Properties of Unsaturated Polyester Resins

Anhydride s/Acids Phthalic anhydride Malice anhydride Adipic acid Isophthalic acid Terephthalic acid Glycols 

Propylene glycol Ethylene glycol Dipropylene glycol Diethylene glycol Methylpropane diol Neopentyl glycol Other 

Low cost, styrene compatibility Chemical resistance, rigidity Flexibility, toughness Toughness, chemical resistance Higher heat resistance 

Lower cost, improved surface, lower chemical resistance 

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Jash and Wilkie [86] reported that even when the fraction of clay was as low as 0.1 wt% the PBQiR in a cone calorimeter was lowered by 40 %. Lee et al. [87] demonstrated that incorporation of 6, 8 and 10 wt% of MMT into epoxy resin increased linearly the char yield firom 9.1 to 15.4 % reducing the thermal degradation of the epoxy matrix. Nazare et al. [88] studied the flammability properties of unsaturated polyester resin with nanoclays using cone calorimetry. The authors verified that the incorporation of 5 wt% of nanoclays reduces the PHRR by 23-27 % and THR values by 4-11 %. While incorporation of condensed-phase flame retardants (such as ammonium polyphosphate, melamine phosphate and alumina trihydrate) reduce the PHRR and THR values of polyester resin, the inclusion of small amounts of nanoclay (5 % w/w) in combination with these char promoting flame retardants causes total reductions of the PHRR of polyester resin in the range 60-70 %. Ammonium polyphosphate, in particular and in combination with polyester-nanoclay hybrids show the best results compared to other flame retardants. 

Melot,D., Escaig, B., Lefebvre, J. M., Eustache, R. R., Laupretre, F. (1994). Mechanical Properties of Unsaturated Polyester Resins in Relation to their Chemical Strcucture.-2. Plastic Deformation Behavior. J. Polymer Sci. PartB Polymer Phys., 32(11), 1805-1811. 

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. 

Alkyds. Alkyd resins consist of a combination of unsaturated polyester resins, a monomer, and fillers. Alkyd compounds generally contain glass fiber filler, but they may also include clay, calcium carbonate, alumina, and other fillers. Alkyds have good heat, chemical, and water resistance, and they have good arc resistance and electrical properties. Alkyds are easy to mold and economical to use. Postmolding shrinkage is small. Then-greatest limitation is extremes of temperature (above 175°C) and humidity. 

Polymer concretes show excellent mechanical properties and chemical resistance compared with conventional cement concretes. Polymer concretes can be cured quickly by the use of curing agents. Thus, the applications of polymer concretes are being increased. One of the popular polymers for polymer concretes is unsaturated polyester (UPE) resin. The properties of UPE resin can be modified by changing its molecular features. For the synthesis of the resin, phthalic anhydride or isophthalic acid as well as maleic anhydride can be employed to modify the mechanical properties or hydrothermal resistance. Terephthalic acid which is also used for the synthesis of poly ethylene terephthalate (PET) enhances the thermal resistance of the cured UPE resin. However, the synthesis of unsaturated polyester resin from terephthalic acid is difficult. One method to synthesize unsaturated polyester from terephthalic acid is the use of recycled PET. 

Huang, Y.J. and Chen, L.D. 1997. Effects of chemical composition and structure of unsaturated polyester resins on the miscibility, sample morphology and mechanical properties of styrene/unsaturated polyester/low-profile additive ternary systems. 1. Miscibility and cured sample morphology. Polymer 39 6631-6641. 

The Sprut-5M adhesive consists of unsaturated polyester resin 100 parts hy weight, ATG-M 80 parts (a mixture of 50 parts of macrodiisocyanate md 30 parts of ATG), polymerization initiator (MEKP(O)) 2 parts. Usually lwt% of CN is integrated additionally into the adhesive base. Sprut-5M can be produced using various polyester resins, but the most applicable one is the adhesive based on PM-I resin owing to its availability and low cost. For this reason we will consider the properties of the adhesive based mainly on this resin although it has adhesion strength 20—40% lower than that of adhesives based on PN-11, NPS 609-21M, and other resins, especially when cementing in water. 

Table 24.1 Physicomechanical properties of unsaturated polyester-isocyanate resins...

A hybrid thermoplastic polyester resin formulated for use in SMC/BMC applications and containing 22% recycled content. The resin provides excellent low profile properties for both structural and zero shrink applications and is soluble in many types of unsaturated polyester resin. It may be thickened using standard alkaline oxides and/or alkaline hydroxides and offers superior hot strength, impact properties and excellent bond and paint adhesion. 

Because of their lesser ability to control shrinkage, the non-polar polymers such as polystyrene and polyethylene are often classified as low shrink rather than low profile additives. Usually, low profile additives are supplied as 30-40% polymer solutions in styrene monomer. Polyester resin manufacturers also package the low profile additives dissolved in their resins. These are referred to as one pack systems. As the industry has expanded, other thermoplastics have been identified which have shrinkage control properties. These are also now used commercially in a variety of applications. Examples of these other polyers are saturated polyesters, polyurethanes, stryene-butadiene copolymers and polycapro-lactones. Polyfvinyl acetate) based materials are probably still the most used low profile additives, being useful with the broadest range of unsaturated polyester resin structures. Relative proportions of the organics used in most formulations are 30-50% polyester alkyd, 10-20% thermoplastic and 40-50% styrene. 

Structural elements of unsaturated polyester resins that affect the properties of the cured products include molecular weight and molecular weight distribution, distribution of various repeating units, type of unsaturation, and ratio of acid to glycol components. An overall concept regarding the structural features of polyester resin and the performance properties of cured product is not available. However, it is known that the structural features determine the values of hardness, impact strength, heat-distortion temperature, water absorption, chemical resistance, and heat resistance. 

Ahmed, T.. and Funke, W.. Structure and properties of radiation cured unsaturated polyesters in absence of vinyl monomers, ACS Polymer Prept, Vol. 1, 34, 725, 1974. Pucic, I., and Ranogajec, E, DC electrical conductivity as a method for monitoring radiation curing of unsaturated polyester resins. 1. Measurement conditions and comparison with extraction analysis data. Radial. Phys. Chem., 46, 365, 1995. 

The versatility of unsaturated polyester resin compositions, properties, and fabrication techniques, the design flexibility that can be achieved, and the relatively easy and economical mass production capability and new developments may be further understood and demonstrated by several other good articles and texts. Extensive patent literature, which is... 

Because of its superior mechanical and chemical properties, thermoset unsaturated polyester resin (UPR) is widely used in fibreglass reinforced plastics and polyester fibres. Driven strongly by the surging consumption, China s demand for UPR has been increasing by 20.3% annually, reaching 365 000 tonnes by 1998. Demand for thermoset polyester reached 678 000 tonnes in 2003, and is currently growing by 13.2% each year. 

Uses. About 35% of the isophthahc acid is used to prepare unsaturated polyester resins. These are condensation products of isophthahc acid, an unsaturated dibasic acid, most likely maleic anhydride, and a glycol such as propylene glycol. The polymer is dissolved in an inhibited vinyl monomer, usually styrene with a quinone inhibitor. When this viscous hquid is treated with a catalyst, heat or free-radical initiation causes cross-linking and sohdification. A range of properties is possible depending on the reactants used and their ratios (97). 

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). 

The applications of the unsaturated polyester resins were increased in the late 1960s by the introduction of water-extended polyesters. In these materials water is dispersed into the resin in very tiny droplets (ca 2-5 p.m diameter). Up to 90% of the system can consist of water but more commonly about equal parts of resin and water are used. The water component has two basic virtues in this system it is very cheap and because of its high specific heat it is a good heat sink for moderating cure exotherms and also giving good heat shielding properties of interest in ablation studies. 

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. 

The surface energy of fibers is closely related to the hydrophilicity of the fiber [38]. Some investigations are concerned with methods to decrease hydrophilicity. The modification, of wood cellulose fibers with stearic acid [43] hydrophobizes those fibers and improves their dispersion in polypropylene. As can be observed in jute-reinforced unsaturated polyester resin composites, treatment with polyvinylacetate increases the mechanical properties [24] and moisture repellency. 

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