Melting points, copolymer

Poly(cycloalkene)s obtained from the vinyl addition polymerization method exhibit extremely high melting points. The high melting points make the polymers unprocessable. For this reason, comonomers, such as ethene or propene are introduced to lower the melting points. Copolymers of this type are addressed as COCs. 

In Chap. 4 we discussed the crystallizability of polymers and the importance of this property on the mechanical behavior of the bulk sample. Following the logic that leads to Eq. (4.17), the presence of a comonomer lowers T for a polymer. Carrying this further, we can compare a copolymer to an alloy in which each component lowers the melting point of the other until a minimummelting eutectic is produced. Similar trends exist in copolymers. 

The many commercially attractive properties of acetal resins are due in large part to the inherent high crystallinity of the base polymers. Values reported for percentage crystallinity (x ray, density) range from 60 to 77%. The lower values are typical of copolymer. Poly oxymethylene most commonly crystallizes in a hexagonal unit cell (9) with the polymer chains in a 9/5 helix (10,11). An orthorhombic unit cell has also been reported (9). The oxyethylene units in copolymers of trioxane and ethylene oxide can be incorporated in the crystal lattice (12). The nominal value of the melting point of homopolymer is 175°C, that of the copolymer is 165°C. Other thermal properties, which depend substantially on the crystallization or melting of the polymer, are Hsted in Table 1. See also reference 13. 

Some cast (unoriented) polypropylene film is produced. Its clarity and heat sealabiUty make it ideal for textile packaging and overwrap. The use of copolymers with ethylene improves low temperature impact, which is the primary problem with unoriented PP film. Orientation improves the clarity and stiffness of polypropylene film, and dramatically increases low temperature impact strength. BOPP film, however, is not readily heat-sealed and so is coextmded or coated with resins with lower melting points than the polypropylene shrinkage temperature. These layers may also provide improved barrier properties. 

Peifluorinated ethylene—piopjiene (FEP) lesin [25067-11-2] is a copolymer of tetiafluoioethylene [116-14-3] (TFE) and hexafluoiopiopylene [116-15-4] (HEP) thus its blanched stmctuie contains units of —CF2—CF2— and units of —CF2—CF(CF2)—. It retains most of the desirable characteristics of polytetrafluoroethylene (PTFE) but with a melt viscosity low enough for conventional melt processing. The introduction of hexafluoropropylene lowers the melting point of PTFE from 325°C to about 260°C. 

The equimolar copolymer of ethylene and tetrafluoroethylene is isomeric with poly(vinyhdene fluoride) but has a higher melting point (16,17) and a lower dielectric loss (18,19) (see Fluorine compounds, organic-poly(VINYLIDENE fluoride)). A copolymer with the degree of alternation of about 0.88 was used to study the stmcture (20). Its unit cell was determined by x-ray diffraction. Despite irregularities in the chain stmcture and low crystallinity, a unit cell and stmcture was derived that gave a calculated crystalline density of 1.9 g/cm. The unit cell is befleved to be orthorhombic or monoclinic (a = 0.96 nm, b = 0.925 nm, c = 0.50 nm 7 = 96%. 

The projected equHibrium melting point of completely linear PE is 146—147°C (5) its highest actual melting point is 133—138°C. In the case of ethylene copolymers with a uniform compositional distribution, the melting point decreases almost linearly with copolymer composition for instance. 

Random insertion of ethylene as comonomer and, in some cases, butene as termonomer, enhances clarity and depresses the polymer melting point and stiffness. Propylene—butene copolymers are also available (47). Consequendy, these polymers are used in apphcations where clarity is essential and as a sealant layer in polypropylene films. The impact resistance of these polymers is sligbdy superior to propylene homopolymers, especially at refrigeration temperatures, but still vastiy inferior to that of heterophasic copolymers. Properties of these polymers are shown in Table 4. 

Some time earlier, Eastman-Kodak has been working on a novel polyester as an entry into the important polyester fiber market and had devised a new ahcychc diol, 1,4-cydohexanedimethanol [105-08-5] effectively made by exhaustive hydrogenation of dimethyl terephthalate. Reaction of the new diol with dimethyl terephthalate gave a crystalline polyester with a higher melting point than PET and it was introduced in the United States in 1954 as a new polyester fiber under the trade name Kodel (5). Much later the same polyester, now called PCT, and a cyclohexanedimethanol—terephthalate/isophthalate copolymer were introduced as mol ding resins and thermoforming materials (6). More recentiy stiU, copolymers of PET with CHDM units have been introduced for blow molded bottie resins (7). 

Properties of PGT. Typical properties of PCT are shown in Tables 5 and 6 (154). Table 5 shows the standard grades and Table 6 the PR grades. This material is in effect a copolymer of terephthaUc acid with two diols, the cis and trans forms of cyclohexanedimethanol. These two isomers do not form a eutectic copolymer with a minimum melting point, but instead the melting point rises monotonically between the two values of the pure... 

Du Pont s Zenite range of LCPs have been reintroduced. These materials are also LCP polyesters based on HBA copolymers with, it is beheved, various amounts of 4,4 -biphenol, terephthaUc acid, and naphthalene-2,6-dicatboxyhc acid (NDA) as comonomers. Their compositions are thus similar to those of XYDAR with added NDA to further reduce the melting point (235,236). 

Similarly, the random introduction by copolymerization of stericaHy incompatible repeating unit B into chains of crystalline A reduces the crystalline melting point and degree of crystallinity. If is reduced to T, crystals cannot form. Isotactic polypropylene and linear polyethylene homopolymers are each highly crystalline plastics. However, a random 65% ethylene—35% propylene copolymer of the two, poly(ethylene- (9-prop5lene) is a completely amorphous ethylene—propylene mbber (EPR). On the other hand, block copolymers of the two, poly(ethylene- -prop5iene) of the same overall composition, are highly crystalline. X-ray studies of these materials reveal both the polyethylene lattice and the isotactic polypropylene lattice, as the different blocks crystallize in thek own lattices. 

It has been discovered that styrene forms a linear alternating copolymer with carbon monoxide using palladium II—phenanthroline complexes. The polymers are syndiotactic and have a crystalline melting point - 280° C (59). Shell Oil Company is commercializing carbon monoxide a-olefin plastics based on this technology (60). 

The effect of different types of comonomers on varies. VDC—MA copolymers mote closely obey Flory s melting-point depression theory than do copolymers with VC or AN. Studies have shown that, for the copolymers of VDC with MA, Flory s theory needs modification to include both lamella thickness and surface free energy (69). The VDC—VC and VDC—AN copolymers typically have severe composition drift, therefore most of the comonomer units do not belong to crystallizing chains. Hence, they neither enter the crystal as defects nor cause lamellar thickness to decrease, so the depression of the melting temperature is less than expected. 

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