Heat distortion temperature epoxies

Because the heat distortion temperature of cured epoxy resins (qv) increases with the functionality of the curing agents, pyromellitic dianhydride is used to cross-link epoxy resins for elevated temperature service. The dianhydride may be added as a dispersion of micropulverized powder in liquid epoxy resin or as a glycol adduct (158). Such epoxies may be used as an insulating layer in printed circuit boards to improve heat resistance (159). Other uses include inhibition of corrosion (160,161), hot melt traffic paints (162), azo pigments (163), adhesives (164), and photoresist compounds (165). 

Meta-phenylenediamine, a crystalline solid with a melting point of about 60°C, gives cured resins with a heat distortion temperature of 150°C and very good chemical resistance. It has a pot life of six hours for a 200 g batch at room temperature whilst complete cures require cure times of four to six hours at 150°C. About 14 pts phr are used with the liquid epoxies. The main disadvantages are the need to heat the components in order to mix them, the irritating nature of the amine and persistent yellow staining that can occur on skin and clothing. The hardener finds use in the manufacture of chemical-resistant laminates. 

In order to obtain cured products with higher heat distortion temperatures from bis-phenol epoxy resins, hardeners with higher functionality have been used, thus giving a higher degree of cross-linking. These include pyromellitic dianhydride IV, and trimellitic anhydride V. 

Heat distortion temperatures of resins cured with pyromellitic dianhydride are often quoted at above 200°C. The high heat distortion is no doubt also associated with the rigid linkages formed between epoxy molecules because of the nature of the anhydride. The use of these two anhydrides has, however, been restricted because of difficulties in incorporating them into the resin. 

In the NMA cured epoxy it appeared that the protonated aromatic lines were not broadened relative to the piperidine cure even though the heat distortion temperature of the NMA cured epoxy was greater. 

While unaffected by water, styrofoam is dissolved by many organic solvents and is unsuitable for high-temperature applications because its heat-distortion temperature is around 77°C. Molded styrofoam objects are produced commercially from expandable polystyrene beads, but this process does not appear attractive for laboratory applications because polyurethane foams are much easier to foam in place. However, extruded polystyrene foam is available in slabs and boards which may be sawed, carved, or sanded into desired shapes and may be cemented. It is generally undesirable to join expanded polystyrene parts with cements that contain solvents which will dissolve the plastic and thus cause collapse of the cellular structure. This excludes from use a large number of cements which contain volatile aromatic hydrocarbons, ketones, or esters. Some suitable cements are room-temperature-vulcanizing silicone rubber (see below) and solvent-free epoxy cements. When a strong bond is not necessary, polyvinyl-acetate emulsion (Elmer s Glue-All) will work. 

Tpo maximize the utility of crosslinked cycloaliphatic epoxy resins in some of the more critical application areas, improved toughness is required. Such improvements can often be made through modification with various flexibilizing agents, but as a rule this improvement is accompanied by a severe degradation of the strength and heat distortion temperature of the cured system. 

Effect of Molecular Configuration of Elastomer. The extent of the impact and strength improvements of ERL-4221 depends on the chemical structure and composition of the elastomer modifier. The data shown in Table I indicate that the carboxyl terminated 80-20 butadiene-acrylonitrile copolymer (CTBN) is the most effective toughening and reinforcing agent. The mercaptan terminated copolymer (MTBN) is considerably less effective as far as tensile strength and heat distortion temperature are concerned. The mercaptan groups are considerably less reactive with epoxides than carboxyls (4), and this difference in the rate of reaction may influence the extent of the epoxy-elastomer copolymerization and therefore the precipitation of the rubber as distinct particles. 

The carboxyl terminated polybutadiene (C-3000) is about equally effective to CTBN in heat distortion temperature and impact but considerably less effective in strength. From the haze data (the percent haze of ERL-4221 modified with 10 phr of CTBN and C-3000 were 17 and 85% respectively) it is quite clear that this elastomer (C-3000) is highly incompatible with the epoxy-hardener system in the cured state. A 2000 molecular weight polybutadiene elastomer, containing no carboxyl groups, was completely incompatible with the epoxy system and segregated in the cured state. 

The cycloaliphatic epoxy resins are characterized by the saturated ring in their chemical structure. They are almost water-white, very low-viscosity liquids. They provide excellent electrical properties such as low dissipation factor and good arc-track resistance, good weathering, and high heat distortion temperature. They are also free of hydrolyzable chlorine, sometimes present in DGEBA resins, which adversely affects certain electronic applications. 

Many different methods can be used to measure the degree of crosslinking within an epoxy specimen. These methods include chemical analysis and infrared and near infrared spectroscopy. They measure the extent to which the epoxy groups are consumed. Other methods are based on the measurements of properties that are directly or indirectly related to the extent and nature of crosslinks. These properties are the heat distortion temperature, glass transition temperature, hardness, electrical resistivity, degree of solvent swelling and dynamic mechanical properties, and thermal expansion rate. The methods of measurement are described in Chap. 20. 

The advantages, disadvantages, and applications for the major types of epoxy curing agents are summarized in Table 5.1. The required mix ratios, curing temperatures, and the resulting heat distortion temperatures of the cured product are provided in Table 5.2. 

Primary and secondary aliphatic amines react relatively rapidly with epoxy groups at room or lower temperature to form three-dimensional crosslinked structures. The resulting cured epoxies have relatively high moisture resistance and good chemical resistance, particularly to solvents. They also have moderate heat resistance with a heat distortion temperature in the range of 70 to 110°C. Thus, short-term exposures of cured adhesive joints at temperatures up to 100°C can generally be tolerated. 

Other amines, such as aromatic or cycloaliphatic, are less reactive and generally require elevated-temperature cures that result in higher heat distortion temperatures (140 to 150°C). However, aromatic amine adducts of liquid epoxies can be accelerated to cure at room temperature. Aliphatic amines can also be accelerated. 

HHPA is generally used in a concentration between 55 and 80 pph depending on the nature of the epoxy resin. The viscosity is generally about 200 cP at 40°C when mixed with a DGEBA epoxy resin. A typical cure schedule for a 0.5 to 2 percent BDMA catalyzed system is 2 h at 80°C plus 1 h at 200°C. Typical of all the anhydride curing agents, the cured epoxy will demonstrate high heat distortion temperatures and excellent chemical resistance. 

Pyromellitic dianhydride (PMDA) is a solid having a melting point of 286°C. It contains two anhydride groups symmetrically attached to a benzene ring. Because of the compactness of the molecule, PMDA achieves very high crosslink densities and, therefore, high heat and chemical resistance. PMDA cured epoxy adhesives have a heat distortion temperature on the order of 280 to 290°C. 

The tertiary amine salts are claimed to provide epoxy formulations with very good adhesion to metal. The cured resins also show a hydrophobic effect when in contact with water or at high humidities. The strength, toughness, and elongation (4.7 percent) of the cured epoxy resin are very good. However, heat distortion temperature is only in the range of 70 to 80°C, and chemical resistance is relatively poor for an epoxy. The physical properties fall off rapidly with any rise in temperature. 

Compared with other catalysts that homopolymerize epoxies, the imidazole offers improved thermal properties and retention of mechanical properties at more elevated temperatures. The cured resin has a heat distortion temperature between 85 and 130°C, which can be further increased by a postcure to about 160°C. 

Hybrid resins have been used to improve the flexibility, thermal shock resistance, elongation, heat distortion temperature, and impact strength of unmodified epoxy adhesives. However, there can also be some sacrifice in certain physical properties due to the characteristics of the additive. These alloys result in a balance of properties, and they almost never result in the combination of only the beneficial properties from each component without carrying along some of their downside. 

The heat distortion temperature is only slightly affected by the incorporation of 20 percent polysulfide polymer, but at a 1 1 ratio the drop becomes significant. This property prevents the use of epoxy-polysulfide adhesives at elevated temperatures. 

The physical and electrical characteristics of the anhydride cured systems are very good over a wide temperature range. Compared to amines, anhydride cured epoxies exhibit better chemical resistance to aqueous acids, but less chemical resistance to some other reagents. When epoxy resins are cured with anhydrides, the product has relatively high heat distortion temperature and low moisture sensitivity. 

Effect of Level of CTBN. In Table V we varied the level of CTBN at a constant amount of piperidine. At 20 parts of CTBN we find a fourfold increase in impact strength with an 11 °C loss of heat distortion temperature. This loss of thermal properties suggests that some of the CTBN flexibilizes the epoxy matrix. The morphology of these systems all shows about the same particle size. However electron micrographs of the fracture surface of the system with 20 parts CTBN show that the particles are somewhat larger and more diffuse. 

An ASA-PBT with improved hydrolysis resistance and reduced warp was reported for a resin composition containing a difunctional epoxy compound such as bis(3,4-epoxycyclohexylmethyl) adipate [81]. To increase the heat distortion temperature of a PBT-ASA blend by 10-20°C, the addition of talc at a... 

To improve high temperature stability over amine cured systems and to give better physical and electrical properties above their heat distortion temperatures, it has been general practice in epoxy resin systems to use anhydride curing agents with DGEBA epoxy resins (8 ). Most anhydride formulations require elevated-temperature cures with the ultimate properties dependent on postcures at temperatures of 150 C or higher. 

In a typical formulation of epoxy resin (Epon 825, Shell) cured with aluminum alkoxide, incorporation of 30% PPE increased the elongation at break from <2% to >17%. The heat distortion temperature increased from 160 to 195°C. The dissolution of PPE in epoxy formulation-raised its viscosity at 200°C from 0.2 to 4 Pas [Anonym., 1991]. 

Known for many years, epoxy oligomers made from tetrabromobisphenol A are still used as the flame retardant in polycarbonates because they minimally affect the heat distortion temperature and even show a positive effect on impact strength. About 6—9 wt% of the epoxy oKgomer is required for achieving V-0 rating and a thermotropic liquid crystal polyester helps to improve melt flow, so that thin-waUed parts can be molded [38]. Antimony trioxide is not normally used in combination with halogen-containing additives in PC, because it causes loss of clarity. 

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