Temperature terpolymers

Terpolymers from dimethy]-a.-methy]styrene (3,4-isomer preferred)—a-methylstyrene—styrene blends in a 1 1 1 weight ratio have been shown to be useful in adhesive appHcations. The use of ring-alkylated styrenes aids in the solubiHty of the polymer in less polar solvents and polymeric systems (75). Monomer concentrations of no greater than 20% and temperatures of less than —20° C are necessary to achieve the desired properties. 

Dithiophosphates. These compounds (13) are made by reaction of an alcohol with phosphoms pentasulfide, then neutralization of the dithiophosphoric acid with a metal oxide. Like xanthates, dithiophosphates contain no nitrogen and do not generate nitrosamines during vulcanization. Dithiophosphates find use as high temperature accelerators for the sulfur vulcanization of ethylene—propylene—diene (EPDM) terpolymers. 

Commercial Forms. Eour different base polymers of VAMAC ethylene—acryhc elastomer are commercially available (Table 1). Until 1990, existing grades of ethylene—acryhc elastomers were based on a single-gum polymer. VAMAC G, defined as a terpolymer of 55% methyl acrylate, ethylene, and a cure-site monomer (5). In 1991, a higher methyl acrylate terpolymer, VAMAC LS, was introduced. The composition of this polymer was specifically chosen because it significantly increases the oil resistance of the polymer while minimizing losses in low temperature fiexibihty (6). 

Post-Curing. Whenever production techniques or economics permit, it is recommended that compounds based on terpolymer grades be post-cured. Relatively short press cures can be continued with an oven cure in order to develop full physical properties and maximum resistance to compression set. Various combinations of time and temperature may be used, but a cycle of 4 h at 175°C is the most common. The post-cure increases modulus, gready improves compresson set performance, and stabilizes the initial stress/strain properties, as chemically the polymer goes from an amide formation to a more stable imide formation. Peroxide-cured dipolymer compounds need not be post-cured. 

Two propylene oxide elastomers have been commercialized, PO—AGE and ECH—PO—AGE. These polymers show excellent low temperature flexibihty and low gas permeabihty. After compounding, PO—AGE copolymer is highly resiUent, and shows excellent flex life and flexibiUty at extremely low temperatures (ca —65°C). It is slightly better than natural mbber in these characteristics. Resistance to oil, fuels, and solvents is moderate to poor. Wear resistance is also poor. Unlike natural mbber, PO—AGE is ozone resistant and resistant to aging at high temperatures. The properties of compounded ECH—PO—AGE he somewhere between those of ECH—EO copolymer and PO—AGE copolymer (22). As the ECH content of the terpolymer increases, fuel resistance increases while low temperature flexibihty decreases. Heat resistance is similar to ECH—EO fuel resistance is similar to polychloroprene. The uncured mbber is soluble in aromatic solvents and ketones. 

A VDF unit also follows FIFP m the structurally much more complex terpo-lymers [30] Dipolymers contain 60 wt % VDF (66% F) and terpolymers contain 33-50 wt % VDF (66-69 5% F) and generally less than 28 wt % TFE Molecular weights range from 1 5 x 10 to 10 Their respective continuous service temperature ranges are -18 to 210 °C and -12 to 230 °C Dipolymer vulcanizates retam over 50% of their tensile strength for more than 1 year at 200 °C or for 2 months at 260 C... 

Adsorption of rubber over the nanosilica particles alters the viscoelastic responses. Analysis of dynamic mechanical properties therefore provides a direct clue of the mbber-silica interaction. Figure 3.22 shows the variation in storage modulus (log scale) and tan 8 against temperature for ACM-silica, ENR-silica, and in situ acrylic copolymer and terpolymer-silica hybrid nanocomposites. 

An oil-based drilling mud can be viscosified with maleated ethylene-propylene elastomers [919]. The elastomers are ethylene-propylene copolymers or ethylene-propylene-diene terpolymers. The maleated elastomers are far more effective oil mud viscosifiers than the organophilic clays used. On the other hand, specific organophilic clays can provide a drilling fluid composition less sensitive to high temperatures [491]. 

Similar copolymers with N-vinyl-N-methylacetamide as a comonomer have been proposed for hydraulic cement compositions [669]. The polymers consist of AMPS in an amount of 5% to 95%, vinylacrylamide in an amount of 5% to 95%, and acrylamide in an amount of 0% to 80%, all by weight. The polymers are effective at well bottom-hole temperatures ranging from 200° to 500° F and are not adversely affected by brine. Terpolymers of 30 to 90 mole-percent AMPS, 5 to 60 mole-percent of styrene, and residual acrylic acid are also suitable for well cementing operations [253]. 

Ethylene-propylene-diene terpolymers (EPDM), with their inherent complexity in structural parameters, owe their tensile properties to specific structures dictated by polymerization conditions, among which the controlling factor is the catalyst used in preparing the polymers. However, no detailed studies on correlation between tensile properties and EPDM structures have been published (l,2). An unusual vulcanization behavior of EPDMs prepared with vanadium carboxylates (typified by Vr g, carboxylate of mixed acids of Ccj-Cq) has been recently reported Q). This EPDM attains target tensile properties in 18 and 12 minutes at vulcanization temperatures of 150 and l60°C respectively, while for EPDMs prepared with V0Cl -Et3Al2Cl or V(acac) -Et2AlCl, about 50 and 0 minutes are usually required at the respective vulcanization temperatures, all with dieyclopentadiene (DCPD) as the third monomer and with the same vulcanization recipe. This observation prompted us to inquire into the inherent structural factors... 

A reversible succession of order-order and order-disorder transition was observed for a poly(ethylene-a/f-propylene)- -poly(ethylene-co-butylene)-b-polystyrene terpolymer, which shows at room temperature non-hexagonally packed PS cylinders. Upon heating, this system reorganizes to a hexagonally packed one, and at higher temperatures dynamic-mechanical analysis indicates the transition to the disordered state [73],... 

The carboxylated types (XNBR) contain one, or more, acrylic type of acid as a terpolymer, the resultant chain being similar to nitrile except for the presence of carboxyl groups which occur about every 100 to 200 carbon atoms. This modification gives the polymer vastly improved abrasion resistance, higher hardness, higher tensile and tear strength, better low temperature brittleness, and better retention of physical properties after hot-oil and air ageing when compared to ordinary nitrile rubber. 

The terpolymer is used in roller production and in many low temperature applications. 

The absence of any polar grouping gives this material superior low temperature performance when compared to the epichlorohydrin terpolymers, but this is at the expense of oil resistance. The unsaturated nature of the main chain confers excellent resistance to oxygen, ozone and UV light. 

Figure 8. Derivative Plot of Weight Loss versus Temperature for the Thermal Degradation of a Vinylidene Chloride/Methyl Acrylate (Five Mole Percent) / 4-Vinylpyridine (0.5 Mole Percent) Terpolymer at 170 °C. 

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