Copolymers mechanical properties

PBT (45 %)/ carbodiimide-functionalized PPE (45 %)/SEBS (10 %) TSE/PPE functionalized in solution with 4,4 -bis (4-cyclohexylcarbodiimido) diphenylmethane/ mechanical properties/copolymer analysis by selective solvent extraction/PET also used Han and Gately 1987... 

The focus of this chapter is on the improvement in compatibilization, which can be achieved in an engineering process. Detailed understanding and analysis of the compatibilization achieved was not evaluated rigorously here. The compatibilization was considered to be successful when some of the key parameters, e.g. mechanical properties, copolymer content, morphology, etc., were significantly improved compared to a simple mechanical mixture of the same polymer components. 

In block copolymers [8, 30], long segments of different homopolymers are covalently bonded to each otlier. A large part of syntliesized compounds are di-block copolymers, which consist only of two blocks, one of monomers A and one of monomers B. Tri- and multi-block assemblies of two types of homopolymer segments can be prepared. Systems witli tliree types of blocks are also of interest, since in ternary systems the mechanical properties and tire material functionality may be tuned separately. 

Block copolymers are closer to blends of homopolymers in properties, but without the latter s tendency to undergo phase separation. As a matter of fact, diblock copolymers can be used as surfactants to bind immiscible homopolymer blends together and thus improve their mechanical properties. Block copolymers are generally prepared by sequential addition of monomers to living polymers, rather than by depending on the improbable rjr2 > 1 criterion in monomers. 

Much more information can be obtained by examining the mechanical properties of a viscoelastic material over an extensive temperature range. A convenient nondestmctive method is the measurement of torsional modulus. A number of instmments are available (13—18). More details on use and interpretation of these measurements may be found in references 8 and 19—25. An increase in modulus value means an increase in polymer hardness or stiffness. The various regions of elastic behavior are shown in Figure 1. Curve A of Figure 1 is that of a soft polymer, curve B of a hard polymer. To a close approximation both are transpositions of each other on the temperature scale. A copolymer curve would fall between those of the homopolymers, with the displacement depending on the amount of hard monomer in the copolymer (26—28). 

Nitrile mbber finds broad application in industry because of its excellent resistance to oil and chemicals, its good flexibility at low temperatures, high abrasion and heat resistance (up to 120°C), and good mechanical properties. Nitrile mbber consists of butadiene—acrylonitrile copolymers with an acrylonitrile content ranging from 15 to 45% (see Elastomers, SYNTHETIC, NITRILE RUBBER). In addition to the traditional applications of nitrile mbber for hoses, gaskets, seals, and oil well equipment, new applications have emerged with the development of nitrile mbber blends with poly(vinyl chloride) (PVC). These blends combine the chemical resistance and low temperature flexibility characteristics of nitrile mbber with the stability and ozone resistance of PVC. This has greatly expanded the use of nitrile mbber in outdoor applications for hoses, belts, and cable jackets, where ozone resistance is necessary. 

Mechanical properties are retained up to 200°C, even in continuous service, which is better than with most plastics. At high temperatures, these copolymers react with duorine, duorinating agents, and molten alkaU metals. They are commercially available under the Du Pont trademark Tedon FEP duorocarbon resin. A similar product is manufactured by Daikin Kogyo of Japan and sold under the trademark Neodon. The People s RepubHc of China also manufactures some FEP products. 

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Mech nic lProperties. Extensive Hsts of the physical properties of FEP copolymers are given in References 58—63. Mechanical properties are shown in Table 3. Most of the important properties of FEP are similar to those of PTFE the main difference is the lower continuous service temperature of 204°C of FEP compared to that of 260°C of PTFE. The flexibiUty at low temperatures and the low coefficients of friction and stabiUty at high temperatures are relatively independent of fabrication conditions. Unlike PTFE, FEP resins do not exhibit a marked change in volume at room temperature, because they do not have a first-order transition at 19°C. They ate usehil above —267°C and are highly flexible above —79°C (64). 

Thermal Properties. Modified ETFE copolymer has a broad operating temperature range up to 150°C for continuous exposure (24). Cross-linking by radiation improves the high temperature capabiUty further. However, prolonged exposure to higher temperatures gradually impairs the mechanical properties and results in discoloration. 

Mechanical Properties. Mechanical characteristics of ethylene copolymers are functions of their stmctural characteristics. 

A family of PEO/PET copolymers has been synthesized and the characterized stmctures found to be close to those expected in theory (41). A wide degradation envelope has been achieved by adjusting the PEO-to-PET ratio. Mechanical properties prove useful for medical appHcations, and the 60/40 PEO/PET composition is reported as optimal. 

Copolymerisation also affects morphology under other crystallisation conditions. Copolymers ia the form of cast or molded sheets are much more transparent because of the small spheruHte size. In extreme cases, crystallinity cannot be detected optically, but its effect on mechanical properties is pronounced. Before crystallisation, films are soft and mbbery, with low modulus and high elongation. After crystallisation, they are leathery and tough, with higher modulus and lower elongation. 

Table 6. Mechanical Properties of High Vinylidene Chloride Copolymers...

The dynamic mechanical properties of VDC—VC copolymers have been studied in detail. The incorporation of VC units in the polymer results in a drop in dynamic modulus because of the reduction in crystallinity. However, the glass-transition temperature is raised therefore, the softening effect observed at room temperature is accompanied by increased brittleness at lower temperatures. These copolymers are normally plasticized in order to avoid this. Small amounts of plasticizer (2—10 wt %) depress T significantly without loss of strength at room temperature. At higher levels of VC, the T of the copolymer is above room temperature and the modulus rises again. A minimum in modulus or maximum in softness is usually observed in copolymers in which T is above room temperature. A thermomechanical analysis of VDC—AN (acrylonitrile) and VDC—MMA (methyl methacrylate) copolymer systems shows a minimum in softening point at 79.4 and 68.1 mol % VDC, respectively (86). 

Copolymers of acrylonitrile [107-13-1] are used in extmsion and molding appHcations. Commercially important comonomers for barrier appHcations include styrene and methyl acrylate. As the comonomer content is increased, the permeabiUties increase as shown in Figure 3. These copolymers are not moisture-sensitive. Table 7 contains descriptions of three high nitrile barrier polymers. Barex and Cycopac resins are mbber-modified to improve the mechanical properties. 

Reportedly, OjoCdiaHylbispheaol A is an attractive comonomer for bismaleimides because the corresponding copolymer is tough and temperature resistant (41). Toughness, however, is a function of the BMI—diaHylbisphenol A ratio employed. In one study optimized toughness properties were achieved when BMI and diaHylbisphenol were employed at a close to 2 1 molar ratio (42). In Table 9, the mechanical properties of BMI—bis(3-allyl-4-hydroxyphenyl)-7 -diisopropylbenzene resias are provided, showiag optimized properties for the 60/40 BMI—diaHylbisphenol composition. The 0,(9 diaHylbisphenol A is commercially available under the trademark Matrimide 5292. Another bisaHylphenyl compound is available from SheH Chemical Company/Technochemie under the trademark COMPIMIDE 121. 

Copolymers of chlorotrifluoroethylene and ethylene were introduced by Allied Chemicals under the trade name Halar in the early 1970s. This is essentially a 1 1 alternating copolymer compounded with stabilising additives. The polymer has mechanical properties more like those of nylon than of typical fluoroplastic, with low creep and very good impact strength. Furthermore the polymers have very good chemical resistance and electrical insulation properties and are resistant to burning. They may be injection moulded or formed into fibres. 

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