Tire Resins

Two-stage resins (novolacs) are produced by the acid-catalyzed reaction of phenol and a portion of the required formaldehyde. Tire resin product is brittle at room temperature. It can be melted, but it will not crosslink. Novolacs can only be cured by the addition of a hardener, almost always formaldehyde supplied as hexamethylene tetramine. Upon heating, the latter compound decomposes to yield ammonia and formaldehyde. 

Drippirrg is a corrrplex behavior tlrat deperrds on tire resin rrratrix, viscosity arrd part design. However, over tire years, it has been fourrd that very low levels of sorrre fluorirrated polyrrrers, rrotably polytettafluoroethylene (PTFE), can sigrrificarrtly reduce drippirrg. 

The situation is more complex when various otlier ingredients are added to PBT. Glass fibers, for instance, may lose adhesion from tire resin due to the action of water on tire glass-PBT interface, independent of the PBT-matrix reaction. This action will depend on specific contact conditions such as time, temperature and pH. In some instances, fiber-to-matrix adliesion can be recovered when tire sample is dried, resulting in tire recovery of some mechanical properties (if tire PBT matrix is not too severely degraded). Other additives can introduce additional complications. 

Polyamides. In 1988, 77% of U.S. demand for adipic acid was for nylon-6,6 fiber, while 11% was used in nyon-6,6 resins (195). In Western Europe only about 66% was for polyamide, because of the stronger competition from nylon-6. The fiber appHcations include carpets (67%), apparel (13%), tire cord (7%), and miscellaneous (13%). Nylon-6,6 resins were distributed between injection mol ding (85%) for such appHcations as automotive and electrical parts and for extmsion resins (15%) for strapping, film, and wire and cable. 

Composites. Various composite materials have evolved over the years as a significant class of high performance textile products. The prototype composite is carbon fiber with an epoxy resin matrix for stmctural akcraft components and other aerospace and military appHcations. Carbon fiber composites ate also used in various leisure and spotting items such as golf clubs, tennis rackets, and lightweight bicycle frames. However, other types of appHcations and composites ate also entering the marketplace. For example, short ceUulose fiber/mbbet composites ate used for hoses, belting, and pneumatic tire components. 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Another important apphcation for 4-/ f2 -octylphenol is ia the production of phenoHc resias. Novolak resias based oa 4-/ f2 -octylpheaol are widely used ia the tire iadustry as tackifiers. The tackiaess of these resias biads the many parts of an automobile tire prior to final vulcanization. A specialty use for novolak resias based oa 4-/ f2 -octylpheaol is the productioa of a ziacated resia, which is formulated as a dispersioa ia water and coated onto paper ia combination with eacapsulated leuco dyes to yield carbonless copy paper (see Microencapsulation). Pressure from writing bursts the encapsulated leuco dye, which is converted from its colorless form to its colored form by the ncated resin (53). Novolak resias based oa 4-/ f2 -octylpheaol are also used ia the productioa of specialty printing inks. 

Some amino resins are used as additives to modify the properties of other materials. For example, a small amount of amino resin added to textile fabric imparts the familiar wash-and-wear quaUties to shirts and dresses. Automobile tires are strengthened by amino resins which improve the adhesion of mbber to tire cord (qv). A racing sailboat may have a better chance to win because the sails of Dacron polyester have been treated with an amino resin (1). Amino resins can improve the strength of paper even when it is wet. Molding compounds based on amino resins are used for parts of electrical devices, botde and jar caps, molded plastic dinnerware, and buttons. 

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). 

Quinone dioximes, alkylphenol disulfides, and phenol—formaldehyde reaction products are used to cross-link halobutyl mbbers. In some cases, nonhalogenated butyl mbber can be cross-linked by these materials if there is some other source of halogen in the formulation. Alkylphenol disulfides are used in halobutyl innerliners for tires. Methylol phenol—formaldehyde resins are used for heat resistance in tire curing bladders. Bisphenols, accelerated by phosphonium salts, are used to cross-link fluorocarbon mbbers. 

Reinforcing Resins. Reinforcement and stiffness of a compound can also be achieved with the use of reactive resins. Resins consisting of two-component systems of resorcinol or resorcinol condensation products and a methylene donor such as hexamethoxymethylmel amine (HMMM) or hexamethyltetramine (HMT) are the most popular in tires. These materials can be prereacted and added to the formula, or for more effective results they can react in situ ie, they can be added separately into the formula and react when the tire is vulcanized. 

Other processing aids utilized in tires are vegetable oils (fatty acids, fatty acid esters/alcohols, and metal salts of these oils), naturally occurring resins such as pine tar, hydrocarbon resins from petroleum stUlbottoms, and vulcanized vegetable oils (WOs). WOs were utilized heavily in the early 1900s, but are no longer used extensively in tires. 

Resin Cure. Resin cure systems yield carbon—carbon cross-links and, consequendy, thermally stable materials. Butyl mbber vulcanised with resins are used as tire-curing bladders, and have a life of 300—700 curing cycles at steam temperature of 175°C at about 20 m/cycle. 

The engineering applications of PET resins include blow-molded botties, films, mol ding, and extmsion. Resins made for the latter two uses and related purposes are called mol ding resins in this article. The huge volumes of PET resin used for textile filaments and industrial fibers, eg, tire cord, are not included here. The PBT resins are mainly used for mol ding and related appHcations. 

November 14, 1987, three people were killed when two explosions and a tire caused extensive damage to the Hoechst Celanese acetic acid and acetic anhydride plant located near Pampa, ( X. Also on the Pampa site was a specialty resins plant operated by Interez, a unit ol RTZ ( orp. vhieh was interrupted because it depends on power supplied from the main Hoechsi Celanese I pc rati on. 

This chapter discusses synthetic polymers based primarily on monomers produced from petroleum chemicals. The first section covers the synthesis of thermoplastics and engineering resins. The second part reviews thermosetting plastics and their uses. The third part discusses the chemistry of synthetic rubbers, including a brief review on thermoplastic elastomers, which are generally not used for tire production but to make other rubber products. The last section addresses synthetic fibers. 

Alkyd resin synthesis. This synthesis consists of two steps. In the first step, a triglyceride oil is reacted at ca. 250°C with polyols, such as glycerol or pentaery-thritol, in tire presence of a basic catalyst to form a monoglyceride. In the second step, phthalic anhydride, with or without another dibasic acid such as maleic anhydride, is added to the reaction medium and reacted at high temperature. The resulting product is a branched polyester (Scheme 2.56). 

Sulfur cross-links have limited stability at elevated temperatures and can rearrange to form new cross-links. These results in poor permanent set and creep for vulcanizates when exposed for long periods of time at high temperatures. Resin cure systems provide C-C cross-links and heat stability. Alkyl phenol-formaldehyde derivatives are usually employed for tire bladder application. Typical vulcanization system is shown in Table 14.24. The properties are summarized in Tables 14.25 and 14.26. 

Composite Particles, Inc. reported the use of surface-modified rubber particles in formulations of thermoset systems, such as polyurethanes, polysulfides, and epoxies [95], The surface of the mbber was oxidized by a proprietary gas atmosphere, which leads to the formation of polar functional groups like —COOH and —OH, which in turn enhanced the dispersibility and bonding characteristics of mbber particles to other polar polymers. A composite containing 15% treated mbber particles per 85% polyurethane has physical properties similar to those of the pure polyurethane. Inclusion of surface-modified waste mbber in polyurethane matrix increases the coefficient of friction. This finds application in polyurethane tires and shoe soles. The treated mbber particles enhance the flexibility and impact resistance of polyester-based constmction materials [95]. Inclusion of treated waste mbber along with carboxyl terminated nitrile mbber (CTBN) in epoxy formulations increases the fracture toughness of the epoxy resins [96]. 

Superior Environmental Products, Inc. introduced a product based on liquid poly sulfide containing 40% of a surface-modified scrap tire mbber. The product, ER-IOOR, is a coating that can temporarily contain chemical, oil, and gasoline spills. Rodriguez [97] reported that an unsaturated polyester resin containing silane-treated CGR showed better mechanical properties than that containing untreated CGR. 

Xu, Z.N., Losur, S., and Gardner, S.D., Epoxy resin filled with tire rubber particles modified by plasma surface treatment, J. Adv. Mater., 30, 11, 1998. 

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