Cured polyethylene

Figure 6 Light transmission of quenched cured polyethylene as a function of the sample thickness (vulcanization temperature 160°C, time 15 min.). 1-sample of normal polyethylene 2 mm thick 2, 3, and 4-quenched cured samples of different thickness 2-1 mm, 3-2 mm, 4-4 mm.

At present, very few compounds are used as thermostabilizers for cured polyethylene. Among them may be listed I,3-dihydro-2,2,4-trimethylquinoline jS-di-naphtyl, -phenylenediamine, zinc mercaptobenzimida-zole [43-45]. 

Po[yamine disulphides do not inhibit peroxide vulcanization of polyethylene, are stable in air up to 300-350°C, exhibit good compatibility and show no sweating out from the polyethylene mass. Table 8 gives the comparison between the efficiency of polyamine disulphides as thermostabilizers of cured polyethylene. 

A series of polyamine disulphides (polyaniline disulphide, polyamine disulphide, and polyparaphenylenedi-amine disulphide) represent effective thermostabilizers of cured polyethylene, and provide a decrease in gel fraction 2.5-3 times as large as that in case of inhibited thermal destruction. Stabilizers of normal polyethylene (Neozone D , Santonox R ) are inefficient as stabilizers of cured polyethylene, these substances decompose and even initiate thermal destruction of cured polyethylene. 

Polyamine disulphides are effective thermostabilizers of cured polyethylene up to 400°C. In presence of polyamine disulphides a decrease in gel fraction is one half as large as that of nonstabilized cured polyethylene over the temperature range from 350-380°C [46]. 

An investigation into the effect of the concentration of polyaniline disulphide on inhibition of thermal destruction in case of cured polyethylene has demonstrated that polyaniline disulphide is efficient even at the concentration of 0.25%. An increase in the concentration over the range 0.25-1.0% results in the increased efficiency, while further increase in the concentration leads to a slight drop in inhibition. 

Polyamine disulphides as inhibitors of thermal destruction of cured polyethylene are effective over a long period of time. 

A drop in gel fraction of nonstabilized cured polyethylene amounts to 50% after 25-h exposure, 75% after 50 hours and after a 75-h exposure the complete fall is observed. At the same time, a decrease in gel fraction in presence of polyaniline disulphide is observed only after a 50-h exposure and comes to only 2%, whereas... 

Table 8 Inhibition of Thermal Destruction of Low-Density Cured Polyethylene in Vacuum (10- torr)...

A large number of polymeric compounds have been investigated, but most modem propellants utilize prepolymers that ate hydroxy-functional polybutadienes (HTPB), carboxy-functional polybutadienes (CTPB), or a family of polyethylene oxides (PEGs) to form urethanes. Typical cure reactions... 

Another use is of minor proportions of polyfunctional aHyl esters, eg, diaHyl maleate, ttiaHyl cyanurate, and ttiaHyl isocyanurate, for cross-linking or curing preformed vinyl-type polymers such as polyethylene and vinyl chlotide copolymers. These reactions ate examples of graft copolymerization in which specific added peroxides or high energy radiation achieve optimum cross-linking (see Copolymers). 

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

Pubhcations on curing polymers with TAIC include TEE—propylene copolymer (135), TEE—propylene—perfluoroaHyl ether (136), ethylene—chlorotrifluoroethylene copolymers (137), polyethylene (138), ethylene—vinyl acetate copolymers (139), polybutadienes (140), PVC (141), polyamide (142), polyester (143), poly(ethylene terephthalate) (144), sdoxane elastomers (145), maleimide polymers (146), and polyimide esters (147). 

At this point in the process, thermoplastic and chlorosulfonated polyethylene (CSPE) membranes are complete and are ready for packaging. In the case of ethylene—propylene—diene monomer (EPDM), the curing step occurs before the membrane is ready for packaging. The curing process is accomphshed by placing the membrane in a large vulcanizer where the material is heated under pressure to complete the cure. 

CSPE. Chlorosulfonated polyethylene (CSPE), a synthetic mbber manufactured by DuPont, is marketed under the name Hypalon. It can be produced as a self-curing elastomer designed to cure on the roof. The membrane is typically reinforced with polyester and is available in finished thicknesses of 0.75 to 1.5 mm. Because CSPE exhibits thermoplastic characteristics before it cures, it offers heat-weldable seams. After exposure on the roof, the membrane cures offering the toughness and mechanical set of a thermoset. The normal shelf life of the membrane for maintaining this thermoplastic characteristic is approximately six months. After the membrane is fully cured in the field, conventional adhesives are needed to make repairs. 

Other Accelerators. Amine isophthalate and thiazolidine thione, which are used as alternatives to thioureas for cross-linking polychloroprene (Neoprene) and other chlorine-containing polymers, are also used as accelerators. A few free amines are used as accelerators of sulfur vulcanization these have high molecular weight to minimize volatility and workplace exposure. Several amines and amine salts are used to speed up the dimercapto thiadiazole cure of chlorinated polyethylene and polyacrylates. Phosphonium salts are used as accelerators for the bisphenol cure of fluorocarbon mbbers. 

Dimercapto-l,3,4-thiadiazole derivatives, accelerated by amines, are used to cross-link chlorinated polyethylene. Polyisobutylene containing brominated i ra-methylstyrene cure functionahty can be cross-linked in polymer blends with dimercapto-1,3,4-thiadiazole derivatives accelerated with thiuram disulfides. Trithiocyanuric acid is suggested for use in polyacrylates containing a chlorine cure site and in epichlorohydrin mbbers. 

Meta.1 Oxides. Halogen-containing elastomers such as polychloropreae and chlorosulfonated polyethylene are cross-linked by their reaction with metal oxides, typically ziac oxide. The metal oxide reacts with halogen groups ia the polymer to produce an active iatermediate which then reacts further to produce carbon—carbon cross-links. Ziac chloride is Hberated as a by-product and it serves as an autocatalyst for this reaction. Magnesium oxide is typically used with ZnCl to control the cure rate and minimize premature cross-linking (scorch). 

Typical substrates for siUcone release coatings are supercalendered kraft paper, glassines, and thermally sensitive films such as polyethylene and polypropylene. Ideal curing conditions are 150°C or lower, and line speeds are as fast as 460 m /min. Key properties for release coatings are cure speed, integrity of cure, and stable release values. 

The tubular positive plate uses rigid, porous fiber glass tubes covered with a perforated plastic foil as the active material retainer (Fig. 2). Dry lead oxide, PbO, and red lead, Pb O, are typically shaken into the tubes which are threaded over the grid spines. The open end is then sealed by a polyethylene bar. Patents describe a procedure for making a type of tube for the tubular positive plate (90) and a method for filling tubular plates of lead—acid batteries (91). Tubular positive plates are pickled by soaking in a sulfate solution and are then cured. Some proceed directiy to formation and do not requite the curing procedure. 

Plasticizers and Processing Aids. Petroleum-based oils are commonly used as plasticizers. Compound viscosity is reduced, and mixing, processing, and low temperature properties are improved. Air permeabihty is increased by adding extender oils. Plasticizers are selected for their compatibihty and low temperature properties. Butyl mbber has a solubihty parameter of ca 15.3 (f /cm ) [7.5 (cal/cm ) ], similar to paraffinic and naphthenic oils. Polybutenes, paraffin waxes, and low mol wt polyethylene can also be used as plasticizers (qv). Alkyl adipates and sebacates reduce the glass-transition temperature and improve low temperature properties. Process aids, eg, mineral mbber and Stmktol 40 ms, improve filler dispersion and cured adhesion to high unsaturated mbber substrates. 

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