Vulcanizing adhesive

THORNTON ET AT. Cathodic Delaminotion of Protective Coatings Table II. Conunercial Vulcanizing Adhesives... 

A true synthetic natural rubber was introduced in the mid-1960s with the exact same chemical structure as latex tapped from a tree. The difference is that natural rubber comes with a variety of other ingredients in the latex that can both add and detract from performance, while polyisoprene is considered relatively pure. In addition, there are some differences in molecular weight distribution that impact performance. Available in both latex and solid forms, this elastomer can be directly substituted for natural rubber in many applications. Adhesives which are not cured tend to have higher creep values than natural rubber, but also exhibit lower tack and green strength properties. Vulcanized adhesive products perform equal to cured natural rubber adhesive products. 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Tire Cord. Melamine resins are also used to improve the adhesion of mbber to reinforcing cord in tires. Textile cord is normally coated with a latex dip solution composed of a vinylpyridine—styrene—butadiene latex mbber containing resorcinol—formaldehyde resin.. The dip coat is cured prior to use. The dip coat improves the adhesion of the textile cord to mbber. Further improvement in adhesion is provided by adding resorcinol and hexa(methoxymethyl) melamine [3089-11 -0] (HMMM) to the mbber compound which is in contact with the textile cord. The HMMM resin and resorcinol cross-link during mbber vulcanization and cure to form an interpenetrating polymer within the mbber matrix which strengthens or reinforces the mbber and increases adhesion to the textile cord. Brass-coated steel cord is also widely used in tires for reinforcement. Steel belts and bead wire are common apphcations. Again, HMMM resins and resorcinol [108-46-3] are used in the mbber compound which is in contact with the steel cord to reinforce the mbber and increase the adhesion of the mbber to the steel cord. This use of melamine resins is described in the patent Hterature (49). 

Insoluble Sulfur. In natural mbber compounds, insoluble sulfur is used for adhesion to brass-coated wire, a necessary component in steel-belted radial tires. The adhesion of mbber to the brass-plated steel cord during vulcanization improves with high sulfur levels ( 3.5%). Ordinary rhombic sulfur blooms at this dose level. Crystals of sulfur on the surface to be bonded destroy building tack and lead to premature failure of the tire. Rubber mixtures containing insoluble sulfur must be kept cool (<100°C) or the amorphous polymeric form converts to rhombic crystals. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Sodium nitrate is also used in formulations of heat-transfer salts for he at-treatment baths for alloys and metals, mbber vulcanization, and petrochemical industries. A mixture of sodium nitrate and potassium nitrate is used to capture solar energy (qv) to transform it into electrical energy. The potential of sodium nitrate in the field of solar salts depends on the commercial development of this process. Other uses of sodium nitrate include water (qv) treatment, ice melting, adhesives (qv), cleaning compounds, pyrotechnics, curing bacons and meats (see Food additives), organics nitration, certain types of pharmaceutical production, refining of some alloys, recovery of lead, and production of uranium. 

Covers for the battery designs in Figures 1 and 2 are typically molded from materials identical to that of the respective case, and vent plugs are frequentiy made of molded polypropylene. Other combinations are possible, eg, containers molded of polyethylene or polypropylene may be mated with covers of high impact mbber for use in industrial batteries. After the cover is fitted over the terminal post, it is sealed onto the case. The cover is heat bonded to the case, if it is plastic it is sealed with an epoxy resin or other adhesive, if it is vulcanized mbber. Vent caps are usually inserted into the cover s acid fiU holes to faciHtate water addition and safety vent gasses, except for nonaccessible maintenance-free or recombinant batteries. In nonaccessible batteries, the vent is fabricated as part of the cover. 

Adhesives in the Tire Industry. Cobalt salts are used to improve the adhesion of mbber to steel. The steel cord must be coated with a layer of brass. During the vulcanization of the mbber, sulfur species react with the copper and zinc in the brass and the process of copper sulfide formation helps to bond the steel to the mbber. This adhesion may be further improved by the incorporation of cobalt soaps into the mbber prior to vulcanization (53,54) (see Tire cords). 

Because of increased production and the lower cost of raw material, thermoplastic elastomeric materials are a significant and growing part of the total polymers market. World consumption in 1995 is estimated to approach 1,000,000 metric tons (3). However, because the melt to soHd transition is reversible, some properties of thermoplastic elastomers, eg, compression set, solvent resistance, and resistance to deformation at high temperatures, are usually not as good as those of the conventional vulcanized mbbers. AppHcations of thermoplastic elastomers are, therefore, in areas where these properties are less important, eg, footwear, wine insulation, adhesives, polymer blending, and not in areas such as automobile tires. 

Changes observed in the composition of the rubber/brass interphase correlated well with results of adhesion tests carried out on brass-plated steel wires embedded in blocks of rubber [46]. The force required to pull the wires out of the blocks decreased steadily as vulcanization temperature increased. This effect was especially pronounced when the specimens were aged at elevated temperature and humidity for several days before the wires were pulled out of the rubber blocks. 

Geon and Seo [47] also determined the effect of vulcanization time on the adhesion of natural rubber to brass-plated steel. For relatively short times, there was a peak at the end of the copper profile that corresponded well with a peak in the sulfur profile. Similarly, peaks in the zinc and oxygen profiles corresponded well. These results showed that copper sulfide and zinc oxide mostly formed at short times but some evidence for formation of zinc sulfide was also obtained. For long times, the peak in the sulfur profile no longer corresponded with that in the copper profile. Instead, the peak in the sulfur profile corresponded to the peak in the zinc profile. It was concluded that the formation of zinc sulfide increased substantially at long times. An increase in vulcanization time correlated well with a decrease in the force required to pull brass-plated steel wires out of rubber blocks. 

Sulfur chemistry [29] has also been used to crosslink rubber/resin PSAs, although the use of elemental sulfur itself yields tapes that can stain substrates. Other patents exemplify the use of typical rubber vulcanizing chemistry such as Tetrone A , dipentamethylenethiuramtetrasulfide, and Tuads , tetramethylthiu-ram disulfide [30], or zinc butyl xanthate [31] for this purpose. Early art [32] also claimed electron beam curing of both natural rubber and other adhesives that were solvent coated on tape backings. Later references to electron beam curing... 

Some rubber base adhesives need vulcanization to produce adequate ultimate strength. The adhesion is mainly due to chemical interactions at the interface. Other rubber base adhesives (contact adhesives) do not necessarily need vulcanization but rather adequate formulation to produce adhesive joints, mainly with porous substrates. In this case, the mechanism of diffusion dominates their adhesion properties. Consequently, the properties of the elastomeric adhesives depend on both the variety of intrinsic properties in natural and synthetic elastomers, and the modifying additives which may be incorporated into the adhesive formulation (tackifiers, reinforcing resins, fillers, plasticizers, curing agents, etc.). 

During World War II, several new synthetic elastomers were produced and new types of adhesives (mainly styrene-butadiene and acrylonitrile copolymers) were manufactured to produce adequate performance in joints produced with new difficult-to-bond substrates. Furthermore, formulations to work under extreme environmental conditions (high temperature, resistance to chemicals, improved resistance to ageing) were obtained using polychloroprene (Neoprene) adhesives. Most of those adhesives need vulcanization to perform properly. 

Structural applications of rubber base adhesives were also obtained using rubber-thermosetting resin blends, which provided high strength and low creep. The most common formulations contain phenolic resins and polychloroprene or nitrile rubber, and always need vulcanization. 

Resistance to weathering. Zinc oxide and magnesium oxide stabilize poly-chloroprene against dehydrochlorination. Further, zinc oxide helps vulcanize the rubber, and magnesium oxide reacts with /-butyl phenolic resin to produce a resinate which improves heat resistance of solvent-borne polychloroprene adhesives. 

Rubber base adhesives can be used without cross-linking. When necessary, essentially all the cross-linking agents normally used in the vulcanization of natural rubber can be used to cross-link elastomers with internal double carbon-carbon bonds. A common system, which requires heat to work, is the combination of sulphur with accelerators (zinc stearate, mercaptobenzothiazole). The use of a sulphur-based cross-linking system with zinc dibutyldithiocarbamate and/or zinc mercaptobenzothiazole allows curing at room temperature. If the formulation is very active, a two-part adhesive is used (sulphur and accelerator are placed in two separate components of the adhesive and mixed just before application). 

NR adhesives perform adequately under peeling stresses. The peel strength can vary from a few N/m in PSA formulations to substrate tear in vulcanized compounds used in hose, belting and tire products. 

Nonvulcanizing NR adhesives typically withstand temperature ranges between —30°C and 65°C. Vulcanized NR adhesives can perform between —40°C and 150°C. 

Reclaimed rubber can be used in non-vulcanizing general-purpose NR adhesives. It can be used for insulation, packaging materials, and bonding of polyethylene, canvas, metals and wood. 

Vulcanizing latex adhesives are used in the manufacture of textiles, rugs and carpets. The vulcanizing ingredients are sulphur, zinc oxide and accelerators (for example, zinc dibutyldithiocarbamate and zinc mercaptobenzothiazole to produce vulcanization at room temperature). 

Like the 1-RTV systems, the two-part room temperature vulcanization systems (2-RTV) cure to produce flexible elastomers that resist humidity and other harsh environments. Interestingly, they display primerless adhesion property to many substrates, and are used in silicone adhesives, sealants, seals, and gaskets, to name a few. 

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