Polyester resins temperature

Fig. 117. Low-temperature explosions of mixtures of potassium perchlorate with some combustible substances /—with polyester resin (temperature of the thermostat 296°C), //—with ethylene glycol (temperature of the thermostat 241°C), (according to Gro-...

Dry chlorine has a great affinity for absorbing moisture, and wet chlorine is extremely corrosive, attacking most common materials except HasteUoy C, titanium, and tantalum. These metals are protected from attack by the acids formed by chlorine hydrolysis because of surface oxide films on the metal. Tantalum is the preferred constmction material for service with wet and dry chlorine. Wet chlorine gas is handled under pressure using fiberglass-reinforced plastics. Rubber-lined steel is suitable for wet chlorine gas handling up to 100°C. At low pressures and low temperatures PVC, chlorinated PVC, and reinforced polyester resins are also used. Polytetrafluoroethylene (PTFE), poly(vinyhdene fluoride) (PVDE), and... 

Polyester sheet products may be produced from amorphous poly(ethylene terephalate) (PET) or partiaHy crystallized PET. Acid-modified (PETA) and glycol modified (PETG) resins are used to make ultraclear sheet for packaging. Poly(butylene terephthalate) (PBT) has also been used in sheet form. Liquid-crystal polyester resins are recent entries into the market for specialty sheet. They exhibit great strength, dimensional stabHity, and inertness at temperatures above 250°C (see Polyesters,thermoplastic). 

Aromatic diacyl peroxides such as dibenzoyl peroxide (BPO) [94-36-0] may be used with promoters to lower the usehil decomposition temperatures of the peroxides, although usually with some sacrifice to radical generation efficiency. The most widely used promoter is dimethylaniline (DMA). The BPO—DMA combination is used for hardening (curing) of unsaturated polyester resin compositions, eg, body putty in auto repair kits. Here, the aromatic amine promoter attacks the BPO to initially form W-benzoyloxydimethylanilinium benzoate (ion pair) which subsequentiy decomposes at room temperature to form a benzoate ion, a dimethylaniline radical cation, and a benzoyloxy radical that, in turn, initiates the curing reaction (33) ... 

Ketone Peroxides. These materials are mixtures of compounds with hydroperoxy groups and are composed primarily of the two stmctures shown in Table 2. Ketone peroxides are marketed as solutions in inert solvents such as dimethyl phthalate. They are primarily employed in room-temperature-initiated curing of unsaturated polyester resin compositions (usually containing styrene monomer) using transition-metal promoters such as cobalt naphthenate. Ketone peroxides contain the hydroperoxy (—OOH) group and thus are susceptible to the same ha2ards as hydroperoxides. 

Flame-Retardant Resins. Flame-retardant resins are formulated to conform to fire safety specifications developed for constmction as well as marine and electrical appHcations. Resins produced from halogenated intermediates (Table 5) are usually processed at lower temperatures (180°C) to prevent excessive discoloration. Dibromoneopentyl glycol [3296-90-0] (DBNPG) also requires glass-lined equipment due to its corrosive nature. Tetrabromophthahc anhydride (TBPA) and chlorendic anhydride (8) are formulated with ethylene glycols to maximize fiame-retardant properties reaction cycle times are about 12 h. Resins are also produced commercially by the in situ bromination of polyester resins derived from tetrahydrophthahc anhydride... 

Stabilizers. Hydroquinone [123-31 -9] (4) is widely used in commercial resins to provide stabiHty during the dissolution of the hot polyester resin in styrene during the manufacturing process. Aeration of the styrene with oxygen (air) is required to activate the stabilizer, which is converted to an equiHbrium mixture of quinone and the quinhydrone (5) (11). At levels of 150 ppm, a shelf life of over 6 months can be expected at ambient temperatures. 

Catalyst Selection. The low resin viscosity and ambient temperature cure systems developed from peroxides have faciUtated the expansion of polyester resins on a commercial scale, using relatively simple fabrication techniques in open molds at ambient temperatures. The dominant catalyst systems used for ambient fabrication processes are based on metal (redox) promoters used in combination with hydroperoxides and peroxides commonly found in commercial MEKP and related perketones (13). Promoters such as styrene-soluble cobalt octoate undergo controlled reduction—oxidation (redox) reactions with MEKP that generate peroxy free radicals to initiate a controlled cross-linking reaction. 

Open-Mold Processes. Polyester resins are fabricated easily in open molds at room temperature. Such processes account for over 80% of production volume, the remaining being fabricated using matched metal dies in high temperature semiautomated processes. 

Materials are also blended with VDC copolymers to improve toughness (211—214). VinyHdene chloride copolymer blended with ethylene—vinyl acetate copolymers improves toughness and lowers heat-seal temperatures (215,216). Adhesion of a VDC copolymer coating to polyester can be achieved by blending the copolymer with a linear polyester resin (217). 

Cobalt salts are used as activators for catalysts, fuel cells (qv), and batteries. Thermal decomposition of cobalt oxalate is used in the production of cobalt powder. Cobalt compounds have been used as selective absorbers for oxygen, in electrostatographic toners, as fluoridating agents, and in molecular sieves. Cobalt ethyUiexanoate and cobalt naphthenate are used as accelerators with methyl ethyl ketone peroxide for the room temperature cure of polyester resins. 

Thermosetting unsaturated polyester resins constitute the most common fiber-reinforced composite matrix today. According to the Committee on Resin Statistics of the Society of Plastics Industry (SPl), 454,000 t of unsaturated polyester were used in fiber-reinforced plastics in 1990. These materials are popular because of thek low price, ease of use, and excellent mechanical and chemical resistance properties. Over 227 t of phenoHc resins were used in fiber-reinforced plastics in 1990 (1 3). PhenoHc resins (qv) are used when thek inherent flame retardance, high temperature resistance, or low cost overcome the problems of processing difficulties and lower mechanical properties. 

Unsaturated polyester resins predominate among fiber-reinforced composite matrices for several reasons. A wide variety of polyesters is available and the composites fabricator must choose the best for a particular appHcation. The choice involves evaluation of fabrication techniques, temperatures at which the resin is to be handled, cure time and temperature desked, and requked cured properties (see Polyesters, unsaturated). 

Organic peroxides need to be stored separately from the polyester resins and promoters. If a peroxide is contaminated with a promoter, violent decomposition can result. Promoters should always be thoroughly mixed into the resin prior to the addition of the peroxide to prevent violent peroxide decomposition. Peroxides can become unstable if stored for too long or at too high a temperature. Peroxide manufacturers advice for storage and disposal must be stricdy followed. 

Most polyesters (qv) are based on phthalates. They are referred to as aromatic-aHphatic or aromatic according to the copolymerized diol. Thus poly(ethylene terephthalate) [25038-59-9] (PET), poly(butyelene terephthalate) [24968-12-5] (PBT), and related polymers are termed aromatic-aHphatic polyester resins, whereas poly(bisphenol A phthalate)s are called aromatic polyester resins or polyarylates PET and PBT resins are the largest volume aromatic-aHphatic products. Other aromatic-aHphatic polyesters (65) include Eastman Kodak s Kodar resin, which is a PET resin modified with isophthalate and dimethylolcyclohexane. Polyarylate resins are lower volume specialty resins for high temperature (HDT) end uses (see HeaT-RESISTANT POLYAffiRS). 

Epoxy resin has a higher strength at elevated temperatures than polyester resins but is not as resistant to attack by some fluids. Some glass-reinforced epoxy-resin pipe is made with a polyester-resin hner. The coefficient of thermal expansion of glass-reinforced resin pipe is higher than that for carbon steel but mu less than that for plastics. 

Glass-reinforced polyester is the most widely used reinforced-resin system. A wide choice of polyester resins is available. The bisphenol resins resist strong acids as well as alkahne solutions. The size range is 2 through 12 in the temperature range is shown in Table 10-17. Diameters are not standardized. Adhesive-cemented socket joints and hand-lay-up reinforced butt joints are used. For the latter, reinforcement consists of layers of glass cloth saturated with adhesive cement. 

This is also known as Bulk Moulding Compound (BMC). It is blended through a mix of unsaturated polyester resin, crosslinking monomer, catalyst, mineral fillers and short-length fibrous reinforcement materials such as chopped glass fibre, usually in lengths of 6-25 mm. They are all mixed in different proportions to obtain the required electromechanical properties. The mix is processed and cured for a specific time, under a prescribed pressure and temperature, to obtain the DMC. 

When the resin temperature drops below the boiling point of the reactive diluent (usually styrene) the resin is pumped into a blending tank containing suitability inhibited diluent. It is common practice to employ a mixture of inhibitors in order to obtain a balance of properties in respect of colour, storage stability and gelation rate of catalysed resin. A typical system based on the above polyester fomulation would be ... 

In the presence of certain aromatic tertiary amines such as dimethylaniline, benzoyl peroxide will bring about the room temperature cure of general purpose polyester resins. 

An interest has been developed in the use of vanadium naphthenates as accelerators. In 1956 the author found that if MEKP was added to a polyester resin containing vanadium naphthenate the resin set almost immediately, that is, while the peroxide was still being stirred in. Whereas this effect was quite reproducible with the sample of naphthenate used, subsequent workers have not always obtained the same result. It would thus appear that the curing characteristics are very dependent on the particular grade of resin and of vanadium naphthenate used. It was also observed by the author that the gelation rate did not always increase with increased temperature or accelerator concentration and in some instances there was a retardation. Subsequent workers have found that whilst the behaviour of the naphthenate varies according to such factors as the resin and catalyst used, certain vanadium systems are of value where a high productivity in hand lay-up techniques is desired. 

Figure 25.9. Typical exotherm curves for polyester resin cured with 1% benzoyl peroxide over a range of bath temperatures. (Test tubes of 19 mm dia are filled to height of 8 cm with a mixture of resin plus peroxide. The tubes are immersed in a glycerin bath to the level of the resin surface. Temperature is measured with a thermocouple needle whose point is half-way down the resin...

Not only does the material have excellent resistance to burning but smoke emission values are reported to be much less than for fire-retardant polyester resin. The laminates are being increasingly used in situations where corrosion is associated with organic media, where corrosion is encountered at temperatures above 100°C as in fume stacks and where both fire retardance and corrosion resistance are desired as in fume ducts. 

Polyester/glass-flake linings can be applied onsite because they cure at ambient temperature. Their corrosion resistance depends on the type of polyester resin used. 

Nowadays the major thermosetting resins used in conjunction with glass fibre reinforcement are unsaturated polyester resins and to a lesser extent epoxy resins. The most important advantages which these materials can offer are that they do not liberate volatiles during cross-linking and they can be moulded using low pressures at room temperature. Table 3.1 shows typical properties of fibre reinforced epoxy. 

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