Electron crosslinking

Although mononitrenes do not act as crosslinking agents themselves, they can generate unpaired electrons in the polymer chains by the abstraction of hydrogen molecules from the polymer. As the result, the polymer chains are crosslinked by the recombinations of these unpaired electrons. Crosslinking by mononitrene in such a way, depends on the activity of the nitrene and may be not necessarily less efficient in some combination of monoazide with the polymer than that by dinitrene as is seen in the case for... 

FIGURE 3.16 Single stage scanned beam accelerator with a range of accelerator voltages from 80 to 300 kV. (Courtesy Electron Crosslinking AB.)... 

A dose reader designed for direct reading from exposed films, offered by Electron Crosslinking AB of Sweden, is shown in Figure 9.1. 

Sulfur chemistry [29] has also been used to crosslink rubber/resin PSAs, although the use of elemental sulfur itself yields tapes that can stain substrates. Other patents exemplify the use of typical rubber vulcanizing chemistry such as Tetrone A , dipentamethylenethiuramtetrasulfide, and Tuads , tetramethylthiu-ram disulfide [30], or zinc butyl xanthate [31] for this purpose. Early art [32] also claimed electron beam curing of both natural rubber and other adhesives that were solvent coated on tape backings. Later references to electron beam curing... 

Figure 1 The transmission electron micrographs of the crosslinked products of MCI cast from benzene, (a) at a 0.05 wt% polymer concentration and shadowed with Cr at an angle of 20°, and (b) at a 0.05 wt% concentration [24].

Unsaturated polyester finishes of this type do not need to be stoved to effect crosslinking, but will cure at room temperature once a suitable peroxide initiator cobalt salt activator are added. The system then has a finite pot life and needs to be applied soon after mixing. Such a system is an example of a two-pack system. That is the finish is supplied in two packages to be mixed shortly before use, with obvious limitations. However, polymerisation can also be induced by ultra violet radiation or electron beam exposure when polymerisation occurs almost instantaneously. These techniques are used widely in packaging, particularly cans, for which many other unsaturated polymers, such as unsaturated acrylic resins have been devised. 

In this case, the elements of the crosslinked structure exhibit higher mobility, the permeability of the crosslinked structure depends on the degree of hydration. It should be noted that the pore size in hydrated crosslinked copolymers is determined by small-angle X-ray scattering or with the aid of electron microscopy using special methods of preparation for the CP samples [15],... 

Fig. 6. Electron microscopy of carboxylic CP MA-DMEG copolymers with different contents of crosslinking agents (mol%) 1) 9 2) 10.5 3) 13.5...

Kloosterboer, J. G. Network Formation by Chain Crosslinking Photopolymerization and its Applications in Electronics. Vol. 84, pp. 1 —62. 

Similar types of lamellar morphologies were observed for triblock copolymers of diphenylsiloxane and dimethylsiloxane having 40 wt% polydiphenylsiloxane, using electron microscopy, 47-148>. The lamellae thickness was approximately equal to the chain length of the rigid polydiphenylsiloxane blocks. These copolymers showed elastomeric properties comparable to those of conventional silica-reinforced, chemically crosslinked silicone rubbers. Tensile tests yielded an initial modulus of 0.5-1 MPa, tensile strength of 6-7 MPa and ultimate elongation between 400 and 800 %. 

Chattopadhyay, S., Chaki, T.K., Bhowmick, A.K., Gao, G.J.P., and Bandyopadhyay, S., Structural characterization of electron-beam crosslinked thermoplastic elastomeric films from blends of polyethylene and ethylene-vinyl acetate copolymers, J. Appl. Polym. Sci., 81, 1936, 2001. 

FIGURE 21 Scanning electron micrographs of crosslinked polymer prepared from a 3,9-bis(ethylidene-2,4,8,10-tetraoxaspiro[5,5]un-decane)/3-methyl-l,5-pentanediol prepolymer crosslinked with 1,2,6-hexane triol. Prepolymer contains 1 mol% copolymerized 9,10-dihydroxys tearic acid. Polymer rods, 2.4 x 20 mm, containing 30 wt% levonorgestrel and 7.1 mol% Mg(OH)2. Devices implanted subcutaneously in rabbits, (a) after 6 weeks, 30x (b) after 9 weeks, 30x (c) after 12 weeks, 25x (d) after 16 weeks, 25x. (From Ref. 18.)... 

Electron microscopy and X-ray diffraction experiments conducted on resilin-containing insect cuticle provided further support for resilin existing in the rubbery state as a crosslinked random network of protein chains. No fine structure was revealed by the electron microscopy experiments and zero crystallinity could be detected from the X-ray diffraction experiments. Furthermore, the diffraction... 

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

Although it has been suggested that crosslinking in the presence of MAH involves coupling of appended MAH radicals with other appended MAH radicals or with polymer radicals (7) the former is improbable due to the tendency for disproportionation rather than coupling between radicals derived from strong electron acceptor monomers such as MAH. 

Stearamide is one of many electron donors which donate an electron to the cationic moiety in excited MAH or in propagating -MAH chains. This results in the inhibition of the homopolymerization of MAH and decreases the crosslinking of polyethylene and the degradation of polypropylene which accompany the peroxide-catalyzed reaction of MAH with these polyolefins (8,9). ... 

Metallophosphazenes are a new type of macromolecule designed to bridge the gap between polymers and metals. Although still at an exploratory stage of laboratory development, they may provide access to electronically-conducting polymers, magnetically-active polymers, macromolecular catalysts, electrode mediator systems, or polymers crosslinked by metal atoms. 

A difference between microcrystallite-based ultrastructure and covalently-crosslinked systems is that microcrystallites melt at specific temperatures, allowing the polymer to be fabricated by heating at modest temperatures. Subsequent cooling of the system below the crystallization temperature allows the physical property advantages of the solid state to become manifest. Liquid crystallinity is also possible if some order is retained in the molten state. Crystalline order not only adds mechanical strength, it also provides opportunities for the appearance of other properties that depend on solid state order—such as electronic conductivity. 

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