Copolymers aging

PMMA-ANT aged copolymer. Aging-induced, increasing electro-optic coefficients were observed in these polymers. 

Adhesives. Acryhc emulsion and solution polymers form the basis of a variety of adhesive types. The principal use is in pressure-sensitive adhesives, where a film of a very low T (<—20 " C) acrylic polymer or copolymer is used on the adherent side of tapes, decals, and labels. Acrylics provide a good balance of tack and bond strength with exceptional color stabiUty and resistance to aging (201,202). AcryUcs also find use in numerous types of constmction adhesive formulations and as film-to-film laminating adhesives (qv). 

Examination of oven-aged samples has demonstrated that substantial degradation is limited to the outer surface (34), ie, the oxidation process is diffusion limited. Consistent with this conclusion is the observation that oxidation rates are dependent on sample thickness (32). Impact property measurements by high speed puncture tests have shown that the critical thickness of the degraded layer at which surface fracture changes from ductile to brittle is about 0.2 mm. Removal of the degraded layer restores ductiHty (34). Effects of embrittled surface thickness on impact have been studied using ABS coated with styrene—acrylonitrile copolymer (35). 

I ew Rubber-Modified Styrene Copolymers. Rubber modification of styrene copolymers other than HIPS and ABS has been useful for specialty purposes. Transparency has been achieved with the use of methyl methacrylate as a comonomer styrene—methyl methacrylate copolymers have been successfully modified with mbber. Improved weatherability is achieved by modifying SAN copolymers with saturated, aging-resistant elastomers (88). 

In 1957, it was discovered that organometaUic catalysts gave high mol wt polymers from epoxides (3). The commercially important, largely amorphous polyether elastomers developed as a result of this early work are polyepichlorohydrin (ECH) (4,5), ECH—ethylene oxide (EO) copolymer (6), ECH—aUyl glycidyl ether (AGE) copolymer (7,8), ECH—EO—AGE terpolymer (8), ECH—propylene oxide (PO)—AGE terpolymer (8,9), and PO—AGE copolymer (10,11). The American Society for Testing and Materials (ASTM) has designated these polymers as follows ... 

Epichlorohydrin Elastomers without AGE. ECH homopolymer, polyepichlorohydrin [24969-06-0] (1), and ECH—EO copolymer, poly(epichlorohydrin- (9-ethylene oxide) [24969-10-6] (2), are linear and amorphous. Because it is unsymmetrical, ECH monomer can polymerize in the head-to-head, tail-to-tail, or head-to-tail fashion. The commercial polymer is 97—99% head-to-tail, and has been shown to be stereorandom and atactic (15—17). Only low degrees of crystallinity are present in commercial ECH homopolymers the amorphous product is preferred. 

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. 

Molecular weight determinations of ECH—EO, ECH—AGE, ECH—EO—AGE, ECH—PO—AGE, and PO—AGE have not been reported. Some solution studies have been done on poly(propylene oxide), and these may approximate solution behavior of the PO—AGE copolymer (33,34). 

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

AGE-Gontaining Elastomers. The manufacturing process for ECH—AGE, ECH—EO—AGE, ECH—PO—AGE, and PO—AGE is similar to that described for the ECH and ECH—EO elastomers. Solution polymerization is carried out in aromatic solvents. Slurry systems have been reported for PO—AGE (39,40). When monomer reactivity ratios are compared, AGE (and PO) are approximately 1.5 times more reactive than ECH. Since ECH is slightly less reactive than PO and AGE and considerably less reactive than EO, background monomer concentration must be controlled in ECH—AGE, ECH—EO—AGE, and ECH—PO—AGE synthesis in order to obtain a uniform product of the desired monomer composition. This is not necessary for the PO—AGE elastomer, as a copolymer of the same composition as the monomer charge is produced. AGE content of all these polymers is fairly low, less than 10%. Methods of molecular weight control, antioxidant addition, and product work-up are similar to those used for the ECH polymers described. 

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. 

During World War II, polychloroprene was chosen as a replacement for natural rubber because of its availability. Two copolymers of chloroprene and sulphur which contain thiuram disulphide were available (Neoprene GN and CG). One of the first successful applications of these polychloroprene adhesives was for temporary and permanent sole attachment in the shoe industry. However, these polychloroprene cements show a decrease in viscosity on ageing and a black discolouration appears during storage in steel drums. Discolouration was produced by trace amounts of hydrochloric acid produced by oxidation of polychloroprene... 

A different variety of copolymer has been prepared by Gramain and Frere who treated 1,10-diaza-l 8-crown-6 with the bisglycidyl ether of bisphenol A. The reaction was conducted at reflux in a mixture of THF and methanol. The polymer, illustrated in Eq. (6.24) was formed 83% yield. The polymer was appparently quite stable, surviving aging tests conducted over a two-year period. 

For partially crystalline ionomers, such as those based on copolymers of ethylene and methacrylic acid, even time or aging at room temperature can have an effect on mechanical properties. For example, upon aging at 23°C, the modulus of the acid form of the copolymer increased 28%, while in the ionomer form, the increase ranged up to 130%, with the specific gain in modulus depending on the degree of conversion and on the counterion that was present [17]. 

Nitrile rubber (NBR) was first commercialized by I.G. Farbindustry, Germany, in 1937, under the trade name of Buna N. Its excellent balance of properties confers it an important position in the elastomer series. Nitrile rubber, a copolymer of butadiene and acrylonitrile, is widely used as an oil-resistant rubber. The acrylonitrile content decides the ultimate properties of the elastomer. In spite of possessing a favorable combination of physical properties, there has been a continuous demand to improve the aging resistance of NBR due to the tougher requirements of industrial and automotive applications. 

---