Rubber sensitizers

Perkalink . [Akzo] Cyanuratesormeth acrylates co-agent u> improve effi ciency of peroxide-induced cross-link ipg of rubber sensitizer for radiation cured compds. 

Tris(allyloxy)triazine 2,4,6-Tris(allyloxy)-1,3,5-triazine 2,4,6-Tris allyloxy)s-triazine. Co-agent to improve efficiency of peroxide-induced crosslinking of rubber sensitizer for radiation-cured compounds. Used in polymers as a monomer and modifier also used as an organic intermediate. Atao Chemie Am. Cyanamid Degussa AG National Starch Chem. UK... 

Other systems investigated by this group are butyl rubber, - natural rubber sensitized with acrylates,chloroprene, chlorobutyl rubber and nitrile rubber.More recently, Perera has examined the relationship between chemical changes in radiation-grafted natural rubber, determined using MAS NMR, and mechanical properties measured using dynamic mechanical analysis. 

Thermoplastic block copolymers were used for pressure rubber-sensitive and hot melt rubber adhesives from the middle sixties. These adhesives found application in packaging, disposable diapers, labels and tapes, among other industrial markets. The formulation of these adhesives generally includes an elastomer (generally containing styrene endblocks and either isoprene, butadiene or ethylene-butylene midblocks) and a tackifier (mainly a rosin derivative or hydrocarbon resin). 

Table 17. Contraceptive devices for rubber-sensitive individuals ...

Norris P, Storrs FJ (1990) Allergic contact dermatitis to adhesive bandages. Dermatol Clin 8 147-152 Nurse DS (1979) Rubber sensitivity. Austr J Dermatol 20 31-33 Nutter AF (1979) Contact urticaria to rubber. Br J Dermatol... 

Diphenylguanidine is a rubber sensitizer which can induce immediate-type reactions and delayed-type... 

Natural-mbber-based pressure-sensitive adhesives can be cured by standard mbber curatives, eg, sulfur plus an accelerator (see Rubber, natural) ... 

Because nitrile rubber is an unsaturated copolymer it is sensitive to oxidative attack and addition of an antioxidant is necessary. The most common practice is to add an emulsion or dispersion of antioxidant or stabilizer to the latex before coagulation. This is sometimes done batchwise to the latex in the blend tank, and sometimes is added continuously to the latex as it is pumped toward further processing. PhenoHc, amine, and organic phosphite materials are used. Examples are di-Z fZ-butylcatechol, octylated diphenylamine, and tris(nonylphenyl) phosphite [26523-78-4]. All are meant to protect the product from oxidation during drying at elevated temperature and during storage until final use. Most mbber processors add additional antioxidant to their compounds when the NBR is mixed with fillers and curatives in order to extend the life of the final mbber part. 

Polymerization processes are characterized by extremes. Industrial products are mixtures with molecular weights of lO" to 10. In a particular polymerization of styrene the viscosity increased by a fac tor of lO " as conversion went from 0 to 60 percent. The adiabatic reaction temperature for complete polymerization of ethylene is 1,800 K (3,240 R). Heat transfer coefficients in stirred tanks with high viscosities can be as low as 25 W/(m °C) (16.2 Btu/[h fH °F]). Reaction times for butadiene-styrene rubbers are 8 to 12 h polyethylene molecules continue to grow lor 30 min whereas ethyl acrylate in 20% emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within hmits. Initiators of the chain reactions have concentration of 10" g mol/L so they are highly sensitive to poisons and impurities. 

There is also a large number of synthetic heterocyclic compounds with other important practical applications, as dyestuffs, copolymers, solvents, photographic sensitizers and developers, as antioxidants and vulcanization accelerators in the rubber industry, and many are valuable intermediates in synthesis. 

In general the nitroso rubbers also suffer from a poor resistanee to ionising radiation, sensitivity to degradation by organie bases, highly toxic degradation products and an exceptionally high cost. The advent of the rubbers based on perfluorofmethyl vinyl ether) considered above and of the phosphonitrilic elastomers considered below would appear to put the commercial future of these materials in extreme doubt. 

A number of higher poly(vinyl ether)s, in particular the ethyl and butyl polymers, have found use as adhesives. When antioxidants are incorporated, pressure-sensitive adhesive tapes from poly(vinyl ethyl ether) are said to have twice the shelf life of similar tapes from natural rubber. Copolymers of vinyl isobutyl ether with methyl acrylate and ethyl acrylate (Acronal series) and with vinyl chloride have been commercially marketed. The first two products have been used as adhesives and impregnating agents for textile, paper and leather whilst the latter (Vinoflex MP 400) has found use in surface coatings. 

Caution 2,4-Dinitrochlorobenzene causes severe skin irritation to some individuals. Sensitive persons are advised to wear rubber gloves. 

Synthetic resins are extensively used, e.g., in surface finishes, in the fabrication and repair of boat and motor vehicle bodies, in the manufacture of laminated boards, for electrical components, in pattern making and in paints and varnishes. Non-rubber adhesives made from fish glues and from cotton derivatives (e.g. cellulose acetate) tend not to be sensitizing but, depending upon composition and the manner of use, many other types may pose significant dermatitic and fume hazards. 

For the above scales, eye protection should be worn and work should be undertaken in a standard fume-cupboard behind a well-anchored polycarbonate screen. It is advisable to wear a protective apron and hand protection whether leather gauntlets or tongs should be used will be dictated by circumstances. Such measures are recommended but it should be ensured that they do not precipitate a hazard as a result of loss of tactile sensitivity (e.g. dropping a flask, overtightening clamps, exerting excessive pressure when assembling apparatus). The material of gloves needs consideration. (PVC but not rubber is suitable for tert-butyl peroxide.)... 

Natural rubber was the first polymer base for the early pressure sensitive adhesives. Their origin may be traced to the early medical plasters formulated in... 

In the earlier art, there was some consideration that partial incompatibility of the tackifier resin with the rubber was responsible for the appearance of tack, but this no longer is seriously held in light of continuing studies by many investigators. Aubrey [38] has addressed this in his review of the mechanism of tackification and the viscoelastic nature of pressure sensitive adhesives. Chu [39] uses the extent of modulus depression with added tackifier as a measure of compatibility. Thus in a plot of modulus vs. tackifier concentration, the resin that produces the deepest minimum is the most compatible. On this basis, Chu rates the following resins in order of compatibility for natural rubber rosin ester > C-5 resin > a-pinene resin > p-pinene resin > aromatic resin. 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

Erwins, E.E., St. Clair, D.J., Erickson, J.E. and Korez, W.H., Thermoplastic rubbers ABA block copolymers. In Satas, D. (Ed.), Handbook of Pressure Sensitive Adhesive Technology. Van Nostrand Reinhold, New York, 1989, pp. 317-373. 

Typical formulation of a pressure-sensitive rubber adhesive... 

Rubber-grade resins are mostly in the softening point range 70-100°C R B. A deviation of 5-10°C in softening point may cause problems. The softening point of a resin affects the properties of adhesives. Hence, for pressure-sensitive rubber adhesives the decrease in the softening point of the resin produces a more tacky adhesive with less cohesive strength. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

Specific formulations of BR and PIB adhesives can be found in [5]. These adhesives are supplied in forms quite similar to those of natural rubber solvent-borne and water-borne dispersions, and pressure-sensitive pre-coated films. 

Gazeley. K.F. and Mente, P.G., Pressure-sensitive adhesives from modified natural rubber latex. Adhesives, Sealants and Encapsulants Conference, Kensington, London, 5th November, 1985. 

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