Crosslinking in rubbers

Figure 1. Scission of polysulfide crosslinks in rubber peelings with refluxing mixture of 2.1 N NaOH and Aliquat 336 in benzene.

Gordon, M., Kucharuk,S., Ward,T. C. The statistics of elastically active network chains and the efficiency of crosslinking in rubbers. Collection Czech. Chem. Commun. 35,3252-3264 (1970). 

BQDI 53 may induce undesirable reduction of the processing safety and efficiency of crosslinking in rubber vulcanization [3]. 

In crosslinked polymers, adjacent linear chains are joined one to another at varions positions by covalent bonds, as represented in Figure 14.7c. The process of crosslinking is achieved either diu-ing synthesis or by a nonreversible chemical reaction. Often, this crosslinking is accomphshed by additive atoms or molecules that are covalently bonded to the chains. Many of the rubber elastic materials are crosslinked in rubbers, this is called vulcanization, a process described in Section 15.9. 

Natural rubber, cis-1,4-polyisoprene, cross-linked with sulfur. This reaction was discovered by Goodyear in 1839, making it both historically and commercially the most important process of this type. This reaction in particular and crosslinking in general are also called vulcanization. 

Stretching a polymer sample tends to orient chain segments and thereby facilitate crystallization. The incorporation of different polymer chains into small patches of crystallinity is equivalent to additional crosslinking and changes the modulus accordingly. Likewise, the presence of finely subdivided solid particles, such as carbon black in rubber, reinforces the polymer in a way that imitates the effect of crystallites. Spontaneous crystal formation and reinforcement... 

In the JKR experiments, a macroscopic spherical cap of a soft, elastic material is in contact with a planar surface. In these experiments, the contact radius is measured as a function of the applied load (a versus P) using an optical microscope, and the interfacial adhesion (W) is determined using Eqs. 11 and 16. In their original work, Johnson et al. [6] measured a versus P between a rubber-rubber interface, and the interface between crosslinked silicone rubber sphere and poly(methyl methacrylate) flat. The apparatus used for these measurements was fairly simple. The contact radius was measured using a simple optical microscope. This type of measurement is particularly suitable for soft elastic materials. 

In an attempt to determine the applicability of JKR and DMT theories, Lee [91] measured the no-load contact radius of crosslinked silicone rubber spheres in contact with a glass slide as a function of their radii of curvature (R) and elastic moduli (K). In these experiments, Lee found that a thin layer of silicone gel transferred onto the glass slide. From a plot of versus R, using Eq. 13 of the JKR theory, Lee determined that the work of adhesion was about 70 7 mJ/m". a value in clo.se agreement with that determined by Johnson and coworkers 6 using Eqs. 11 and 16. 

Vulcanization changes the physical properties of rubbers. It increases viscosity, hardness, modulus, tensile strength, abrasion resistance, and decreases elongation at break, compression set and solubility in solvents. All those changes, except tensile strength, are proportional to the degree of cross-linking (number of crosslinks) in the rubber network. On the other hand, rubbers differ in their ease of vulcanization. Since cross-links form next to carbon-carbon double bonds. 

Langley, N.R. and Polmanteer, K.E., Relation of elastic modulus to crosslink and entanglement concentrations in rubber networks. J. Polym. Sci. Polym. Phys. Ed., 12(6), 1023-1034 (1974). 

Crosslinked polymers are rather peculiar materials in that they never melt and they exhibit entropic elasticity at elevated temperatures. The present review on the influence of crosslink density is structured around model polymers of uniform composition but with widely varying numbers of crosslinks. The degree of crosslinking in the polymers was verified by use of the theory of rubber elasticity. 

Vulcanisation is the term used for the process in which the rubber molecules are lightly crosslinked in order to reduce plasticity and develop elasticity. It was originally applied to the use of sulfur for this purpose, but is now used for any similar process of cross-linking. Sulfur, though, remains the substance most widely used for this purpose. 

Recent work has focused on a variety of thermoplastic elastomers and modified thermoplastic polyimides based on the aminopropyl end functionality present in suitably equilibrated polydimethylsiloxanes. Characteristic of these are the urea linked materials described in references 22-25. The chemistry is summarized in Scheme 7. A characteristic stress-strain curve and dynamic mechanical behavior for the urea linked systems in provided in Figures 3 and 4. It was of interest to note that the ultimate properties of the soluble, processible, urea linked copolymers were equivalent to some of the best silica reinforced, chemically crosslinked, silicone rubber... 

Commercial polyisobutylene is often copolymerised with a few percentage of isoprene in order to allow for crosslinking (butyl rubber). 

A term apphed to vulcanisation systems in which sulphur or a sulphur donor is used very efficiently for crosslinking the rubber. EV systems produce vulcanisates with crosslinks that are mainly monosulphidic, which are thermally and mechanically stable. 

This term was originally limited to the chemical reaction of rubber with sulphur to bring about the following effects (a) reduced thermoplasticity, (b) increased tensile strength and resistance to abrasion, and (c) reduced solubility in organic solvents. Since many other substances can bring about the above changes the term has now been widened to include any treatment which will introduce crosslinks in the rubber matrix. Vulcanised Latex... 

To convert an elastomer into ebonite, the glass transition temperature, Tg, has to be raised to above 20 °C, or above the operating temperature of the product, in order to remain rigid in use. This is achieved by crosslinking the rubber with a large amount of sulphur. Typically, 25 to 50 phr is used for natural rubber ebonites. Ebonites can be produced from NR, BR, IR, SBR and NBR. Rubbers with low unsaturation, e.g., HR and EPDM, do not form ebonites. 

The influence of ZnCFO concentration (3,0 5,0 7,0 phr) on formation of properties complex of the unfilled rubber mixes and their vulcanizates on the basis of isoprene rubber of the following recipe, phr isoprene rubber - 100,0 sulfur - 1,0 di - (2-benzothiazolyl) -disulfide - 0,6 N, N -diphenylguanidine - 3,0 stearic acid - 1,0, was carried out in comparison with the known activator - zinc oxide (5,0 phr). The analysis of Rheometer data of sulfur vulcanization process of elastomeric compositions at 155°C (fig. 5) shows, that on crosslink density and cure rate, about what the constants of speed in the main period (k2) testify, they surpass the control composition with 5,0 phr of zinc oxide. Improvement of the complex of elastic - strong parameters of rubbers with ZnCFO as at normal test conditions, and after thermal air aging (tab. 1), probably, is caused by influence of the new activator on vulcanization network character. So, the percent part of polysulfide bonds (C-Sx-C) and amount of sulfur atoms appropriating to one crosslink (S atoms/crosslink) in vulcanizates with ZnCFO are decreased, the percent part of disulfide bonds (C-S2-C) is increased (fig. 62). 

It is known that aromatic azides are photodecomposed to give active nitrenes as the transient species, which react with the environmental binder polymers to crosslink them. However, the mechanism of these photocrosslinking polymers has not been studied in detail. L.S.Efros et al. have proposed that the rubber polymer is crosslinkes in such a way that the aromatic nitrene inserts into an unsaturated bond of the polymer to give an aziridine ring. The experimental evidence for this, however, has not been given (8). 

MPR competes with crosslinked nitrile rubber for demanding applications (in the automotive sector, for example) needing oil and grease resistance, noise dampening, stress relaxation similar to vulcanized rubber, good bonding to PVC, PC, ABS. 

Scission of Polysulfide Crosslinks in Scrap Rubber Particles. Throughout this study, we used a single lot of scrap rubber peelings having the average composition described in the Experimental Section. We began our studies with Aliquat 336 as the phase transfer catalyst because of its proven effectiveness in simple systems and its commercial availability. When devulcanization is performed in a refluxing benzene/aqueous NaOH mixture, the chemical crosslink density (M... 

These products find use in specialty applications requiring better thermal stability than available in the sulfur vulcanized elastomers. Other processes are also used to crosslink polydiene rubbers (Secs. 9-2c and 9-2d). 

The vulcanization of polychloroprene (Neoprene) is carried out in different ways. Vulcanization by sulfur, even with an accelerator, is not practiced to a large extent. Vulcanizations by metal oxides (without diamine), either alone or in combination with sulfur (sometimes together with an accelerator), give the best physical properties for the crosslinked product. Halogenated butyl rubber is crosslinked in a similar manner. The mechanism for crosslinking by metal oxide alone is not established [Stewart et al., 1985 Vukov, 1984]. 

Morrison, N. J. andM. Porter, Crosslinking of Rubbers, Chap. 6 in Comprehensive Polymer Science, Vol. 

Here, v is Poisson s ratio which is equal to 0.5 for elastic materials such as hydrogels. Rubber elasticity theory describes the shear modulus in terms of structural parameters such as the molecular weight between crosslinks. In the rubber elasticity theory, the crosslink junctions are considered fixed in space [19]. Also, the network is considered ideal in that it contained no structural defects. Known as the affine network theory, it describes the shear modulus as... 

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