Polybutadiene , impact resistance

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). 

If high impact resistance is required, the PA can be modified with rubber particles.11,15 The blends are usually made by reactive compounding from maleic-anhydride-modified rubbers, such as, EPDM, EPR, polybutadiene, or SEBS. Partial amorphous PA with a high Tg combines to give a high dimensional stability and good solvent resistance with transparency. 

The tendency of polybutadiene to undergo chain transfer reactions can be used for the preparation of impact-resistance polymer where polystyrene has been grafted to polybutadiene as under ... 

The first move in this direction was to improve the weatherability of impact-resistant polystyrene. Because polybutadiene, the most widely used rubber in impact-resistant polystyrene, is unsaturated, it is sensitive to photooxidation, and impact-resistant polystyrene is therefore not suitable for outdoor applications. A saturated rubber might be able to help here. In the ABS sector this has been successfully tried out with acrylate rubber (77) and EPDM (78, 79), and the latter has also been used in impact-resistant polystyrene (80, 81) This development has elicited satisfactory responses only in certain areas and more work still has to be done. For instance, attempts have been made to improve resistance to weathering by using silicone rubber (82 ). This approach is effective, but economic factors still stand in its way. Further impetus may also be expected from stabilizer research. Hindered secondary amines (83), to which considerable attention has recently been paid, are a first step in this direction. 

High-impact grades present better impact resistances even at low temperature, higher flexibility and environmental stress cracking resistance (ESCR). The butadiene-styrene block copolymers are transparent but the alloys made of polystyrene and polybutadiene are not. 

Styrolux is an example of a nanostructured polymer which is used in food packaging. It is a polystyrene-polybutadiene block copolymer where polymer chains are build up of alternating polystyrene and polybutadiene blocks. These blocks appear as dark lamellae in the TEM image due to the staining of the polybutadiene with OSO4. This structured nanoscale architecture of the pol5mier, which can be controlled during manufacture, allows the optimum combination of impact resistance and transparency. 

Under the conditions of Example 5-23 the rubber phase of the end product shows an interesting micro-morphology. It consists of particles of 1-3 microns diameter into which polystyrene spheres with much lower diameters are dispersed. These included polystyrene spheres act as hard fillers and raise the elastic modulus of polybutadiene. As a consequence, HIPS with this micro-morphology has a higher impact resistance without loosing too much in stiffness and hardness. This special morphology can be visualized with transmission electron microscopy. A relevant TEM-picture obtained from a thin cut after straining with osmium tetroxide is shown in Sect. 2.3.4.14. 

Transparent, Impact-Resistant, Styrene/ Methyl Methacrylate Copolymer Grafted onto Polybutadiene... 

Acrylate rubbers which are employed in ASA contain no double bonds. For that reason, ASA is substantially more resistant to weathering than ABS. Owing to the polar acrylate component, ASA is also more resistant to stress cracking than ABS. ABS in turn has significant advantages in low-temperature impact resistance on account of the very low glass transition temperature of the polybutadiene rubber. 

The most important current graft copolymers include impact-resistant polystyrenes, in which a rubber, like polybutadiene (1-28) is dissolved in styrene ... 

The impact resistance of polypropylene at low temperature has been improved by polyblending with EPDM or E-P rubber to make possible the application of this material in the automotive industry. The low-temperature properties of polyamides such as nylon 6 and nylon 66 have been improved by polyblending with ethylene copolymers or specially grafted polybutadiene (45). 

Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer. The acrylonitrile and styrene copolymer is grafted onto polybutadiene. The properties of SAN are combined with a greatly improved impact resistance and heat distortion resistance. ABS terpolymers And application as engineering plastics, in household appliances, luggage, telephone housings, automotive parts, and many more. 

In addition to ABS, with polybutadiene as the elastifying component, there is another forerunner among the polymer products formulated for low-temperature impact resistance, PVC-U. Elastifying ligands include EVAC, EVAC/VC graft polymer, PAEA C (polyacrylic acid ester/vinyl chloride copolymer), ACE (acrylic ester/MMA graft polymer) as well as the chlorinated low-pressure polyethylene PE-C in use for over 35 years. All of the polymer blends listed here are suitable for outdoor applications since they contain no unsaturated components. Polybutadiene-modified products are better suited to interior applications, for example MBS, a methylmethacrylate/butadiene/styrene graft polymer [55]. 

Figure 2.4. Rubber membrane structure of impact-resistant polystyrene (6% polybutadiene 22% rubber phase volume). This graft-copolymer morphology, containing a fine structure within the discontinuous phase, is brought about by agitation during the early stages of polymerization. (Wagner and Robeson, 1970.)...

Poly(vinyl chloride) (PVC) homopolymer is a stiff, rather brittle plastic with a glass temperature of about 80°C. While somewhat more ductile than polystyrene homopolymer, it is still important to blend PVC with elastomer systems to improve toughness. For example, methyl methacrylate-butadiene-styrene (MBS) elastomers can impart impact resistance and also optical clarity (see Section 3.3). ABS resins (see Section 3.1.2) are also frequently employed for this purpose. Another of the more important mechanical blends of elastomeric with plastic resins is based on poly(vinyl chloride) as the plastic component, and random copolymers of butadiene and acrylonitrile (AN) as the elastomer (Matsuo, 1968). On incorporation of this elastomeric phase, PVC, which is ordinarily a stiff, brittle plastic, can be toughened greatly. A nonpolar homopolymer rubber such as polybutadiene (PB) is incompatible with the polar PVC. Indeed, electron microscopy shows... 

Figure 3.15. Effect of blend type and rubber content on Izod impact resistance of polybutadiene/polystyrene blends. (Haward and Mann, 1964 Lannon and Hoskins, 1965.)...

Graft polymerization of the monomer from which the matrix is built-up, onto the dispersed phase, e.g., graft polymerization of styrene onto polybutadiene during the preparation of impact-resistant polystyrene,... 

MABS is similar to ABS except for the addition of an additional monomer, usually methyl methacrylate. MABS is an amorphous, clear, transparent material with thermal and mechanical properties like ABS. The transparency is achieved by matching the refractive indices of the matrix resin (the transparent acrylate—acrylonitrile—styrene polymer) with the polybutadiene rubber impact modifier. MABS has the highest impact resistance of all the styrenic plastics. Sometimes called transparent... 

Generally, ABS resins are produced in the form of a bimodal type comprised of two kinds of particle sizes for better surface and impact resistance properties. In this case, either (1) the graft polymerization is also accomplished in the concurrent presence of two kinds of polybutadiene latex having different particle sizes, or (2) respective polybutadiene latexes, after the graft polymerization is accomphshed, may be mixed in a certain ratio to prepare the product. The particle size is generally in the range of 0.1 to 0.4 xm. 

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