Polyester Resins ‘Tim Pepper, Ashland Chemical Company UNSATURATED POLYESTER (UPE) RESIN is used for a wide varity of industria and consumer applications. In fact, more than 108 billion kg (17 Billion Ib) was consumed in the United States in 1999. This consumption can ‘be spit info two major categories of sppliea- fons: reinforced and nonreinforeed. In rein oreed applications, resin. and reinforcement, such as fberplass, are used together t produce ‘2 composite with improved physical properties ‘Typical reinforced applications are boats, cay Hower stalls building panels, and corrosion- resistant tanks and pipes. Nonfiber reinforced ap- Plications generally have a mineral “filer” in- Porporated. into. the composite for property ‘molfcation. Some typical nonfiber reinforced “plications are sinks, bowling balls, and cost- igs Polyester resin composites are cost effec: tive because they require minimal setup costs fand the physical properties can be tailored 10 Specific ‘applications, Another advantage of Polyester resin composites is that they can be Peres in a variety of ways without altering the physical properties of the finished part. Couse- ‘Maonly, polyester resin composites compete far ‘orably i custom markets. Polyester Resin Chemistry Polyesters are macromolecules that are pre- pared by the condensation polymerization of di ‘Rnctional acids or anhydrides with difctional lcohols or epoxy fesins. Unsaturated polyester fesins commonly refered t0 as "polyester res ins." ae the group of polyesters in which the cid component part ofthe estris partially com> ‘of fumsric acid, a 1.2-eylenically’ unsst~ ested material. Maleic anhydrides the predom- fant source of this famarate. Maleic anhydride js incorporated into the polyester backbone and then isomerized to provide fumarate esters (Com only refered to as unsaturated polyesters). In Iost cases, the polymer is dissolved in styrene fo provide «solution that wil typically have & Misosity in the range of 0.2 to 2 Pa ~ s 200 13000 cP). Other reactive vinyl monomers, such ‘vinyl toluene, diallyl phthalate, or methy! tnethacrylate may be used to obtain, specific erties. The resin viscosity is tailored for spe- ine fabrication processes in which the resin is imately “cured” via a free-radical process. A Final formulation may include resin, inonganic filler, fiberglass reinforcement, and a free-radical initiator, such as an organic peroxide. This final formulation is formed against mol prior tothe ‘Crosslinking reaction between the unsaturated folymer and the unsaturated, monomer. The Touring” is a cross-linking chain reaction, con verting the low-viscosity solution into a thee Uimensional thermoset plastic (Ref 1). This is {fered to as the cure. Teminology bas devel- ped to distinguish between various (pes of UPEs General-purpose resins area group of resins ‘generally ased Because of their low cost. While Frocessing parameters can effect this, the cost of Te raw materials tends to limit the type of un nturted polyesters selected. The resis used in {his area are commonly refered to as PET, CPD, and ortho resins. While PET (potyeth- ‘lene terephthalic) resin and orthophthaic an Hydride are sources of low-cost saturated acids, ICED (dicyclopentadiene) is typically coupled with maleic anhydride during an initial step, prior to both the isomerization andthe condet Pion pelymesization, Dicyclopentadiene im- proves the solubility of te polyester resin in sy Fone, AS one drives toward lower-cost resins, ‘Solubility in stytene is a serious concera, Dicy- “lopentadiene offers a lowcost solution. Due to goverment regulations aimed at minimizing ffyrene emissions in open molding, a subset of ‘Beneral-purpose resins, “Tow-styrene” resis, has {een developed. These resins tend t0 have @ higher dependency on DCPD and are cooked to ‘ower molecular weight. Tis allows les sty- Tene to be used to achieve the desired viscosity, tnd performance generally suffers. sophthalic resins are based on isophihaic acid and maleic anhydride, The incorporation of |Soptnhalic acid creates ahigh-molecuas-weight Feofa with good chemical and thesmal resistance land good mechanical properties. The use of non polar elyeols contributes to improved aqueous F&Sstance, which is required to protect the fber- lass Bisphenol A (BPA) fumarate resins are pre pared by the reaction of propoxylated BPA with Famasic acid. The result sa relatively nonpolar polyester with a reduced numberof ester link ee The reduced number of ester linkages con tributes to excelent corrosion resistance. Bis phenol A famarates were once the workhorse of The corrosion resistant composite industry. Ine tent years, they ave been replaced by iso- ‘hthalic resins for milly corosive applications End bisphenol A epoxy based vinyl esters in hore aggressive environments. Currently, BPA famarates are used almost exclusively in appl- Cations requiring excepdional comosion resis- tance fo caustic environments. ‘Chlorendic resins are prepared using either chlorendic anhydride or ehlorendie (HET) acid {Ret 2) reacted with maleic anhydside, Compos- Stes made from these resins have excellent chett- jeal resistance and some fie retardancy because ‘fhe presence of chlorine. Chlorendic resins are tod in applications requiting exceptional resis- tance to acidic or oxidizing environments, In many ofthese environments, metals are attacked ‘guile aggressively, while chlorendic resin com- posites generally perform much better ‘Vinyl ester resin isthe common name for sores of unsaturated resins that are prepared by the reaction of # monofunctional unsaturated eid typically methacrylic acid, with an epoxy sin, The epoxy resin is “end-capped” with an Tnsaturated ester to form the vinyl ester resin ‘The resulting polymer, which contains unsatu fated sites only in the terminal postions, is nixed with an unsafurated monomer, generally yrene, AC this point, the sppearance, handling properties, and curing characteristics of vinyl es {er resins are the same as conventional polyester resins. However, the corrosion resistance and Inectanical properties of vinyl estee composites tre much improved over standard polyester resin ‘Table 1 ASTM test methods for Characterizing mechanical properties of “Teale cng ma Dass tn oosesion ‘pont steno mol pw ‘Conganve paca ne bess ‘iu a comenston on rk tas ipa ass es dorson Dew Pari hans D283 |Table 2_ Mechanical properties of clear-cast (unreinforced) polyester resins Polyester Resins / 91 soa So ete Such _Flewraimatune ae ‘comer Maia wee eg Onto a er 2 See asa) os pie ‘@ 3 ot 3 ow, 3% m ob 39 02 ts ‘fora x o's 2 oat a no i338 bad 10S ss Chowne o a 3 = Of m1 398 bs) tao as Niner 3 boa 38 on is mo 3am Ose i 2 Table 3 Mechanical properties of fiberglass-polyester resin composites (glass content, 40 wt%) I Tawa os — aa Sct nem “ren ao pet Met swat i Gp nga MG Ontceae 159 ss i mo 6s ope s i? 20 Bo fe ik aig 5) dit rh trate o mm i ote 12 io 2 30 13 wt Chirac o mo om 7 1g a mo 97 a mF Mugler ieee mR 99 13 ‘composites, These improved properties have en abled vinyl ester resins to become the workhorse ofthe polyester eustom corrosion industry. How= ever, the properties of vinyl ester resins are not 1s easily tailored to a specific application as are Standard unsaturated polyester resins. This com= bined with the use of higher-cost raw materials. ‘has somewhat limited the ability of vinyl ester resins to penetrate the unsaturated polyester resin ‘market ‘Within each of these five resin classifications, specific polyesters can be formulated by varying the starting materials. Specific properties such as. flexibility, thermal properties, fire retardancy, and hydrophobicity can be aliered (Ref 3) by ‘varying the typeof dihydee alcoholepoxy resin ‘used or by varying the fumaricfsaturated acid ra- tio Low-profile additives (LPAs) are a class of, saturated resins that reused for dimensional st- bility. Although these materials are not UPEs, they play a very important role in the use of UPEs, One ofthe problems associated with the use of UPEs is that they shrink volumetrically about 6 to 8% upon curing. This creates chal- lenges in fabricating a high-quality surface and/ ‘or maintaining the dimensional stability of a part. Low-profile additives offer a unique solu- tion to this problem when processing at elevated temperatures. Addition of an LPA to a UPE for. mulation reduces or eliminates shrinkage. Some formulations using LPAs can actually have ex- pansion greater than the original mold or form ‘size, Since the LPA does not chemically react ‘with the UPE or styrene, care shouldbe taken in determining the type and amount of LPA used. ‘Mechanical properties are often the exitcal ‘actor in seleting a polyester resin fora specie application. Table I lists the common test meth- ‘ds ofthe American Society for Testing and Ms- terials (ASTM) that are used to characterize the ‘mechanical properties of polyester resin com- posites ‘While the physical properties of polyester composites sre predominately controlled by re- inforcement, the physical properties of the pol ester resin do affect the durability and thermal performance, Representative examples of clear- ‘ast polyester resin data are shown in Table 2 It should be noted that within each class of resins, ‘modifications are made to the polymer. These modifications effectively trade off thermal per- formance for increased toughness (Table 2). Ts ble 2 highlights the differences among’ the classes of polyesters. kophthalic resins tend to show higher tensile and Nexural properties than ‘orthoplthaic resins. This may be because iso- phihalies usually form more linear, higher ‘molecular-weight polymers than orthophthalics. In contrast, the BPA fumarate and chlorendic resins are formulated for service in aggressive corrosive conditions and consequently are much ‘more rigid, This results in clear castings tht are britle and have low tensile clongation and strength. The vinyl ester, because of its bis: ‘phenol diepoxide content, exhibits excellent ten- Table 4 Effect of glass content on mechanical properti sile and flexural properties as well as high elon- gation In this article, itis impossible to discuss thor- oughly the effets that ditydric alcohols, acids, levels. of ‘unsaturation, monomer types and amounts, and cure temperatures have on me- ‘chanical properties; however, Ref 4 provides an ‘excellent review. In general, increasing the chain length of the ditydrc alcobol increases the flex- ibility of the eoss-linked resin. The same occurs ‘with saturated acids. Aromatic groups, in ether the dihydsic alcahol oe acid component, increase stiffness and hardnes. Using a reinforcing fiber to produce a poly ‘ester composite dramatically improves both the tensile and flexural properties, Table 3 lists the same five samples a Table 2; however, Table 3 shows the mechanical properties ofthe fiberglass reinforced polyester resin composites, In Tables ‘and 5, the properties obtained were dependent ‘on the amount and type of glass fber used. The last ewo entries in Table 5 show the influence of Fiberglass orientation. Both contained 70 wi% lass fiber, but the unidirectional composite showed much higher tensile properties and flex- ‘ural modulus when tested in the glass fiber di- of fiberglass reinforced polyester composites Tasteswegt, Teleco sre ses omy _ ithe “Onions 4s 00 phate 2 i Bou im a #6 PA fame no [758 to ty Mos) 1S) me oa t@ tae eee aise ti Moat x 9a ta ian is o m 365 a is Vater = Mo ie Sa 099 ta 2s G5 ones ss wo Ma $2 1 154 Bas ws iss 20 oo moo ae 12) Bo ted 0| Ss eS 92 / Constituent Materials fable Effect of glass type and amount on mechanical properties of fiberglass och eens ey cpetguatnrninienet _Cmeniati stents’ ihe es _Gh_ SRS ce pit estound ss ° non cene0n eestt 390 Oss copped rand ot s 12S go nome 3 Laisa * ee eet ee wa zig 10 232 Roving abe o im 3h os ss ta 38 Bons ia 78 ‘More es abe a we So as 37s is 30 m6 Tater vig fic n Gh oe ast am Ba ame 26313 able 6 Comparative properties of fiberlas reinforced polyester composites and various metals Tene eg Tsuna aero oes Moa ee ee Wet Trieste piso, dD 0 20 ele Ee ee ‘nites gs reve tet a is ‘ns 2s : as Chipped at > iy outing sous toa mg ‘nu set ny ai ee woe OR Sele ste 2 ky ts mE BE Tonsoni 50 90 ee mo np eth ‘eal enti vesttet__ cnet et a sean © TS ee ne ee Ta coin teed game eed IS a 3 1a Oat 5 ‘side! song. be is be a 4 12 oat 5 (Congested | ie Oe eas oe ee ‘soma eet x0 Oot ibcteno © asnose 022023 20-8 Sines at BO aig ase in RSFSR it ts.20 operon se Ss wo ee) oat-aas onnon IIS recon, The properties of nidietonl com- end polyesters emt igh fener eae) Aexural modulus was only 5% for the vinyt posites ae even more anisotropic than typical Pejyester laminates. Mechanical properties mes Put transverse to the glass direction will - roach those observed for clear castings. The Pirusin or filameat-winding process comme Pally produces polyester composites employing tinidirectonal reinforcements. They can be wsed I atructural applications where strength or sit ‘eos is requed in only one direetion. In Table & physical properties of fiberglass reinforced polyester resin composites are compared to those of various ‘As mentioned eatler, diferent types of rei forcement affect mechanical properties. While E-pias is the most commonly used reinforce: ment in polyester resins, S-plass,aramigh and Tarbon fibers can also be used. Table 7 compares Naty of reinforcements in bath orhopbiiaie polyester and vinyl ester resins, While the tensile Frongth ofthe ortophthalic polyester was much {improved with aramid, no such improvement was seen withthe vinyl este. Thorganic fillers aze commonly used in poly- ester resin composites. While they do improve Sulfess, as shown by an increase in modulus {gee Table 8), they have litle effect on other GrSogth characteristics. They are used primarily to reduce cost ‘As expected, mechanical properties at cle voted emperatres vary significantly among the [eoeral classifications of polyester resins (Fi fy The extreme rigidity and high glass transition temperature (7, of BPA fumarate and chlo- Tetention upto 120°C (250 F). Vinyl esters also advantages over isophiaic studies (Fig. 2, Ref 5). The eadmatage of vinyl ester was evident at elevated (Ret 6), At 105 °C (220 °F), vinyl show performance polyesters in fatigue temperature tester and isopithal lass) were cycled MPa (9-10 ksi). After enue! stent. MPA 1100160 20250 20880 a6 T° chore rl 0 BPA tunaras| 1 dl | lo Ny ae as eT 1 lexral stongh venus temperate, s-pohe (Ste cmponts of 0% gs ic polyester composites (60% to a sres level of 60 t0 70 "200,000 eyeles, the drop fester, compared to 12% forthe isophthalie poly ster The thermal performance of vinyl estes, SSmbined with ther excellent mechanical prop- Srl and toughness, explains why they ae often ‘chosen for structural resin composites. ‘Thermal and Oxidative Stability Polyester resins are commonly used in ele ‘yated-temperature applications, especially in the ‘cetrcal and corrosion-resistance areas, Atte erates above 130 °C G02 “F), the polymer Begins to slowly dissociate chemically. The tem “a which this decomposition occurs de~ Peds on te structure ofthe polyester used. Re fardless of the polymer composition, at EEnperatures near 300 °C (S10 “F), the cured polyester resin will undergo spontaneous decom phate : vel ae xl 1 ee cyclo ttre Fig. 2 Fecal fata stenathTable 7_ Effect of reinforcement on :I properties of polyester-matrix Polyester Resins / 93 a he composes 7 ferasedenel ~~ era dg I i Ms { Srthopntatic ophtatictnyrne” PS. cs , ‘| Espo : T oa oe Seas a F | L See eased 2 center wd = | Is “Ambient temperature 1 0 103 149 4] —- 5 ~ Seep eae ee = = Oe eo Amewenelete ta 207 12s 1 20 "B 4 cornoste when aged a1 200°C 090°) ested oe ee ee Sos 50°C (125 °F) 192 279 11416622 smal stability of glass-polyester composites at i BCU BL 2 te tee 2g Figs 3 Thematenbavofgasepoyener cm * Raa ‘S-plass-vingl ester. = =e re t BSED BEA 1 2 petmtnmspatnmomentanr | apices a ‘Monomer type also plays an importantrole in § [ ‘Ambient temperature 189 274 121 176 18, the thermal stability of a polyester resin. Forex- 2 5} = 7 28 ute a2 ‘superior thermal stability when compared to the % E Spree «A CCC Sep cqole’ ts Reuedecetme tt position. This is characteristic of vinyl polymers and is caused by their depolymerization to form, 'moomeric species. ‘Among polyesters, high-molecular-weight LUPEs and epoxy vinyl esters show better stabil- ity above 150 °C 302 °F) than low-molecular- weight UPEs. High-molecular-weight iso: phthalic, PET, DCPD, and BPA fumarate resins, ‘when formulated properly, can perform very Wel in thermal applications Fig. 2). In thermal stability, nonalogenated resins outperfoam ha- logenated resins. While some chlorinated resins have respectable thermal stability, brominated ‘resins universally have poor thermal stability with aromatic bromides performing somewhat better than aliphatic bromides, Low-styrene (general-purpose) resins also exhibit poor ther- ‘mal stability. The same is rue for orthophihalic resins, as they tend to e low-miolecular- weight resins. In spite of thei poor thermal sablity, corthophihalic resins perform well in moderate- 'o low-temperature applications and are often rate unsaturation. Even after aging at 200 °C (390°F), an isophihalc resin in vinyl toluene has beter flexural strength retention than an is0- phthalic resin in styrene (Fig. 4). While viayl Toluene versions of an isophthalic polyester and 4 BPA fumarate showed comparable perfor- ‘mance at 200 °C 390 "P), the BPA fumarate had much beter flexural retention at 220°C (430 °F) Fig. 5) and 240 °C (465 °F) Fig. 6), Chemical Resistance Polyester resins have been used for many years in applications requiring resistance t0 ‘chemical atack. Parts made from UPES have cortosion-resistant properties that complement ‘most metals. As an environment increases in po- lacy, it becomes less aggressive toward parts made from UPEs. Numerous applications for corrosion-resistant tanks, pipes, ducts, and ners can be found in the chemical process and pulp and paper industries. Resin selection depends on ig. 5 oars srengh wean of sper Fig 5 Soha uhun galt 00 heed tiem nga the specific chemical environment to be con- tained, Table 9 shows how four diferent classes of polyester resin perform in several environ- ments. Isophthalic fesias perform well in both mild aqueous and mild organic environments, Generally, they are the most economic resin choice. Vinyl ester resins are typically used in more aggressive environments, A. properly se- lected vinyl ester resin wll perform Wellin many applications. When the environment becomes ‘more aggressive, premium polyesters are pre: ‘erred, Premium polyester resins offer improved corrosion resistance for specific applications CCnlorendic resins are chosen for strong acid and oxidizing environments, especially at elevated temperatures, while BPA fumarate resins ae bet ter in caustic environments. Using glass fiber Table 8 Effect of filler and glas fiber reinforcement on mechanical properties of polyester resins sre Sri “ndengh Tema — gga, pact tact ma oT 2 7 Neat esi ating (A may 167 3 asm 790 1al as 0307 30 SS 0 poh A 20 pe CACO, (Baten) ie ak en ee ts ee M3265 Gio Osss eae ase Saas) 74 yt 28 ph 2m og shaped ed (C mati) ened F250 1 den 182. EA Soe Re94 / Constituent Materials Table 9 Corrosion resistance of glass er polyester resin composites v1 BPA j tol a. ro “75% HS, 15% Ne ‘325% NaOCl ‘Ryese —elolaed water ‘Seavatee " a TE, Gaim Bae; hate oreaan wien z ipa = 5 * . §, Sete = z t é . : / en arse : : : : t hop Vener 5 t z En ton oe sd Table 10 Effect of methyl methacrylate on Table 11 Electrical properties of lass- : Taeiass retention of weathered polyester polyester composites 2} panels Gone eal oF | | ree i ti seats saeh Vn 8) di} tt Somme Te Reem), Reseesy ope BOs @ WG Spiyaep idem ony EIST eats Ses 2 8 mm 7 > 6 nec! sean water of gangorece Siaarns $2 Bs Bs ih eo 22 ig. 6 Nether aE Hed a te is atvoomerpuure tit Su —@F i ‘oie ni-a0at des not improve the comesion resistance of on the surface. The negative effects of UV geet 022 polyester resins and, in some cases, actually re- ‘haces performance. Ths is especially ue in hy- drofluorc acid or sttong caustic environments ‘where the chemicals actully attack and dissolve glass. In this and other special cases, reinforcing fmatevals, such as carbon fibers, may be pre- fered (Ref 7). Polyester resins are used in many outdoor ap- plications. They caa survive exposure tothe ele- Incas for peciods exceeding 30 years, although ‘ome discoloration and oss of siength will c- ‘cur The onset of surface degradation is marked by a yellow discoloraon that becomes progres fvely darker as erosion and surface stress craz- ng occur. In transient systems, this UV radi- dation causes yellowing of the composite as whole, although the colori usually more intense posure can be effectively eliminated with the ad Stion of UV stabilizers to the outermost resin layer. Monomer selection also affects UV stabil ity, Styrene and other aromatic vinyl monomer desvatives ere more susceptible to oxidative ‘degradation and are usually supplemented with more resistant acrylate or methacrylate mon0- ners, Of the acrylate monomers, methyl meth- forylate (MMA) is the most common. When MMA is copolymerized with styrene, the cured polyesters have superior durability, color reten- tion, and resistance to fiber erosion (Ref 8). "The improved UV resistance with MMA is evident in Table 10, which compares four poly- xter resins composed of identical polymers ad our different monomer systems. These resins ‘were used to prepare glass fiber reinforced pan- Us thar were exposed to outdoor weathering for five years. The gloss retention fr styrene/MMA ‘monomer blends was much greater than for ei- {Ger monomer alone. The refractive index of sent ‘MMA is also lower than that of styrene, allowing the formulation of polyester resins witha refac~ tive index matched tothe glass fibers. This, com bined with improved UV resistane, has resulted in the use of MMA polyesters to fabricate glass reinforced transparent building panels that can be used in greenhouses, skylights, and other sp- plications. Using UV-absorbing chemical addi fives, Sich as the substituted benzophenones or Denzotrazoles, can further reduce the effect of radiation. Electrical Properties Most organic polymers have medium t0 ex cellent electrical properties. Wide ranges of ther ‘ose and thermoplastic materials are used inthe Table 12. Hlectrical properties of isophthalic polyester 3.2 mm (Ys in.) laminates with various flrs ia meats are meta i in ae Me aa thes ere vu 2 EE SR ee ee eo a oe ea ee comecor 0 4G tan ie one eon wt te te hu Bl ) oe re re a a se eta po bd i ee : Table 13. Electrical properties of BPA furarate polyester 3.2 mm (hn) laminates with various fillers : voc ie gee ee ee te Mae a rm Sate ast cece “men Se hte” ect cae, SS ie a a | a a a a a a ee) , a i.e eee. Gmemesoy 33 AE Ate Stas om mS oir Mo 8 ME Uk te Sh ttm i mt we 8 emi pene hn on iy ne aneelectrical and electronics industries. Applica. tions in which polyester resins have been used. include the insulation of motor windings, encap- sulation of electrical components, fabrication of printed circuit boards, high-voltage standoff in- Sulators, switcrboxes and miscellaneous &uip- ‘ment for high-voltage line work. Typical electi- cal properties of polyester resins are shown in ‘able TI, Tables 12 and 13 show specific data ‘on an isophthalc polyester and a BPA fumarate ‘as well as the iafluence of filler type. Because many electrical applications require performance at elevated temperatures, polyester resin composites must have good thermal stabil- ity, Thermal stability and electrical performance at elevated temperatures are directly related, as can be seen by comparing the retention of di- electric strength at 200 °C (390 “P, shown in Fig. 7, with the retention of flexural strength at 200 °C (390 ‘P, shown in Fig. 4. As with flex ‘ural strength, © vinyl-tluene-based polyester ‘outperforms & styrene-based polyester At tem- peratures above 200 °C (390 °F), vinyl-toluene- based BPA fumarstes outperform vinyl-toluene- based isopthalic polyesters (Fig. 8, 9). Large cletrcal equipment, sich as high-volt- age motors or generators, often operate at ele vated temperatures. In such application, the cleetrcal property of greatest concer isthe ds- Sipation factor, especially the dissipation factor versus the temperature. Polyester resins ean be formulated for a low dissipation factor at ele- vated temperatures (Fig. 10), They are used as clectrical varnishes at continuous-use temper tures up to 180°C (355 “F. Flame-Retardant Polyester Resins All organic materials, including polyesters, will bur in the presence of a flame. In many applications, polyester resins are required t0 hhave some degree of resistance to burning. This can be accomplished by using ether a filler ora specially formulated Aame-retardant polyester resin, depending on the degree of resistance re= quired. The addition of filer isthe more eco omical route to achieving flame retardancy in parts made from UPEs. However, the addition of filler increases weight and compromises tensile ropertics. Teorporaing halogen into a polyester resin is an effective way of improving flame retardance. ‘This can be accomplished using a halogenated x so —— CPanel ean ee + ef pL cleo § ‘ apmremeney |e =| = ee /aaleel a - 7 2g | evanimarteninytttuene i rd feo FF ve} —|— boo & veotatinonne| BE : Nee EE aL a No ma 8 3 ie 200° vs 20°C ievpsynnt Fig, 8 Olceae sen nfeon of sacar ig, 7 Delcrc tenth rtetion Fis. 7 CSppote wien ape 200 880°, aed Compote when age st 220°C 40°F ted Polyester Resins / 95 dibasic acid, such as chlorendic anhydride ort ttabromophthalic ashydrde, cr ahalogenated di- Ihydzc alcohol, such as dibromoneopentyl glycol ‘of tetrbromobisphenol A. At equivalent con- centrations, bromine is much more effective than chlorine, Additives such a antimony oxides and ferrous oxide act as synergists with halogenated polyesters and improve their flame-retardancy properties (Ref 8). ‘Burning rate and smoke generation are mes- sured using the Steiner Tunnel Test (ASTM E $4). In this est, a gas bumer is placed at one end fof 8 $3 em by 7.6m (21 in. by 25 fd) section ‘The distance the lame travels and the amount of smoke generated are measured (bythe obscura- tion of a photoelectric beam). These are com pared toto standards: red oak board, which is ‘given ating f 100 for flame spread and stoke ‘generation, and asbestos cement, which is given 4 rating of 0 for both flame spread and smoke ‘generation. Smoke generation is also measured ‘with an NBS smoke chamber, which uses a pho- toelectic cell to messure smoke buildup in a closed chamber. The sample is bumed either ‘with or without a direct lame. When NBS smoke ‘chamber testing is used, it is often common to use ASTM E 162, Flame Spread Index, to mes- ‘sure this variable ‘Table 14 compares the pecformance of several resins using the above-mentioned fire and smoke tests, In each of these test, the halogenated resin clearly outperforms the orthophthalic resin. Fer- tous oxide also reduces smoke generation inthe NBS chamber when compared to antimony ox- ide “Table 15 compares various filled and unfilled polyester resin composites. The improvement of fan ortophthalic resin by the incorporation of ‘lumina tbydrate (ATH) is dramatic, the flame spread is reduced from 380 w0 64, However, ha- Togenated resins reach this level of performance Table 14 Performance of selected polyester composites in fire tests arm eee strom ena = * ae Tame) 180) 0) eae ne 9 Mn sae ws ot fanaa * oo +. a eel Fomor i : jo $ oa P| netmntet sat oes NI 8 fa 4 E ; sit Bog ae ASME : 4 ae et mop ox : ies BRB A | \ 3 a can ning mde / } cia mm spay one i — a RH ; fan le ‘ st ne re ae, oma as ao an vee a20°C « ee i te a a re cae Fig. 9 Osiscric svenghretelon of sss pty: B® “conga hon apd 00 Gs 7 ed Temperature," Fig. 10. toptthalic poe t 2.4 kvm (0 Bn) {2 Trin 30K (HET Seof unfilled and filled polyester hss enforced laminates 3.2mm in tick, conning 30% ls, tes in acodance wih ASTM E 84 Conpunnt oe wpery ial), 1B) 100) tN) Od) fone) — 0g) Tou To Tasted stem ‘Amory xe 5 han ped os Fed syste Atoms, pir 1001) ‘mimony ence a Bane ad Bop ‘Sake eisin a om om 5 5 5 ® 8 GF » 6 wf mT ook 0 100 10m) 5 5 3 3 3 5 3 Ss fo wo Ce ee (Cope i.) HE i A 268 Hd i 8246 Cl. (Datei 18 Be) DR ‘eels nn heen HB See lS without the incorporation of any filler. Haloge- nated resins witha synergis show only a slight reduction in flame spread when ATH is added, but smoke emission is greatly reduced. When comparing brominated and chlorinated resins, 26% Cl gave comparable Name and stoke re- sults as 18% Br, ACKNOWLEDGMENT ‘This revised article is largely built around the original artite “Polyester Resins" by ChatlesD. Dudgeon, Ashland Chemical Company, from Composites, Vol 1 of the Engineered Materials Handbook. REFERENCES 1. M. Grayson and D. Eckroth, Ed, Encyclo- pedia of Chemical Technology, 34 e4., VoL 418, John Wiley & Sons, 1982, p 375, 2. P.Robitschek and CT. Bean, Flame Resis- tant Polyesters from Hexocklorocyclopen- tadiene, Ind. Eng. Chem., Vol 46, 1954, p 1628 3. EN. Doyle, The Development and Use of ce 10. Polyester Products, McGraw-Hill, 1969, p 258 HY. Bosnig, Unsaturated Polyestrs: Structure and Properies, Elsevier, 1964 B. Das, HS. Loveless, and SJ. Moris, Bf- feos of Structural Resins and Chopped Fi- ber Lengths on the Mechanical and Surface Properties of SMC Composites, 36th An- ‘ual Conference ofthe Reinforced Plastics Composites Institute, The Society of the Plastics Industry, 1981 PK. Mallick, Fatigue Characteristics of High Glass Content SMC Materials, 37% Annual Technical Conference, Society of Plastics Engineers, 1979, p $89 HS. Kliger and ER. Barker, A Compara- tive Study of the Corrosion Resistance of (Carbon and Glass Fibers, 390h Annual Con- ference of the Reinforced Plasties/Compas- ites Insti, The Society ofthe Plastics In- dustry, 1984 AL Smith and J.R. Lowry, Long Teem Du- rnbilty of Acrylic Polyesters versus 100% Acrylic Resins in Glass Reinforced Con- ‘structions, 15th Annual Conference of the Reinforced PlastieyComposites Institute, The Society ofthe Plastics Industry, 1960 E. Dorfman, WT. Schwartz, Jr, and RR. Hindersinn, "Fire-Retardant Unsaturated Polyester” U.S. Patent 4,013,815, 197 LLE. Seley and PW. Vaccarella, Controlling ‘Flammability and Smoke Emissions in Re inforeed Polyesters, Plast. Eng., Vol 35, 1979, p43