Rubber melting point

Fig. 32). Using a fine pipette insert about i cm. length of the liquid into the bottom of the tube. Now place in the tube A a fine inverted melting-point tube B of about i mm. diameter, sealed at the upper end. Fasten the capillary tube to the ther- Fio. 32. mometer by means of a rubber band and place in a melting-point apparatus. Heat slowly until a stream of bubbles rises from the bottom... 

Prepa.ra.tlon, There are several methods described in the Hterature using various cobalt catalysts to prepare syndiotactic polybutadiene (29—41). Many of these methods have been experimentally verified others, for example, soluble organoaluminum compounds with cobalt compounds, are difficult to reproduce (30). A cobalt compound coupled with triphenylphosphine aluminum alkyls water complex was reported byJapan Synthetic Rubber Co., Ltd. (fSR) to give a low melting point (T = 75-90° C), low crystallinity (20—30%) syndiotactic polybutadiene (32). This polymer is commercially available. 

An unusual method for the preparation of syndiotactic polybutadiene was reported by The Goodyear Tire Rubber Co. (43) a preformed cobalt-type catalyst prepared under anhydrous conditions was found to polymerize 1,3-butadiene in an emulsion-type recipe to give syndiotactic polybutadienes of various melting points (120—190°C). These polymers were characterized by infrared spectroscopy and nuclear magnetic resonance (44—46). Both the Ube Industries catalyst mentioned previously and the Goodyear catalyst were further modified to control the molecular weight and melting point of syndio-polybutadiene by the addition of various modifiers such as alcohols, nitriles, aldehydes, ketones, ethers, and cyano compounds. 

Well, that is the case at the low temperature, when the rubber has a proper modulus of a few GPa. As the rubber warms up to room temperature, the Van der Waals bonds melt. (In fact, the stiffness of the bond is proportional to its melting point that is why diamond, which has the highest melting point of any material, also has the highest modulus.) The rubber remains solid because of the cross-links which form a sort of skeleton but when you load it, the chains now slide over each other in places where there are no cross-linking bonds. This, of course, gives extra strain, and the modulus goes down (remember, E = [Pg.61]

This situation is identical to the previous one and occurs for example when paraffin wax is mixed into rubber above the melting point of the wax. On cooling, the wax starts to crystallise, some of it forming a bloom on the rubber surface. Such a bloom assists in protecting a diene rubber from ozone attack. 

Replacement of some or all of the —CONH— hydrogens by alkyl or alkoxy-alkyl groups to reduce hydrogen bonding which results in softer, lower melting point and even rubber polymers (A-substitution). 

A typical phase diagram for such polymers is given in Fig. 18.9. With such crystdline polymers the melting point replaces the as the factor usually determining the maximum service temperature of thermoplastics and minimum service temperature of rubbers. However, being more complicated than amorphous polymers it is more difficult to make generalisations about properties. The following remarks may, however, be pertinent for crystalline polymers ... 

When a thermoplastic polyurethane elastomer is heated above the melting point of its hard blocks, the chains can flow and the polymer can be molded to a new shape. When the polymer cools, new hard blocks form, recreating the physical crosslinks. We take advantage of these properties to mold elastomeric items that do not need to be cured like conventional rubbers. Scrap moldings, sprues, etc. can be recycled directly back to the extruder, which increases the efficiency of this process. In contrast, chemically crosslinked elastomers, which are thermosetting polymers, cannot be reprocessed after they have been cured. 

The copolymerization of butadiene in trans configuration with suitable comonomers represents a second route for obtaining a wide range of strain induced crystallizable elastomers, with melting point tailorable in a wide range of temperatures. These copolymers can be used, in particular, in blends with other crystallizable rubbers (e.g. synthetic cis-l,4-polyisoprene) in order to improve their "green strength". 

Since it is not possible to commercially produce a polymer that is based on the cis 1,4 form, commercial polymers are based on the Irons 1,4 form which has a crystalline melting point, Tm, of +75 °C and a Tg of -45 °C. Pure 1,4 trans polychloroprene thus crystallises readily and would normally be considered to be of limited use for a rubber. Such a polymer, however, does not crystallise when dissolved in a solvent, but will do so when the solvent evaporates. This feature is used to good effect in the production of contact adhesives. 

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