Rubber polychloroprene

Polychloroprene rubber, such as is used for the Selby Conveyor belt, is a chlorinated derivative of isoprene. Fig. 20.5. 

RSH is the alkyl mercaptan chain transfer agent M stands for monomer 

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Substituted dipyhenylamines 4,4 -Dioctyldiphenylamine (III) Yes Moderate antioxidants. Some use in polychloroprene rubbers. 

The hydrohalide is usually prepared by passing hydrogen chloride into a solution of masticated high-grade raw rubber in benzene at 10°C for about six hours. Excess acid is then neutralised and plasticisers and stabilisers are added. The benzene is removed by steam distillation and the product washed and dried. Alternatively the solution is cast on to a polychloroprene rubber belt, leaving a tough film after evaporation of the solvent. 

The diffusion process in natural and polychloroprene rubber adhesives can be explained by Campion s approach [1] which considers the concept of molecular free volume. This free volume is mainly affected by the solvent mixture of the adhesive (which will determine the degree of uncoiling of rubber chains) and by the ingredients in the formulation (mainly the amount and type of tackifier). 

Both side groups and carbon-carbon double bonds can be incorporated into the polymer structure to produce highly resilient rubbers. Two typical examples are polyisoprene and polychloroprene rubbers. On the other hand, the incorporation of polar side groups into the rubber structure imparts a dipolar nature which provides oil resistance to these rubbers. Oil resistance is not found in rubber containing only carbon and hydrogen atoms (e.g. natural rubber). Increasing the number of polar substituents in the rubber usually increases density, reduces gas permeability, increases oil resistance and gives poorer low-temperature properties. 

In some cases, diene polymers (for instance polychloroprene rubbers) can add to the growing polymer chain by 1,2 addition (also called vinyl addition). This creates labile hydrogen or reactive halogen on tertiary carbon atoms. A few percent of this type of structure in the rubber will assist cross-linking reactions. 

The elastomers considered in this section have been selected considering the most commonly used in rubber base adhesives natural rubber butyl nibber and polyisobutylenes styrene-butadiene rubber nitrile rubber polychloroprene rubber (neoprene). Typical properties of these rubbers are shown in Table 2. 

Polychloroprene rubber (CR) is the most popular and versatile of the elastomers used in adhesives. In the early 1920s, Dr. Nieuwland of the University of Notre Dame synthesized divinyl acetylene from acetylene using copper(l) chloride as catalyst. A few years later, Du Pont scientists joined Dr. Nieuwland s research and prepared monovinyl acetylene, from which, by controlled reaction with hydrochloric acid, the chloroprene monomer (2-chloro-l, 3-butadiene) was obtained. Upon polymerization of chloroprene a rubber-like polymer was obtained. In 1932 it was commercialized under the tradename DuPrene which was changed to Neoprene by DuPont de Nemours in 1936. 

Chemistry of polychloroprene rubber. Polychloroprene elastomers are produced by free-radical emulsion polymerization of the 2-chloro-1,3-butadiene monomer. The monomer is prepared by either addition of hydrogen chloride to monovinyl acetylene or by the vapour phase chlorination of butadiene at 290-300°C. This latter process was developed in 1960 and produces a mixture of 3,4-dichlorobut-l-ene and 1,4-dichlorobut-2-ene, which has to be dehydrochlorinated with alkali to produce chloroprene. 

Solubility of resins can be predicted in a similar way as for the solubility of polychloroprene rubbers in a solvent mixture (see Section 5.5) by means of solubility diagrams (plots of the hydrogen bonding index (y) against the solubility parameter (5). Another more simple way to determine the solubility of resins is the determination of the cloud point, the aniline and the mixed aniline points. 

Most rubbers used in adhesives are not resistant to oxidation. Because the degree of unsaturation present in the polymer backbone of natural rubber, styrene-butadiene rubber, nitrile rubber and polychloroprene rubber, they can easily react with oxygen. Butyl rubber, however, possesses small degree of unsaturation and is quite resistant to oxidation. The effects of oxidation in rubber base adhesives after some years of service life can be assessed using FTIR spectroscopy. The ratio of the intensities of the absorption bands at 1740 cm" (carbonyl group) and at 2900 cm" (carbon-hydrogen bonds) significantly increases when the elastomer has been oxidized [50]. 

Rubbers differ in their resistance to ozone. All the highly unsaturated rubbers (natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber) are readily cracked while the deactivated double carbon-carbon bonds rubber (such as polychloroprene rubber) shows moderate ozone resistance. 

Polychloroprene rubber possesses the characteristics of natural rubber and has the advantage of higher polarity. 

Lee [242] studied the dependence of the physico-mechanical properties of Wollastonite-filled polychloroprene rubber on the type of agent used to pre-treat the filler. The composition contained 26.9 part (weight) of the filler per 100 parts (weight) of the rubber (compositions CR-1100, CR-174, CR-151). The finishing agents were y-aminopropyl triethoxysilane (CR-1100 and CR-174) and vinyl triethoxysilane (CR-151). The mechanical properties of the compositions are listed in Table 7 below. The author proposed an empirical equation to relate the modulus with the equilibrium work of adhesion in the following form ... 

Better cross-linking with the latter also improves post Tg viscoelastic responses of the rubber vulcanizates. Similar effect has also been observed with polychloroprene as investigated by Sahoo and Bhowmick [41]. Figure 4.8 represents the comparative tensile stress-strain behavior of polychloroprene rubber (CR) vulcanizates, highlighting superiority of the nanosized ZnO over conventional rubber grade ZnO [41]. 

In one of the first reports on fiber reinforcement of rubber, natural rubber (NR) was used by Collier [9] as the rubber matrix, which was reinforced using short cotton fibers. Some of the most commonly used rubber matrices for fiber reinforcement are NR, ethylene-propylene-diene monomer (EPDM) rubber, styrene-butadiene rubber (SBR), polychloroprene rubber, and nitrile rubber [10-13]. These rubbers were reinforced using short and long fibers including jute, silk, and rayon [14—16]. 

Ashida, M., Composites of polychloroprene rubber with short fibres of polyfethylene terephthalate) and nylon, in Short Fiber-Polymer Composites, De, S.K. and White, J.R. (Eds.), Woodhead Publishing, Cambridge, 1996, Chapter 5. 

Maleimides Alkyl and aryl maleimides in small concentrations, e.g., 5-10 wt% significantly enhance yield of cross-link for y-irradiated (in vacuo) NR, cw-l,4-polyisoprene, poly(styrene-co-butadiene) rubber, and polychloroprene rubber. A-phenyhnaleimide and m-phenylene dimaleimide have been found to be most effective. The solubihty of the maleimides in the polymer matrix, reactivity of the double bond and the influence of substituent groups also affect the cross-fink promoting ability of these promoters [82]. The mechanism for the cross-link promotion of maleimides is considered to be the copolymerization of the rubber via its unsaturations with the maleimide molecules initiated by radicals and, in particular, by allyfic radicals produced during the radiolysis of the elastomer. Maleimides have also been found to increase the rate of cross-linking in saturated polymers like PE and poly vinylacetate [33]. 

Polychloroprene rubbers are not efficiently vulcanized by sulfur. The chlorine atoms deactivate the double bonds toward reaction with sulfur. Vulcanization is achieved by heating with zinc and magnesium oxides. Crosslinking involves the loss of... 

During 1973, at a chloroprene polymerization plant in the United States, airborne concentrations of chloroprene were found to range from 14 to 1420 ppm [50-5140 mg/m ] in the make-up area, from 130 to 6760 ppm [470-24 470 mg/m in the reactor area, from 6 to 440 ppm [22-1660 mg/m ] in the monomer recovery area and from 113 to 252 ppm [409-912 mg/ni l in the latex area (Infante et al., 1977). Concentrations in the air inside a Russian polychloroprene rubber plant were 14.5-53.4 mg/m (Mnatsakayan et al., 1972). In a Russian chloroprene latex manufacturing facility, chloroprene concentrations varied from 1 to 8 mg/m (Volkova et al., 1976). 

Neoprene is the generic name for polychloroprene rubber. It has been produced commercially since 1931 and had rapid and wide acceptance because it is much superior to natural rubber for heat and oil resistance. Heat resistance is far better than NR, BR or SBR. but less than EPDM. When heated in the absence of air, neoprene withstands degradation better than other elastomers which are normally considered more heat resistant, and retains its properties fifteen times longer than in the presence of air. Compression set at higher temperature is better than natural rubber and 100°C is typically the test temperature rather than 70°C. Abrasion resistance is not as good as natural rubber but generally better than most heat resistant and oil resistant rubbers. This is also true for tear strength and flex resistance. 

Synthetic elastomers, e.g. styrene-butadiene rubber, polychloroprene rubber, nitrile-butadiene rubber... 

Neoprene, or polychloroprene rubber (CR) was one of the very first synthetic rubbers produced. It was a material of choice for exterior applications such as profiles used in vehicles, building seals, and cables. Many more marketable products have benefited from this plastic. Except for SBR and IR, neoprene (CR) elastomers are perhaps the most rubberlike of all materials, particularly with regard to its dynamic response (Table 2.6). CRs are a family of elastomers with a property profile that approaches that of NRs (natural rubbers) but has better resistance to oils, ozone, oxidation, and flame. CRs age better and do not soften up on exposure to heat, although their high-temperature tensile strength may be lower than that of NRs. They are suitable for service at 250C (480F). 

Solvents produce different effects than do corrosive chemicals. Both silica and carbon black filled natural rubbers were more resistant to solvents than unfilled rubber. Also, the cure time was important, indicating that the bound rubber plays a role in the reduction of a solvent sorption. The diffusion coefficient of solvents into rubbers decreases with longer cure times and higher fillers loadings. Polychloroprene rubber swollen with solvent has a lower compression set when it is filled with carbon black. 

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