Epoxide resins additives

AH of the amine hydrogens are replaced when MDA or PMDA reacts with epoxides to form amine based polyols. These polyols can be used in reactions with isocyanates to form urethanes or with additional epoxide to form cross-linked thermo set resins. 

A cement slurry additive consisting of methylcellulose, melamine-formaldehyde resin, and trioxane has been proposed for better bonding of cement to the casing string [20]. Bisphenol-A epoxide resins, with amine-based curing agents, sand filler, and a mixture of n-butanol and dimethyl benzene as a diluent, have been proposed as additives to increase adhesion properties of cement [572]. 

Y. R. Leonov, M. E. Lamosov, S. A. Ryabokon, V. A. Mosin, B. G. Dzetl, F. G. Mamulov, O. G. Bobrov, and V. M. Savoskin. Plugging material for wells in the oil and gas industry—contains mineral binder and powder waste from production of epoxide resins as epoxide resin-based additive. Patent RU 2036297-C, 1995. 

In addition to the use of peroxides for crosslinking, metal oxide, polyfunctional alcohols, amines and epoxide resin cure systems can be used with CSM rubbers. In the metal oxide based cure systems it is usual to add a weak acid, such as stearic acid, and accelerators, such as MBT, MBTS or TMTD magnesium or lead oxides are generally used. 

As an additional component, various thermoplastic polymers can be used. As a binder for copper clad laminates, a solution of solid epoxide resin (Epikote 1001), BPA/DC prepolymer, Zn acetate and poly(phenylene sulfide) was used [83], Other binders for reinforced plastics contain polysulfone. Such compositions consist of liquid BPA/ECH epoxide resin, BPA/DC prepolymer, polysulfone and bis(4-hydro-xyphenyl)sulfone [85]. Bis(4-aminophenyl)sulfone can be also added [86]. In such systems the bisphenol reacts with the epoxide resin as a chain extension agent, whereas the diamine crosslinks the diepoxide. The Tg values are close to 200 °C. They can be increased a little, if the BPA/ECH epoxide resin is replaced by the tetra-epoxide A,A,A, A -tetrakis(2,3-epoxypropyl)diaminodiphenylmethane [87]. 

As in the cyanate/epoxide compositions, polysulfone is used as an additive in cyanate/epoxide/maleimide systems. As an example, a composition for carbon-fiber composites should be mentioned. It contains BPA/DC-BMI prepolymer, epoxide resin and polyethersulfone [111-113] Zn acetate and dicumyl peroxide are added. Polyethersulfone powder was added to the three-component system with 4,4 -diamino-diphenylmethane-based tetraepoxide as one of the epoxy resins used [114]. 

To overcome these drawbacks, in recent years much attention has been paid to the development of resins which cem be f2d ricated with the same processes as those for conventional polyester resins, but having superior properties. Vinyl ester resins are the result of such development efforts (4-6). Vinyl ester resins are addition products of Vcurious epoxide resins and ethylenically unsaturated mono-carboxylic acids ( ). It condsines the excellent mechcuiical, chemical cuid solvent resistemce of epoxy resins with the properties found in the unsaturated polyester resins. In general, the cured vinyl ester resin has physical properties superior to the cured conventional ester resin, particulcurly corrosion resistcuice. This arises from the differences in the number and arremgement of polar groups such as ester and hydroxyl groups eind ccurbon-to-ccirbon double bonds present in the polymer chains. 

The variety of substances used as additives in polymers is considerable. For example, the fillers may include china clay, various forms of calcium carbonate, talc, silicas (diatomaceous silica), silicates, carbon black, etc. The impact modifiers typically include other polymers. Plasticizers include certain polymers with low (oligomers), dialkyl phthalates, dialkyl sebacates, chlorinated paraffin waxes, liquid paraffinic fractions, oil extracts, etc. Heat stabilizers include heavy metals salts such as basic lead carbonate, basic lead sulfate, dibasic lead phosphite (also acting as a light stabilizer), dibasic lead phthalate, stearates, ricinoleates, palmitates and octanoates of cadmium and barium, epoxide resins and oils, amines, diphenylurea, 2-phenylindole, aminocrotonates. The antioxidants include tris-nonyl phenyl phosphite, 2,6-di-ferf-butyl-p-cresol (BHT), octadecyl-3,5-di-terf-butyl-4-hydroxyhydrocinnamate, etc. The UV stabilizers include modified benzophenones and benzotriazoles. Processing lubricants include calcium stearate, stearic acid, lead stearate, various wax derivatives, glyceryl esters and long-chain acids. Fire retardants include antimony oxide, some pyrophosphates, etc. 

Several factors are thought to be involved in the mechanism of durability improvement. The objective of this study was to examine compounds which are capable of interacting chemically with the steel surface. In addition, reaction with the epoxide resin is also desirable. The polyfunctional mercaptoester compounds meet both of these requirements in that the mercaptoester moiety provides a means of chelating iron cations and in addition is very reactive towards the epoxide group in the presence of an amine. The polyfunctional nature of this compound enables it to attach to the steel surface at more than one site and provides a group which can chemically attach to the resin. The dramatic improvement in bond durability supports such a hypothesis. 

Dopico et al. [73] prepared 5- and 6-based furan resins which, after acid-catalyzed polymerization, were subjected to epoxidation with thiokol in different proportions. In a second series of experiments, 6-7% of 2 was added to the epoxidized resins. They showed that all these resins presented a lower flexure resistance compared to unmodilied totally furanic binder. Moreover, the addition of 2 was found to induce negative effects on the mechanical properties of metal-to-metal assemblies. 

Table 3.2 also includes data for the advanced thermoplastic resins (PEEK) and for a thermosetting resin, an end-capped bismaleimide (BMI) called PMR-15. Moisture contents tend to be lower for these advanced materials [12,13]. One way to overcome the environmental sensitivity of epoxide resins is to employ these advanced resins, as demonstrated in Table 3.2. However, changing to other resin systems brings with it other concerns. For example, PEEK relies on crystallinity for its higher temperature performance. Its glass transition temperature is only 143°C and a change in modulus can be observed at that temperature. In addition, higher process temperatures are required both for high performance thermosets and thermoplastics. The consequent higher residual thermal stresses can off-set some of the advantages of a higher service temperature, in comparison with advanced epoxy resins.

Vinyl ester resins are produced by the addition of ethylenically unsaturated carbo acids (methacrylic or acrylic acid) to an epoxide resin (usually of the bisphenol epichlorohydrin type). The reaction of acid addition to the epoxide ring (esterification exothermic and produces a hydroxyl group without the formation of by-products. Appropriate diluents and polymerization inhibitors are added during or after esterification. 

Amine curing agents may be primary or secondary amines, aliphatic, alicyclic or aromatic. The reaction with an epoxide resin is an addition reaction where the amine links directly with an epoxide group to form a... 

In addition to the stripping of terminal groups, cleavage of bonds among carbon atoms in the aliphatic portions of the chains of the epoxide resin is also possible. In this case low-molecular-weight volatile products can be formed. 

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