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    © All Rights Reserved
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    9 views12 pages

    4 Epoxy Resins

    Uploaded by

    Ali Rafique
    Epoxy Resin - Baiscs

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    of 12
    Epoxy Resins ‘Aaureen A. Boyle, Cary J. Martin, and John D. Neuner, Hexcel Corporation ‘THE FIRST PRODUCTION OF EPOXY AESINS occurred simultaneously in Europe and A the United States in the late 1930s and early ‘40s. Creit is most often atributed to Pierre estan of Switzerland and S.0. Greenlee of the “ited States who investigated the reaction of Sisphenol-A with epichlorohydrin. The families af epoxy resins that they commercilized were jest used 4s casting compounds and costings fhe same resins are aow commodity materials haat provide the basis for most epoxy formula Sons (Ref 1-3). ‘Bpory resins area class of thermoset materials ased extensively in structural and specialty com Seite applications because they offer @ unique ombination of properties that are unattainable ‘vith other thermoset resins. Available in a wide ‘ariety of physical forms from low-viscosity liq- tid to high-meling solids, they are amenable fo ft wide range of processes and applications. Ep- nies offer high strength, low shrinkage, excel Tent adhesion to various substrates, effective clecttical insulation, chemical ad solvent resis- {ance, low cost, and low toxicity. They are easily {Cured without evolution of volatiles or by-prod- tts by a broad range of chemical specie. Epoxy resins are also chemically compatible with most ‘Substrates and tend to wet surfaces easily, mak ng them especially wel suited to composites ap- plications Epoxy resins aze routinely used as adhesives, ‘coatings, encapsulates, casting materials, potting ompounds, and binders, Some oftheir most n- teresting applications are found inthe aerospace fand recreational industies where resins and fi- bers are combined to produce complex compos- ite structures, Epoxy technologies satisfy a v Hey of noametalic composite designs in ‘Commercial and military aerospace applications, including flooring panels, ducting vertical and horizontal stabilizes, wings, and even the fuse- Tage. This same chemistry, developed for aero- space applications, is]aow being used to produce Tightweight bieycle frames, golf clubs, snow: ‘boards, racing cars, and musical instruments "To suppor these applications, epoxy resins are ommalated to generate specific physical and me- ‘chanical properties. The designers ofthese sy3- tems must balance the litations of the raw ma~ terials and the chemistry with the practical needs Of the part fabricator. While the simplest for- ulations may combine a single epoxy resin ‘wih a curative, more-complex recipes wil in- ‘lade multiple epoxy resins, modifiers for tough tess or flexibility or ame/smoke suppression, Jnr filers for flow contol or coloration, and a ‘curative package that drives specific reactions at specified times. ‘When selecting a thermoset resin, considera- tion is usualy given to tensile strength, modulus fand strain, compression strength and modulus, fotch sensitivity, impact resistance, heat deflec~ tion temperature or plas transition temperature (7), lasnmability, durability i service, material Availablity, ease of processing, and price. Epoxy reins are of paticuar interest to structural ex fineers because they provide a unigue balance ‘fchemical and mechanical properties combined ‘wih extreme processing versatility In all cass, thermoset resins may be tailored to some degree to satisfy pantcula requirements, o formulation land processing information are often maintained as tudo secrets. ‘The three basic elements of an epoxy resin formulation that must be understood when se- fecting a thermoset system are the base resi, cratives, and the modifiers. When formulating ‘an epoxy resin fora particular use, its necessary to know what each ofthese components contrb- ‘testo the physical and mechanical performance ‘ofthe pat during and aftr fabrication. The sub Sequent sections may be used as a practical in- troduction to formulary components and epoxy resin selection. Base Resins ‘The term “epoxy resin” describes a broad class of thermoseting polymers in which the pet mary cross linking occurs through the reaction fof an epoxide group. In general, an epoxy resin fan be thought of as a molecule containing & three-membered ring, consisting of one oxygen ‘tom and two carbon atoms (Fig. 1) "While the presence of this functional group defines « molecule as an epoxide, the molecular base to which itis attached can vary widely, Yielding various classes of epoxy resins. The Zommercial success of epoxies is due in pat to the diversity of molecular structures that can be produced using similar chemical processes, In combination with judicious selection ofa curing fgent and_ appropriate modifiers, epoxy resins tan be specifically tailored to ft a broad range ‘of applications eis important to understand basic production techniques in order to appreciate the available resins and how they differ from each other. Ep- ‘xy resins are produced from base molecules Containing an unsaturated carbon-carbon bond. ‘There are two processes that can be use to con- vert this dauble bond into an oxiane ring: de- hhydrohalogenation of a hatohydrin intermediate land direct peracid epoxidation. While both pro- ‘esses are used to produce commercial epoxy tesns, the halohyrin oute is more common and Fs used to produce a wider variety of materials, (Ref), "The most important raw material used in ep- ‘oxy resin production is epichlorohydrin, which, ‘with the exception of the cycloaliphatic resins, js used asa precursor for nearly every commer- cially available epoxy resin, Catesonics and Defining Characteristics Epoxy resins wsed in commercial composite sp plications can be loosely categorized as those Suitable for structural or hih-temperatare appli- tations, and those best sited to nonstructral or ow-tempersture applications. A. primary indi ‘ctor of service of Use temperature of & poly= meric composite isthe glass transition tempera- ture (.). The 7, isthe temperature below which f polytner exists in the glassy state where only ‘ibrational motion is present, whereas above this temperature, individual molecular segments are fable to move relative to each other in what is termed the “rubbery state.” The modulus of & material above its 7, i typically several orders ‘of magnitude lower than ifs value below the 7, fo this becomes an important. consideration ‘when selecting an epoxy resin. The T, is also ‘Stongly affected by the presence of Absorbed moisture or solvents, Thus, exposure fo moisture ‘or solvents must also be taken into account when Q Z™ 1 asc ceria eucture of epory sou R scteting oc designing esis for paula - plications "The glass transition temperature ofa cured ep- ‘oxy resin is dependent upon the molecular struc- ture that develops in the matix during cure, ‘which i driven by characteristics such a‘eross- link density, stiffess of the polymer backbone, and intermolecular interactions. Tt is generally agreed, however, that cured resin formulations suitable for elevated temperature applications are largely determined by cross-link density. The T, is therefore closely related to cure temperature and will change as th cure temperature changes, 0 aresin system cured at alow temperature will havea lower T, than the same system cured ata higher temperature. Every system, however, Wil have an ultimate T, determined by its formula tion that cannot be enhanced by an increase in ‘cure temperature, In most cured epoxy resins, T, Will 1g cure temperature by 10 0 20 °C (20 16 £35 °F) Tis important to remember thatthe mo- lecular stricture and other characteristics of the ‘cured product are equally dependent on the base resin, the curing agent, and modifiers employed in the formulation. In addition to service temperature, there are many other physical and chemical differences between the commercially available epoxy res- ins that dictate both their ultimate use and how they ae processed, Primary physical differences between uncured epoxy resins products within a family are material form and viscosity at room temperature, which can range from very thin lig- uids to solids. Application or processing guide lines often dictate what viscosity of form is re- ‘quired. For example, 2 solid or semisolid ‘candidate is inappropriate in a wet lay-up appli- cation where low viscosity at room temperatare is required, AS processing capabilities are de- veloped or modified, new material forms become fvailable. The most commonly used resins can ‘be purchased as powders, liquids, solutions pro swo pen 10D, 1002 1004 007,109 (Se GT 6063, 0, 3 (ant) DER, 662 (Dm) Epickon Tost 20, us, 4030, 1080 (IC) Pipi tera pte guia 2 165-190 2-7 2400-7000 xpua 86 Stal GY 26, 282, 288 (Vr) DER S54 SHLY (Don Pon 60, 38 DI) Peo ov Seni anaes 7020 vmiey vais PN TISH 199 119, 10 (Um) DEN 81, 438 (DOW) N38, 720, 7100010) Crs nveae Seid arse 0-265 vasey vais BUN273 1250, 1285129, 9811 Cnc) N60, (5,6 707, 0, 0,6 (DIC) Bispheaet A nvaic Semi ta sv 25,48 Gea) Dijelopentaine avec Sou 210 “ac 55 (Yano) P7200 (DIC) Trgylylener ef wuptentmetae Sod 3 iso “ace 12 (ao) ‘Tenet peopel. ia 3 SiS 058-5 ——$56.8000 MY son OSI (Vase) ELME-100 Samim) ‘eoapyausimetiee danine Ligaen oi MY 70, 721,651, 612,964, 635,956 (imo) plea 49 (DIG) LAG (Suton) {A epongecatenyinti iit a Tas 02s-045 250-480. CY DMA (Vanco) VRIES 110 (Uson ‘eponyyenioane oryae ‘cube) 80 / Constituent Materials ‘inated resins ao used to impart flame retar ddancy into the final product and are commonly tsed in electrical applications. Multiple forms lire available with various bromine contents and molecular weight ranges. This category of resins ranges from nearly pure diglyeidy! ether of te- trabroma bisphenol-A to high molecular weight fnalogs similar to those available with the stan- ‘ard bisphenol-A resin, "Another type of phenolic epoxy resin isthe iglycidyl ether of bisphenolF. This material has a lower viscosity fan most DGEBA resins tnd is commonly vsed to reduce mix viscosity ‘while Limiting reductions in glass transition tem- perature, Moderate improvements in chemical Fsislance are seen when bis-F resins are used in place of bis-A resins, Unlike the bisphenol-A- ‘Based resins, high molecular weight versions are not readily available (Ref 5) ‘Phenol and eresol novolaes ate another to types of aromatic glycidyl ethers (Fig. 3). These ‘Reins are manufeetured in @ tworstep process ‘Combining either phenol or cresol with formal fenyde produces polyphenol that is subse- ‘quently reacted with epichlorohydrin to generate the epoxy. High epoxy resi. functionality and high cured 7, characterize these resins and di ferentate them from the difunctional bisphenol- ‘AIF resins, ‘The phenol novolacs are high-vis- ost liquids while eresot novotacs are typically Solids at room temperature. They are of general fnterest because excellent temperature perfor. mance can be achieved at a relatively modest cost. ‘Other important epoxy novolac include bi phenol-A novolacs and aovolacs containing ° y ¢g oy Ay i eff how TR Fig. 3 Chemical race of phenl nowlae A creat ‘Solacconans x may group on each Een i s Fi cyelopentadiene, Bisphenol-A novolaes achieve ‘reellent high-temperature performance. Dicy- ‘opentadiene novolacs impart increased mois- ture resistance to a resin (Ref 6). ‘Glycidyl amines are formed by reacting ¢p- jechlorohycrin ‘with an_amine, with aromatic “mines being preferred for high-temperature sp- plieaions The most important resin in this class, Tetraglyeidyl methylene dianline (TGMDA), is shown ia Fig. 4 ‘This resin is used extensively in advanced composites for aerospace applications dus to its ‘xeellent high-temperature properties. In gen ‘ra, these resins are more costly than either the Alifunctionalbisphenols or the various novolac, ‘Advantages of TGMDA resin include excellent ‘mechanical properties and high glass transition temperatures. Glyeidyl amines are high-viseos- ity Liquids or semisotis at room temperate. AS twih the DGEBA resins, a variety of grades are {vailable, again dependent upon purity, molec- tlar weight, and particle size "Another elycidyl amine, tighyeidylp-amino- phenol CIGPAP), consists of three epoxy groups [tached to a single benzene ring. This resin &X hibits exceptionally low viscosity at room tem- perature, from 0.5 to 5.0 Pa- s (500 to $000 cP), ‘The mechanical properties and glass transition temperatures approach those obtained with the {etralunctional resins. Because of its low viscos: ity, TOPAP resins are commonly blended with tlie epoxies to modify the flow or tack of the formulated system without loss of Ty. The pri- inary disadvantage is cost, which can be 6 10 8 times that of commodity bis-A resins ‘Other commercial. glycidyl amines include iglyeidyl aniline and tetaglycidyl meta-xylene ‘amine, The primary advantage of these resins fs ther low room-temperature viscosity, which makes them useful for applications requiring ‘ery high resin flow, such as lament winding oF liquid molding. CCyeloaliphatics are differentiated from other ponies by containing an epoxy group that ign {ermal to the rng stcture rather than external or pendant (Fig. 5) Very low viscosity (0.25-0.45 Ba ss, or 250-450 cP, at 25 °C, or 77 $F) and relatively high thermal-mechanical performance (for an aliphatic resin) characterize this class of Inatedals The high T,s possible with eycloali- DPhatics are primarily due to the difference in Fracture formed upon cross-linking. The cross Tink formed upon curing is attached directly to the eyelic backbone structure. While this eyelic CV 4 Chemical suc of tragedy methylene anne TGMON) stucture is aliphatic and therefore more flexible than the aromatic material described previously, the distance between cross-links is reduced. ‘While many materials hve been desribed inthe Titerature, 28 of 2000, only afew are available on the open market (Ref 7, 8). Itmay be important to note that unlike bis-A epoxies, cycloaliphatic pores react very slowly with some amines at ‘oom temperature. ‘Other resins. A wide vaiety of other epoxy resins ae availabe, including epoxidized oils tnd specialty, low-volume or experimeatal high performance resins, These matevals are concep- ually similar to those discussed previously. "A list of commonly used epoxy resins and thie suppliers may be found in Table I Epoxy Resin Curatives Epoxy resins will react witha large number of chemical species called curaives or hardeners. {Other terms often used, sometimes ineorecty, fe catalysts and accelerators.) The most com- monly used chemical classes of curatives are mines, amine. derivatives, and_ anhydrides ‘Other classes of curing agents are mentioned ‘eft atthe end of ths section. Those seeking f moce comprehensive guide to epoxy resin CO- fatives should refer to one of several books on the subject (Ref 9,10) ‘When selecting zesin-curative combinations, the application or end use defines the resin char teterstes that must be built info a particular system, Epoxy resins can be formuleted in an infinite number of ways to manipulate charac- teristics such as system stability, cure kinetics, physical form, T mechanical performance, and Ehemical resistance, Cure times can range from Seconds {0 days, with some heat-actvated sys tems being latent for months to years al room temperature. The uncured formulated resin can be solid, rubbery or guid, tacky or dey, and can ‘cre at femperatures from 5 10 260 °C (40-500 SP), The cued product can be soft and pliable or gid and glassy, with glass transition tempera tures ranging from below room temperate to 260°C (300 °F) and tensile elongation from 1% to over 100%. The following sections are meant to give a quick overview of commercially avail- ble curatives as of 2001. The materials have been separated into the general categories of room-temperature cure, room or elevated-tem perature cure, elevated-tempersture cure, and ‘iscellaneous curtives. In some cass, a single ‘curative or class of curatives may itn more than. Fig. 5. chen acu oan cosh: oxyresin cone ofthese estegories, however, 0 effort has ‘oon made identify where classfetions over wp, ‘Room temperature curing agents include sliphase amines, polyamides, nd amioatines. ‘Alias amines are the caraives most often ated with epoxy eins When he functionality nd cure mechanism ofeach component is un- derstod, these materials are sed in stoihio- tne amounts, though mix raion are more of- ten determined experimentally and curative levels recommended in wits of pr (parts cure five per 100 pars bis-A epoxy). The reaction mechanisms of epoxy resin with primary, sec- ‘ondary’ and trary amines ae ilusvated in Fig 6: Primary and secondary amines proceed as ad- dicion reactions where one nitogen-hydrogen froup reacts with one epoxy group. Reaction ‘with trary amines reals from the unshared Electron pur onthe itogen, Since tere are 10 Secondary hydroxyl groups generated, the resin ray be said to homopoiymerize. Numerous combinations are available since the varius ep- foxy structures available may contain one, evo, tree, oF more resctve sites and the amine ean contain. mliple aitogen-hydrogen "s20ups Both the number andthe distance between Fe active groups affect material pecformance. The distance between reactive props can vay, with few, widely spaced sts yielding sot an very flexible prodacs while feequent, shor sepera- tions yet hard and bride products (Ref 12). ‘Commonly used primary amines are dithy- Jeve amine (DETA), Wietylene tevamine CTEPA), teveelyleepentanine (TEPA), and Neamincethyrpiperazin (N-AEP). Even hough these amines wll cue at room temperature, T, and subsequeatuse temperate are often im proved by an elevael-emperatire cure or post fe, Th enhanced T, ofthese baked materials however, will aways be 10-10 20 °C (20 to 35, “F below cae temperature. “The reactivity of some primary amines allows them to eure under adverse conditions where the substrate and surounding envionment may be cold and damp. Primary amines are highly exo- thermic and may be addueted with epoxy resins, ethylene or propylene oxides to render curstives With higher viscosity, less reactivity, and less toxicity than the pure amines. Amine basicity must be carefully controlled in applications ‘where workers come into contact with uncured materials ‘Other aliphatic amines sometimes used as ep- ‘oxy curatives are mete-xylenediamine (MXDA) tnd the polymeric form of MXDA, which are available as liquids. These curatives contain an sromatic ring but react as ali ‘which gives them cured properties close to that of the aromatic amines. olyetheramines, also known by the trade name Jffamine (Texaco Inc), are an interesting class of curative that are available as difunetional for tfunctional liquids with low viscosity and ‘vapor pressure. These materials contain primary famines located on secondary carbons, which ssves them relatively long pot lives due to the ‘methyl groups adjacent to the nitrogen. They can ‘oe accelerated with nonyl phenol or proprietary ‘compounds available from Huntsman Chemical Low shrinkage, ood clarity, and high toughness or flexibility characterize the cured products. ‘When cured with a standard bis-A epoxy, tensile elongation can vary from 2 10 aver 100% with tensile strengths from 7 to 70 MPa (1 to 10 ksi) Ref 13). "Tertiary amines (Lewis bases) react by cata lytic anionic polymerization (Fig. 7) (Ref 14) ‘The reactivity of tertiary amines varies widely as the electron density around the nitrogen changes. ‘The composition and location of hydrocarbon groups on the amine will affect the electron den- ‘iy. Homopolymerization results in higher glass transition temperaues, beter chemical resis- tance, and a more brittle product than a resin that thas cured through an addition reaction. They ‘may be used as sole cuatives at a level of ap- proximately 110 6>phroras accelerators for other gents, such as polyamides, amidoamines or anhydrides. Examples of tertiary amines are Q A fe (RNa Hee CH-CHy-B ———» R-N-CHp- GHB Pimay Epa on fn ‘Secondary amine and a scones yo A W RN sHC- CHC B ANC, 0-H -B Secenday—Epoxide oH ine Tear arin a 2 second era A K EVR HgS~CH— ChB ———> Fgh (CHy-C- Oh, Telay Epa m8 ‘hatearyanrium peter Fig. 6 Eeonfunine reacts) The primary amine group reacts withthe epoxide group to previ secondaryamine [Boupe. The seconday sme pov fur eat wh the epode fours tnd genet eta ane ‘poup.Inbath intances te hyo soup ae food, which are believed to caalyze the anne exe reacbon 3) fhe tiny amine poup exer 2 coal eet ad eases the sponse pou t sek-solymarize orm » ply, Sources Rett Epoxy Resins /81 Dyridine, ethylamine, and 2,4,6-ts( ‘ethylaminomethyd)phenol (Ref 15). (Cyeloaliphatic amines are charsctrized by having a least one amino group attached directly tw a saturated ring. Examples are isophoronedi- amine (PDA) and methylene- fibit more rigidity in the cured backbone result- 1 Bene on” soit SA er LV a Gi ai 5 po se SL SoH See we NAT Oe ba Fig. 7-tpoxyteiary amine tenis bss reacton ech ; wy le oO Fig. 8. cham srucue ofa polyamide 82 / Constituent Materials ing in a higher 7, Amidoamines are low- cosity amber liquids thathave very ong pot ives fnd afford good toughness, flexibility, and ad- hesion, particularly to concrete. They are used ‘when iow volatility and minimal skin iitation axe desired. This class of curative also tends to yield better moisture resistance than aliphatic polyamines, Both polyamides and amidoamines ‘nay be only marginally compatible with epoxy resins, which means that they must be very ther ‘oughly mixed before use. When stirred, the ep- foxy-curative may need to partially react before they become fully compatible with each other (Ref 16, 17). ‘Selection Factors. Cylosliphatc amines, pol- _yamides, and amidoamines canbe used ata wide ange of stoichiometic ratios to generate the de- ‘Sted handling or cured properties. Although both an amine value unetionality ofthe amine) sand equivalent weight are available from the Vendor, these curatives are generally. com pounded following recommended use levels fiven in units of phe. Glass transition tempera- tures vary between 5 and 55 °C (40 and 130°F) after cure at room temperatre and may be in freased substantlly with elevated temperatare for posteure. Tensile stzengths range between 21 land 59 MPa (3 and 8.5 ksi) and clongations be- toreen 3% and 8.5% (Ref 16) ‘Alipatio amines, their adducts, and deriva- tives are availabe from a number of companies ‘who offer a profusion of products (Table 2). The Sheer numberof options may seem confusing to the formulator, so it becomes important to note that a number of vendors have unigue designs- tions or trade names for what are basicaly the ‘ame prodoet, Selection may hinge on purity, form, packaging, availability, or price. Many other products are proprietary adducts and ‘mixtures that may contain accelerators and cO- feactats, such a8 fec-aliphatic amines, benzyl Alcohol, nonyl phenol, phenol, and salicylic acid. It is also important to undersund that multiple Formulations using different curing agents and cllfeent epoxies may yield the same cured prop- fries but differ inthe other parameters, such 38 mix viscosity, pot life, cre time, or appearance. Uses can range from electronics and encapsula- tion to thermoseting adhesives, floring grout, find trowel coatings. A general performance Comparison ofthe major aliphatic amine types, ‘which represeat the bulk of room-temperature Curatives, can be found in Fig. 10 (Ref 16). Room or Elevated Temperature Curing ‘Agents, Unike the amines and amides discussed tare, the following (wo classes of curatives, [BF, complexes and imidazoles, contain variants that may be cured safely aroom temperature and 7 ty Fig. 9. chemical seucuce of an amidoamine at elevated temperature. Instead of pot lives of ‘minutes to hours, dues compounds may be mod ified to remain Tafent at room temperature for perieds ranging from hours to days. They are Dften used a5 accelerators in conjunction with ‘other epoxy cuatives. ‘Boron riforide-amine complexes (Lewis ac» fds) cure epoxy resins by catalytic cationic po- Iymerization. The mechanism is shown in Fig. Ti (Ref 18). Pure boron triluoride (BF,) reacts ‘with standard bis-A epoxy in seconds, $0 room temperature stability is built into the molecule by adducting BF, with various amines. These cearatves, most of which are proprietary, may be Stabilized bythe addition of excess amine, which falso reduces the elevated-emperature reactivity ‘The complexes ae avilable as liquids that vary jn latency, activation temperature, and cured properties, Systems can be formolated to cure in FRours at room temperature or they may be de- signed as stable at room temperature and require flevated-emperature cures. Boron trifuoride complexes are used to generate resin castings fand coatings with T,s of up to 200 °C (390 "F) ‘Ss with amine cures, the product 7, will wally Jag behind the cure temperature ‘by approxi- mately 20 °C (36 “P). ‘With standard epoxy resins the cure reaction is rapidly triggered and highly dependent on temperate, 50 elevated-temperature cures can be long and often occur in a step-wise manner to prevent uncontrollable exotherms that can de- trade physical properties, making a par unuse be, One ofthe benefits ofthis lass of curative ig that they are used at relatively low levels 17 pars to 100 parts epoxy) Ref 19). Substituted imidazoles axe a unique class of ccuratives that find applications in eleetronic, ‘Stuctural adhesive, atomotive, and aerospace ‘composites They ste generally employed as ac- ‘elerators for the reaction between epoxies and ther curatives but can also be highly effective fs sole curing agents. They are one ofthe most ficient of the Lewis bases, initiating anionic SS & Se St _ Foon ger, S Sem = Se Ppt tt oh Ot | sci ae eee make | ee gh ep on. Ata ie hin | Bi oe a ee eh | AAbtaIeA poyanide Oye. Oye estcine | opie PO lei | sa | deme | Povaride PME aricoamine Aiphatc-A Aliphatic Poiamida Amidoamine Alphatic 1 er pee doh bed 2 we Fig, 10. comparson of some amine crave clases. A, adduct crate MB, Mannich baesype curate e 7) & f 2 7 ex R= [| eae fewer fe * vain MR] Sango o @ @ Terinon exe anda 00, ROH exon +H Fig, 11 Epooytewis ac veacton mechanism ° ———— Ihomopolymetiation ofthe epoxy resin at very ow loadings (<8 ph). Imidazole curatives are tailored by substitution with organic groups on the ring, chemically blocking active amine hy- drogen on the sing, and by salt formation with ting nitrogen. These modifications result it mol- ‘cules that are rendered Itent through steric hin- drance or insolbilty in room-temperature ep- ‘oxy resin, Imidazole cures are characterized by high glass transition temperatures (which usual exceed the cure temperature), room-temperature Jatency that ranges fom several hours to 6 ‘months, and rapid cure beyond the activation temperature. Initial cures are generally 1.5 to 2 ‘hat 80 to 100 °C (175 to 210°) while posteures range from 2to 4 hat 150 to 200 °C (300 to 390 5, The chemical resistance ofthe cured product is similar to that achieved with aromatic amines, and 7,s can exceed 200°C (390 °F) Imidazoles ae also used as accelerators in anhydride cures (Ref 20). Elevated Temperature Curatives include ar- fomatic amines and anhydrides. ‘Aromatic amines are generally fine-powder curatives that are blended or melted into epoxy resin. Some of the products mentioned subse- ‘quently wil also be available as supercooled lig- ids or eutecde blends to facilitate mixing at room temperature. The aromatics tend to be ‘more expensive than the aliphatic amines and ewer variants see availabe, An aromatic amine has the nitrogen of the nitrogen-hydrogen group iredy bound to an aromatic ring. The aromatic famines are used in high-performance composites and generally requite high- temperature cures 10 ‘yield superior 7,s and greater chemical resis tance than the same epoxy resins cured with al- {nhatic amines. The reaction of aromatic amines ‘with epoxy resins follows the same mechanisms seen in Fig. 6, The reaction is slower due to lower nucleophiliciy and steric factors, 80 for- mulated systems can show extended room-tem- perature out times. Although not as toxic as al ‘phatic amines, most aromatic amines are considered to be skin sensitizers or ivtants and ‘must be handled withthe proper precautions. ‘One ofthe first aromatic ansines used in in- dustry, 4,4"iaminodipbenyl methane (eepre- sented as DADM, MDA, or DDM in the litera- ture), exhibits one of ‘the best balances of properties available from a curative; however, it Js currently used infrequently since it has been identified as a suspected carcinogen. The toxie nature of MDA has impeded the introduction of, ‘ew avomatic amines With related structures be- cause they too would be suspected carcinogens. ‘The alkyi-substituted versions of this molecule, such as methylene-bs(dimethylaniline) and rethylene-bis(disopropylaniline) (MPDA), are less toxie and are commercially available. The henylenediamines follow the same pattem, ‘with the ally-substited derivatives such a6 iethyltoluenediamine being significantly less toxie than the base molecule, When the meth- ylene group of MDA is replaced with a sulfone, the result is diaminodiphenylsulfone (DDS), which is well known and widely used in the aerospace industry, When cured with bis-A ep- ‘oxy, DDS will yeld higher ,, tensile modulus, ‘and elongation than either MDA or MPDA. In ‘dition, DDS tends to be more latent at room temperature ‘Anhydrides are another major class of epoxy curing agents (Fig, 12) (Ref 21), that are aval- able in a varity of pysical forms from various ‘suppliers. Most of the products in use in epoxy. ‘compesite applications are low viscosity liquids or moderste-viscosity eutectic blends; nonethe- less, some solid anhydrides are also available ‘The reaction mechanism between an anaydride curing. agent and epoxy resin is complex, be- ‘cause three competing eactions take place. The anhydride reacts with the epoxy hydroxyls 10 form half-esters. The half-ester containing the free carboxyl group is then available to react with an epoxide ring, which generates another hydroxyl. The newly formed hydroxyl can react with another anhydride or, inthe presence of free cd, it ean react With another epoxy to form an. ether Fnkage. Formulating with anhydrides requires some ‘experimentation because the desired ratio of an- hydride to epoxy can vary widely depending on ‘materials selected, the concentration of hydroxyl groups in the formulation, and the presence of fn accelerator. Anhydrides are usually used at becween Oud to 1.1 equivalent to the epoxy. AS with amine curaives, the equivalent weight is

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