Delayed cross-linking

Delayed Cross-Linking Systems. As illustrated in Figure 16, high magnitudes and long periods of shear reduce the viscosity of HPG-titanium... 

Polymer thickened foams to which time-delayed cross-linking agents have been added, gelling foams, can be used to improve the efficiency of... 

The free radicals initially formed are neutralized by the quinone stabilizers, temporarily delaying the cross-linking reaction between the styrene and the fumarate sites in the polyester polymer. This temporary induction period between catalysis and the change to a semisoHd gelatinous mass is referred to as gelation time and can be controUed precisely between 1—60 min by varying stabilizer and catalyst levels. 

The action of redox metal promoters with MEKP appears to be highly specific. Cobalt salts appear to be a unique component of commercial redox systems, although vanadium appears to provide similar activity with MEKP. Cobalt activity can be supplemented by potassium and 2inc naphthenates in systems requiring low cured resin color lithium and lead naphthenates also act in a similar role. Quaternary ammonium salts (14) and tertiary amines accelerate the reaction rate of redox catalyst systems. The tertiary amines form beneficial complexes with the cobalt promoters, faciUtating the transition to the lower oxidation state. Copper naphthenate exerts a unique influence over cure rate in redox systems and is used widely to delay cure and reduce exotherm development during the cross-linking reaction. 

Retarders were originally arenecarboxylic acids. These acidic materials not only delay the onset of cross-linking but also slow the cross-linking reaction itself. The acidic retarders do not function weU in black-fiUed compounds because of the high pH of furnace blacks. Another type of retarder, A/-nitroso diphenylamine [86-30-6] was used for many years in black-fiUed compounds. This product disappeared when it was recognized that it trans-nitrosated volatile amines to give a several-fold increase in airborne nitrosamines. U.S. production peaked in 1974 at about 1.6 million kg. 

In more recent years, lining compounds have been developed that vulcanise at ambient temperatures. Most polymers can be used for such compounds, although most materials are based on natural rubber, acrylonitrile-butadiene rubber and polychloroprene. These compounds contain accelerators which usually give rise to a material which has a delay in the onset of vulcanisation with a subsequent rapid rise in cross-link formation to give full vulcanisation in 6 to 8 weeks. Such materials, unless to be used within a few days of manufacture, are refrigerated to arrest the sel f-vulcanisation. 

Borated starch compositions are useful for controlling the rate of cross-linking of hydratable polymers in aqueous media for use in fracturing fluids. The borated starch compositions are prepared by reacting, in an aqueous medium, starch and a borate source to form a borated starch complex. This complex provides a source of borate ions, which cause crosslinking of hydratable polymers in aqueous media [1552]. Delayed crosslinking takes place at low temperatures. 

Chlornitrofen and nitrofen conditions for GC/MS column, cross-linked methyl silicone capillary (12 m x 0.22-mm i.d., 0.33- am film thickness) column temperature, 60 °C (1 min), 18 °C min to 265 °C inlet, transfer line and ion source temperature, 260, 200 and 200 °C, respectively He gas column head pressure, 7.5 psi injection method, splitless mode solvent delay, 3 min electron ionization voltage, 70 eV scan rate, 0.62 s per scan cycle scanned mass range, m/z 100-400. The retention times for chlornitrofen and nitrofen were 11.8 and 11.3 min, respectively. The main ions of the mass spectrum of chlornitrofen were at m/z 317, 319 and 236. Nitrofen presented a fragmentation pattern with the main ions at m/z 283, 202 and 285. ... 

One example of a relatively new technique for the non-invasive, non-destructive characterization of network structures involves pulse-propagation measurements [288,289]. In this technique, the delay Af in a pulse passing through the network is used to obtain information on the network structure, for example, the chain length between cross-links or between entanglements. The technique is illustrated schematically in Figure 12 [282]. 

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