block or graft copolymer during the process of mixing butadiene rubber (SKB) and styrene-containing rubber (SKS-30A) was postulated by Slonimskii and Reztsova (49). They claimed that the anomalies observed in the dependences on composition of the mechanical properties of a mixture of two mutually insoluble rubbers after vulcanization may be reduced by increasing the part played by the mechanical mixing (inert atmosphere, reduction of radical acceptors, intensity of mechanical action). 

Styrene monomer and a styrene/butadiene copolymer are fed to the first reaction zone. The polymerization is initiated either thermally or chemically. Many chemical initiators are available such as ferf-butyl peroxybenzoate and ferf-butyl peracetate. Conditions are established to prevent a phase inversion or the formation of discrete rubber particles in the first reaction zone. The conversion in the first reaction zone should be 5-12%. An important function of the first reaction zone is to provide an opportunity for grafting of the styrene monomer to the elastomer (8). 

PVC can be blended with numerous other polymers to give it better processability and impact resistance. For the manufacture of food contact materials the following polymerizates and/or polymer mixtures from polymers manufactured from the above mentioned starting materials can be used Chlorinated polyolefins blends of styrene and graft copolymers and mixtures of polystyrene with polymerisate blends butadiene-acrylonitrile-copolymer blends (hard rubber) blends of ethylene and propylene, butylene, vinyl ester, and unsaturated aliphatic acids as well as salts and esters plasticizerfrec blends of methacrylic acid esters and acrylic acid esters with monofunctional saturated alcohols (Ci-C18) as well as blends of the esters of methacrylic acid butadiene and styrene as well as polymer blends of acrylic acid butyl ester and vinylpyrrolidone polyurethane manufactured from 1,6-hexamethylene diisocyanate, 1.4-butandiol and aliphatic polyesters from adipic acid and glycols. 

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