Rubber reaction with

The products of the Prins reaction with rubbers are thermoplastic polymers that possess fan-resistance to acids and bases. Free hydroxyl groups in the products are available for crosslinking with diisocyanates or by other means. The Prins reaction can be carried out directly on rubber latexes. It is also possible to just mill the rubber together with formaldehyde and then heat the resultant mixture in the presence of anhydrous metal chlorides to get similar results. ... 

This article reviews literature on ozone reaction with diene rubbers. Physical and chemical phenomena of rubber ageing by ozone and mechanisms of ozone reaction with rubbers are described. Possibilities of improving ozone resistance of rubbers and vulcanisates made from... 

Apparatus 4-1 flask (see Fig. 2) for the reaction with lithium amide 3-1 silvered Dewar flask, provided with a rubber stopper and a gas outlet for the hydroxyalkylation (no stirring was applied). 

The reaction is of practical importance in the vulcanization of siUcone mbbers (see Rubber compounding). Linear hydroxy-terrninated polydimethyl siloxanes are conveniently cross-linked by reaction with methyldiethoxysilane or triethoxysilane [998-30-1]. Catalysts are amines, carboxyflc acid salts of divalent metals such as Zn, Sn, Pb, Fe, Ba, and Ca, and organotin compounds. Hydroxy-terrninated polysiloxanes react with Si—H-containing polysiloxanes to... 

The first type includes vulcanising agents, such as sulphur, selenium and sulphur monochloride, for diene rubbers formaldehyde for phenolics diisocyanates for reaction with hydrogen atoms in polyesters and polyethers and polyamines in fluoroelastomers and epoxide resins. Perhaps the most well-known cross-linking initiators are peroxides, which initiate a double-bond... 

Tsai et al. have also used RAIR to investigate reactions occurring between rubber compounds and plasma polymerized acetylene primers deposited onto steel substrates [12J. Because of the complexities involved in using actual rubber formulations, RAIR was used to examine primed steel substrates after reaction with a model rubber compound consisting of squalene (100 parts per hundred or phr), zinc oxide (10 phr), carbon black (10 phr), sulfur (5 phr), stearic acid (2 phr). 

Positive SIMS spectra obtained from plasma polymerized acetylene films on polished steel substrates after reaction with the model rubber compound for times between zero and 65 min are shown in Fig. 44. The positive spectrum obtained after zero reaction time was characteristic of an as-deposited film of plasma polymerized acetylene. However, as reaction time increased, new peaks appeared in the positive SIMS spectrum, including m/z = 59, 64, and 182. The peaks at 59 and 64 were attributed to Co+ and Zn, respectively, while the peak at 182 was assigned to NH,J(C6Hn)2, a fragment from the DCBS accelerator. The peak at 59 was much stronger than that at 64 for a reaction time of 15 min. However,... 

Fig. 44. Positive TOF-SIMS spectra of plasma polymerized acetylene film after reaction with a model rubber compound for (A) 0 and (B) 15 min. Positive TOF-SIMS spectra of plasma polymerized acetylene film after reaction with a model rubber compound for (C) 35 and (D) 65 min. Reproduced by permission of Gordon and Breach Science Publishers from Ref. [56].

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. 

Ozone cracking is a physicochemical phenomenon. Ozone attack on olefinic double bonds causes chain scission and the formation of decomposition products. The first step in the reaction is the formation of a relatively unstable primary ozonide, which cleaves to an aldehyde or ketone and a carbonyl. Subsequent recombination of the aldehyde and the carbonyl groups produces a second ozonide [58]. Cross-linking products may also be formed, especially with rubbers containing disubstituted carbon-carbon double bonds (e.g. butyl rubber, styrene-butadiene rubber), due to the attack of the carbonyl groups (produced by cleavage of primary ozonides) on the rubber carbon-carbon double bonds. 

A hydroxy-terminated oligomer can be converted into a carboxy-terminated one by reaction with an anhydride [37]. Such an oligomer can also be used to synthesize a methacrylated rubber as above [38]. 

Where resorcinol adhesives are not suitable, resins can be prepared from modified resorcinol [128], Characteristic of these types of resins arc those used for tyre cord adhesives, in which a pure resorcinol-formaldehyde resin is used, or alternatively, alkyl resorcinol or oil-soluble resins suitable for rubber compounding are obtained by prereaction of resorcinol with fatty acids in the presence of sulfuric acid at high temperature followed by reaction with formaldehyde. Worldwide more than 90% of resorcinol adhesives are used as cold-setting wood adhesives. The other most notable application is as tyre cord adhesives, which constitutes less than 5% of the total use. 

Polyurethane adhesives are formed by the reaction of various types of isoeyanates with polyols. The polar urethane group enables adhesion to various surfaees. Depending on the raw materials, glue lines with rubber-like elastic to brittle-hard behavior ean be aehieved. The presence of reactive terminal groups provides a ehemieally hardened adhesive. When polymerized to a high enough molecular weight, the adhesive ean be physically rather than chemically hardened, i.e. a hot melt. 

The checkers employed a sealed ampoule of bromomethane of b.p 5° (obtained from Eastman Organic Chemicals) which was cooled to 0° and opened. After a boiling chip had been added to the ampoule, it was connected to the gas-inlet tube of the reaction apparatus with rubber tubing, and the ampoule was warmed in a water bath to distil the bromomethane into the reaction vessel. 

Sulfur reacts very slowly with rubber, and so is compounded with rubber in the presence of accelerators and activators. Typical accelerators are thia-zoles and a typical activator is a mixture of zinc oxide and a fatty acid. The chemistry of the vulcanisation reactions is complicated, but generates a three-dimensional network in which rubber molecules are connected by short chains of sulfur atoms, with an average of about five atoms in each chain. 

Carbon blacks are the most widely used fillers for elastomers, especially vulcanised natural rubber. They cause an improvement in stiffness, they increase the tensile strength, and they can also enhance the wear resistance. Other particulate fillers of an inorganic nature, such as metal oxides, carbonates, and silicates, generally do not prove to be nearly so effective as carbon black. This filler, which comes in various grades, is prepared by heat treatment of some sort of organic material, and comes in very small particle sizes, i.e. from 15 to 100 nm. These particles retain some chemical reactivity, and function in part by chemical reaction with the rubber molecules. They thus contribute to the crosslinking of the final material. 

Chen et al. utUized a direct chemical reaction with a given solution (wet treatment) to modify the surface of the silicone rubber. The presence of a layer of PEO on a biomaterial surface is accompanied by reductions in protein adsorption, and cell and bacterial adhesion. In order to obtain a PEO layer on top of the silicone rabber surface, the surface was firstly modihed by incorporating an Si-H bond using (MeHSiO) , and followed by PEO grafting to the surface using a platinum-catalyzed hydrosilylation reaction. These PEO-modified surfaces were demonstrated by fibrinogen adsorption both from buffer and plasma, as well as albumin adsorption from buffer. Reductions in protein adsorption of as much as 90% were noted on these surfaces. 

The reaction of ozone with olefinic compounds is very rapid. Substiments on the double bond, which donate electrons, increase the rate of reaction, while electron-withdrawing substituents slow the reaction down. Thus, the rate of reaction with ozone decreases as follows polyisoprene > polybutadiene > polychloroprene [48]. The effect of substiments on the double bond is clearly demonstrated in Tables 15.2 and 15.3. Rubbers that contain only pendant double bonds such as EPDM do not cleave since the double bond is not in the polymer backbone. 

The most effective antiozonants are the substituted PPDs. Their mechanism of protection against ozone is based on the scavenger-protective film mechanism [68-70]. The reaction of ozone with the antiozonant is much faster than the reaction with the C=C bond of the rubber on the rubber surface [56]. The rubber is protected from the ozone attack tUl the surface antiozonant is depleted. As the antiozonant is continuously consumed through its reaction with ozone at the mbber surface, diffusion of the antiozonant from the inner parts to the surface replenishes the surface concentration to provide the continuous protection against ozone. A thin flexible film developed from the antiozonant/ozone reaction products on the mbber surface also offers protection. 

Mechanical adhesion. Cracks and pits are produced on the treated rubber surface which favor the mechanical interlocking with the adhesive. Eurthermore, unreacted solid prismatic TCI crystals on the treated rubber surface can be dissolved by the organic solvent into the adhesive, favoring the reaction with the adhesive. 

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