Polyamide melting transition

We studied the polyamidation in the solid phase process of nylon 4,6, which has a high melting transition (264 - 320 C) and... 

These first polyester fibers had melt transitions (T ) too low for use as textile fibers, and they were not investigated further. Carothers then turned his attention to the reactions of dicarboxylic acids and diamines to form polyamides and, in 1934, synthesized nylon 66, the first purely synthetic fiber. Nylon 66 is so named because it is synthesized from two different monomers, each containing six carbon atoms. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

In the area of moleculady designed hot-melt adhesives, the most widely used resins are the polyamides (qv), formed upon reaction of a diamine and a dimer acid. Dimer acids (qv) are obtained from the Diels-Alder reaction of unsaturated fatty acids. Linoleic acid is an example. Judicious selection of diamine and diacid leads to a wide range of adhesive properties. Typical shear characteristics are in the range of thousands of kilopascals and are dependent upon temperature. Although hot-melt adhesives normally become quite brittle below the glass-transition temperature, these materials can often attain physical properties that approach those of a stmctural adhesive. These properties severely degrade as the material becomes Hquid above the melt temperature. 

With DMA the effect of temperature on the modulus can be studied. By increasing the temperature from -150 to 300°C, one encounters several transitions in PA (Fig. 3.1). There is a transition at about —120°C, the y-transition, which is due to the mobilization of methylene units. There is also a transition at —30°C, which is present in wetted aliphatic PA this is due to non-H-bonded amide units and is termed the /J-transition. At about 50°C the glass Uansition (Tg) (a-transition) of the aliphatic polyamides PA-6 and PA-6,6 occurs. At this Uansition, the modulus is lowered considerably. For partially aromatic PA, the Tg occurs above 100°C. The last transition is the flow temperature, at which temperature the material melts the flow temperature and the melt temperature, as measured by DSC, correspond well. The modulus is a measure of dimensional stability and increases with crystallinity and filler content (Fig. 3.12). 

TDI isomers, 210 Tear strength tests, 242-243 TEDA. See Triethylene diamine (TEDA) Telechelic oligomers, 456, 457 copolymerization of, 453-454 Telechelics, from polybutadiene, 456-459 TEM technique, 163-164 Temperature, polyamide shear modulus and, 138. See also /3-transition temperature (7)>) Brill temperature Deblocking temperatures //-transition temperature (Ty) Glass transition temperature (7) ) Heat deflection temperature (HDT) Heat distortion temperature (HDT) High-temperature entries Low-temperature entries Melting temperature (Fm) Modulu s - temperature relationship Thermal entries Tensile strength, 3, 242 TEOS. See Tetraethoxysilane (TEOS)... 

Another transition appeared at about 130 °C on the rescanning after rapid cooling of the molten sample. It seems to be a glass transition point. The polyamide prepared in bulk at 70 °C also melted sharply at 250—260 °C. On the other hand, the crosslinked polymer, which was prepared in bulk at 100 °C in a high conversion, has nothing but a broad endothermic curve up to near 300 °C as shown in Fig. 9. 

An additional major transition which is observed in DSC scans of stratum comeum is a doublet endotherm which peaks at 194 °C and 210°C in dry samples and at 120°-130°C in wet samples (Figure 14). These transitions are also characteristic of the more extensively investigated keratin-containing wool (49, 65). Polyamides such as the various nylons also show melting endotherms above 200 °C (63). 

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