Ethylene distortion

Incorporating an oxygen atom into a three membered nng requires its bond angle to be seriously distorted from the normal tetrahedral value In ethylene oxide for exam pie the bond angle at oxygen is 61 5°... 

The use of ABS has in recent years met considerable competition on two fronts, particularly in automotive applications. For lower cost applications, where demands of finish and heat resistance are not too severe, blends of polypropylene and ethylene-propylene rubbers have found application (see Chapters 11 and 31). On the other hand, where enhanced heat resistance and surface hardness are required in conjunction with excellent impact properties, polycarbonate-ABS alloys (see Section 20.8) have found many applications. These materials have also replaced ABS in a number of electrical fittings and housings for business and domestic applications. Where improved heat distortion temperature and good electrical insulation properties (including tracking resistance) are important, then ABS may be replaced by poly(butylene terephthalate). 

This polymer has a slightly stiffer chain and hence slightly higher melting point and heat distortion temperatures than poly(ethylene terephthalate). Films are available (Kodel-Kodak) which have been biaxially stretched about 200% from polymer with molecular weights of about 25 000. They are similar electrically to poly(ethylene terephthalate), are weaker mechanically but have superior resistance to water and in weathering stability. Some properties are given in Table 25.6. 

It has already been shown (e.g. Chapters 20 and 21) that the insertion of a p-phenylene into the main chain of a linear polymer increased the chain stiffness and raised the heat distortion temperature. In many instances it also improved the resistance to thermal degradation. One of the first polymers to exploit this concept commercially was poly(ethylene terephthalate) but it was developed more with the polycarbonates, polysulphone, poly(phenylene sulphides) and aromatic polyketones. 

Proper selection of plastic matrix fire retardants and property enhancers offers acceptable combinations of impact properties and heat-distortion temperature (HDT) values for fire retardant plastics. This can be demonstrated by fire retardant styrenics. Fire retardant enhancers have special interest as property enhancers for example the addition of a highly flammable material such as ethylene propylene diene terpolyer (EPDM), dramatically improves the bromine efficiency of octabromodiphenyl oxide in ABS by increasing char-forming without changing the Sb-Br reaction. 

Plastomer, a nomenclature constructed from the synthesis of the words plastic and elastomer, illustrates a family of polymers, which are softer (lower hexural modulus) than the common engineering thermoplastics such as polyamides (PA), polypropylenes (PP), or polystyrenes (PS). The common, current usage of this term is reshicted by two limitahons. First, plastomers are polyolehns where the inherent crystallinity of a homopolymer of the predominant incorporated monomer (polyethylene or isotactic polypropylene [iPP]) is reduced by the incorporahon of a minority of another monomer (e.g., octene in the case of polyethylene, ethylene for iPP), which leads to amorphous segments along the polymer chain. The minor commoner is selected to distort... 

Figure 9.8. A cartoon showing (a) the conical intersection for the [2+2] photocycloaddition of two ethylenes, drawn in the branching space corresponding to the distance between the two ethylenes R (Xj) and a trapezoidal distortion (Xj), and (b) an avoided crossing in a cross-section R (Xi).

Multiple bonds can be treated as ring structures with bent bonds. The distortions dealt with in the preceding paragraph must be taken into account. For example, in ethylene every C atom is surrounded tetrahedrally by four electron pairs two pairs mediate the double bond between the C atoms via two bent bonds. The tension in the bent bonds reduces the angle between them and decreases their repulsion toward the C-H bonds, and the HCH bond angle is therefore bigger than 109.5°. 

The bis(tV,7V -[dithiobis(ethylene)](4,6-dimethoxysalicylideneiminato)) zinc complex is characterized as a distorted tetrahedral complex with an N202 donor set from the tetradentate ligand.878... 

Relatively small changes in comonomer content can result in significant changes in physical or chemical properties. Polymer resin manufacturers exploit such relationships to control the properties of their products. The composition of a copolymer controls properties such as stiffness, heat distortion temperature, printability, and solvent resistance. For example, polypropylene homopolymer is brittle at temperatures below approximately 0 °C however, when a few percent ethylene is incorporated into the polymer backbone, the embrittlement temperature of the resulting copolymer is reduced by 20 °C or more. 

The interactions between the [W(calix)] metal fragment and the ethylene moiety has been analyzed using the extended Huckel calculations (see Chart 4).22b As supported by the structural parameters of 31, the dxz is no longer available for -it donation from the calixarene oxygens in the xz plane, thus explaining the strong C2v distortion of the [ [ Bu -cal ix 14]-(0)4 W] unit observed in the X-ray structure of 31, with the two WO bonds in the metal-ethylene plane ca. 0.2 A longer than... 

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