Hydrocarbons polymers

The possibility of distortions in several polymers, besides polyacetylene, have also been studied using NSBA and RVB ansatze (see, for instance Refs. 22 and 23). For the sake of space limitation, here we only report the ground-state Heisenberg energy for the undistorted polymeric strips (see Table 4). 

In Ref. 30 the values of Awd of Sec. 6.1 for w ranging from one to twelve and D from zero to (w — b)/2 (with Aw(-b-D) = Awd) have been obtain by a dimer-covering-counting transfer-matrix method as follows. 

the number of dimer-covering states in a Hf, subspace is 

Since for any dimer-covering singlet Dn- = Dn+i, fCnfCn+i is a block-diagonal symmetric matrix which does not depend on n (apart from the direction of the arrows in the local states that it relates) we can omit the sub-index. For L oo, the highest eigenvalue of the D block dominates, and 

Therefore, for iu=even, the ground state belongs to the non-degenerate D = 0 subspace, with 

Polymeric materials used as fuel components of pyrolants are classified into two types active polymers and inert polymers. Typical active polymers are nitropoly-mers, composed of nitrate esters containing hydrocarbon and oxidizer structures, and azide polymers, containing azide chemical bonds. Hydrocarbon polymers such as polybutadiene and polyurethane are inert polymers. When both active and inert polymers are mixed with crystalline oxidizers, polymeric pyrolants are formed. 

Azide polymers contain -N3 bonds within their molecular structures and burn by themselves to produce heat and nitrogen gas. Energetic azide polymers burn very rapidly without any oxidation reaction by oxygen atoms. GAP, BAMO, and AM-MOare typical energetic azide polymers. The appropriate monomers are cross-Hnked and co-polymerized with other polymeric materials in order to obtain optimized properties, such as viscosity, mechanical strength and elongation, and temperature sensitivities. The physicochemical properties GAP and GAP copolymers are described in Section 4.2.4. 

Hydrocarbon polymers (HCP) are used not only as fuel components but also as binders of crystalline oxidizers and metal powders in the formulation of pyrolants, similar to composite propellants and plastic-bonded explosives. There are many types of HCP, the physicochemical properties of which are dependent on their molecular structures. The viscosity, molecular mass, and functionality of the poly- 

Typical examples of HCP are hydroxy-terminated polybutadiene (HTPB), car-boxy-terminated polybutadiene (CTPB), hydroxy-terminated polyether (HTPE), hydroxy-terminated polyester (HTPS), and hydroxy-terminated polyacetylene (HTPA). The physicochemical properties of various types of HCP are described in Section 4.2.3. 

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Two main viscosity additive families are used hydrocarbon polymers and polymers containing ester functional groups. 

Generally speaking, hydrocarbon polymers are compatible with mineral oils and are undergoing considerable development. 

Polymethacrylates are less soluble than hydrocarbon polymers in mineral oils, they thicken less at low temperatures and are more effective at high temperatures. In this respect, it is important to note that the modification of rheoiogical properties is based on interactions between polymer and oil it will therefore be always dependent of the nature of oil. 

Hydrocarbon cracking Hydrocarbon feedstocks Hydrocarbon oils Hydrocarbon oxidation Hydrocarbon polymers... 

Hydrocarbon Polymers. It is difficult to produce perfluorocarbon polymers by the usual methods. Many monomers, such as hexafluoropropylene, polymerize only slowly because of the steric hindrance of fluorine. Furthermore, some monomers are not very stable and are difficult to synthesize. Direct fluorination can be used for the direct synthesis of fluorocarbon polymers (68—70) and for producing fluorocarbon coatings on the surfaces of hydrocarbon polymers (8,29,44—47,49,68—71). 

Some of the most difficult heterophase systems to characterize are those based on hydrocarbon polymers such as mbber-toughened polypropylene or other blends of mbbers and polyolefins. Eecause of its selectivity, RuO staining has been found to be usehil in these cases (221,222,230). Also, OsO staining of the amorphous blend components has been reported after sorption of double-bond-containing molecules such as 1,7-octadiene (231) or styrene (232). In these cases, the solvent is preferentially sorbed into the amorphous phase, and the reaction with OsO renders contrast between the phases. 

Other high molecular weight hydrocarbon polymers are not biodegradable, but oligomers of <7j -l,4-isoprene (83), butadiene (84), and styrene (85), are degradable. And there has been further confirmation of biodegradation of oligomeric ethylene (86). 

During this early period, a very ingenious free-radical route to polyesters was used to introduce weak linkages into the backbones of hydrocarbon polymers and render them susceptible to bio degradabihty (128—131). Copolymerization of ketene acetals with vinyl monomers incorporates an ester linkage into the polymer backbone by rearrangement of the ketene acetal radical as illustrated in equation 13. The ester is a potential site for biological attack. The chemistry has been demonstrated with ethylene (128—131), acryhc acid (132), and styrene (133). 

Introducing long aliphatic chains into a stabilizer molecule decreases volatility and increases solubility in hydrocarbon polymers. This improves performance. However, it also increases the equivalent weight of the active moiety. Di- and polyphenoHc antioxidants combine relatively low equivalent... 

Pitches can be transformed to a mesophase state by further chemical and physical operations. Heat treatment of conventional pitches results in additional aromatic polymeriza tion and the distillation of low molecular weight components. This results in an increase in size and concentration of large planar aromatic molecular species whereupon the precursor pitch is transformed to a mesophase state exhibiting the characteristics of nematic Hquid crystals (1). Additional heat treatment converts the mesophase pitch to an infusible aromatic hydrocarbon polymer designated as coke. 

This, the mass per unit volume, is a function of the weight of individual molecules and the way they pack. The hydrocarbons do not possess heavy atoms and therefore the mass of the molecule per unit volume is rather low. Amorphous hydrocarbon polymers generally have specific gravities of 0.86-1.05. Where large atoms are present, e.g. chlorine atoms, the mass per unit volume is higher and so PVC, a substantially amorphous polymer, has a specific gravity of about 1.4. 

The oxidation of hydrocarbons, including hydrocarbon polymers, takes the form of a free-radical chain reaction. As a result of mechanical shearing, exposure of ultraviolet radiation, attack by metal ions such as those of copper and manganese as well as other possible mechanisms, a hydrocarbon molecule breaks down into two radicals... 

Materials that promote the decomposition of organic hydroperoxide to form stable products rather than chain-initiating free radicals are known as peroxide decomposers. Amongst the materials that function in this way may be included a number of mercaptans, sulphonic acids, zinc dialkylthiophosphate and zinc dimethyldithiocarbamate. There is also evidence that some of the phenol and aryl amine chain-breaking antioxidants may function in addition by this mechanism. In saturated hydrocarbon polymers diauryl thiodipropionate has achieved a preeminent position as a peroxide decomposer. 

Manganese, copper, iron, cobalt and nickel ions can all initiate oxidation. Untinned copper wire can have a catastrophic effect on natural rubber compounds with which it comes into contact. Inert fillers for use in rubbers are usually tested for traces of such metal ions, particularly copper and manganese. The problem is perhaps less serious in saturated hydrocarbon polymers but still exists. 

Where there is a danger of contamination of a hydrocarbon polymer with such ions it is common practice to use a chelating agent which forms a complex with the metal. It is, however, important to stress that a chelating agent which effectively slows down oxidation initiated by one metal ion may have a prooxidant effect with another metal ion. Table 7.5 summarises some work by... 

Since polyethylene is a crystalline hydrocarbon polymer incapable of specific interaction and with a melting point of about 100°C, there are no solvents at room temperature. Low-density polymers will dissolve in benzene at about 60°C but the more crystalline high-density polymers only dissolve at temperatures some 20-30°C higher. Materials of similar solubility parameter and low molecular weight will, however, cause swelling, the more so in low-density polymers Table 10.5). 

Amongst hydrocarbon polymers polypropylene has been uniquely successful as a fibre. Its comparatively low cost and excellent wear together with resistance to staining have led to a major use in carpets as the tufting material. It has also found some use for blankets. As softer grades of fibre become available and... 

Many monomers have been copolymerised with ethylene using a variety of polymerisation systems, in some cases leading to commercial products. Copolymerisation of ethylene with other olefins leads to hydrocarbon polymers with reduced regularity and hence lower density, inferior mechanical properties, lower softening point and lower brittle point. 

Like NR, SBR is an unsaturated hydrocarbon polymer. Hence unvulcanised compounds will dissolve in most hydrocarbon solvents and other liquids of similar solubility parameter, whilst vulcanised stocks will swell extensively. Both materials will also undergo many olefinic-type reactions such as oxidation, ozone attack, halogenation, hydrohalogenation and so on, although the activity and detailed reactions differ because of the presence of the adjacent methyl group to the double bond in the natural rubber molecule. Both rubbers may be reinforced by carbon black and neither can be classed as heat-resisting rubbers. 

As already mentioned in previous sections ethylene may also be copolymerised with several non-hydrocarbon polymers. Some of these copolymers are elastomeric and they also have a measure of oil resistance. Two monomers used commercially are vinyl acetate and, the structurally very similar, methyl acrylate ... 

As a class the aliphatic polyalkenamers have low values due to a combination of low chain stiffness and low interchain attraction. The presence of double bonds has the effect of increasing the flexibility of adjacent single bonds (see Chapter 4) and overall this leads to a reduction in. Thus in the sequence from polydecenamer down to polypentenamer an increase in the double bond concentration leads to a lowering of Tg. On the other hand the Tg of polybutenamer, i.e. poly butadiene, is somewhat higher than that of polypentenamer, presumably because the proportion of stiff links, i.e. double bonds, becomes sufficiently high to override the flexibilising effect on adjacent chains. Consequently the polypentenamers have the lowest Tg values known for hydrocarbon polymers (cis- -114°C, trans- -97°C). 

The pure hydrocarbon nature of polystyrene gives it excellent electrical insulation characteristics, as a result of both the fundamentally good characteristics of the material and to the low water absorption of such a hydrocarbon polymer. The insulation characteristics are therefore well maintained in humid conditions. 

More to be expected of a more hydrocarbon polymer than PET is a somewhat lower water absorption, typically about 70% that of PET. With appropriate flame retardants, grades can have a UL V-0 rating at 0.8 mm thickness. 

Oil resistance demands polar (non-hydrocarbon) polymers, particularly in the hard phase. If the soft phase is non-polar but the haid phase polar, then swelling but not dissolution will occur (rather akin to that occurring with vulcanised natural rubber or SBR). If, however, the hard phase is not resistant to a particular solvent or oil, then the useful physical properties of a thermoplastic elastomer will be lost. As with all plastics and rubbers, the chemical resistant will depend on the chemical groups present, as discussed in Section 5.4. 

Brewis et al. used TOF-SIMS to determine the surface composition of hydrocarbon polymers after electrochemical pretreatment with nitric acid alone or in the presence of silver ions [58J. AgNO was generated by electrolysis of a 0.1 M solution of silver nitrate in 3.25 M nitric acid in the anode compartment of a... 

Standard two-compartment H cell. The catholyte consisted of 3.25 M nitric acid and was separated by a medium-porosity sintered glass frit. Experiments were also carried out to determine if surface oxidation of hydrocarbon polymers could be obtained in an electrolyte consisting only of nitric acid. 

Modification of the top electrode may also be achieved. This was done by adding a small amount of surfactant, such as an ether phosphate or an ether sulfate, to the spin-coal solution of the luminescent polymer [89[. The lipophobic ether chains segregate at the surface of the (predominantly) hydrocarbon polymer, becoming available for complexation with the aluminum cathode which is deposited on top. Thus, the dipole in the surfactant points away from the electrode and lowers its work function to improve the injection of electrons. 

In Figure 3-6 are plotted the k values (ordinates) for various chlorinated hydrocarbon polymers, the chlorine contents as determined analytically after fusion with sodium peroxide being the abscissas. The x-ray results were obtained in about one tenth the time required for the conventional analyses. The experimental points lie close to the solid line in Figure 3-6. The deviations from the solid line may be due to any one or any combination of the following causes. 

Fig. 3-6. Chlorine contents of chlorinated hydrocarbon polymers. Absorptio-metric results compared with those from conventional analyses. Crosses = experimental values dots = calculated values. (Liebhafsky, Smith, Tanis, and Winslow, Anal. Chem., 19, 861.)...

Chlorine, determination by x-ray emission spectrography, 328 in chlorinated hydrocarbon polymers, determination by x-ray absorptiometry, 79-82... 

The most spectacular case of products arising from a catalyst invention is that of the stereospecific hydrocarbon polymers made possible by the Ziegler-Natta work on aluminum alkyl/transition metal halide combinations around 1950. Until these catalysts existed, polypropylene, polyiso-prene, and cis-polybutadiene could not be made, and linear polyethylene could not be made cheaply. For each of these products, very large investments were needed in big plants and in market development before they were competitive with the established, big thermoplastics and rubbers. Entrance fees ran into tens of millions of dollars. 

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