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  • Polyimide Resins

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    André R. Marcondes
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    Polyimides

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    Polyimides

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    42 просмотров15 страниц

    Polyimide Resins

    Загружено:

    André R. Marcondes
    Polyimides

    Авторское право:

    © All Rights Reserved
    Скачайте в формате PDF или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    из 15
    Polyimide Res Danie! A. Scola, University of Connecticut ins POLYIMIDE MATERIALS can be catego- rized by their temperature capabilities into hose with an upper limit of 230 °C (450 °F) for ex- tended time periods, snd those capable of ex- fended use up t0315 °C (600°F). Bismaleimides, phenylethynyl-coataining polyimides, and some Condensation polyimides sbch as Avimid-K3 bo- Tong in the former category, while those mate~ rials such as PMR-15, LARC-TPI, Avimid-N and BPDA/TFMB belong in the later In terms of chemistry, there are two general types of com- ‘mercial polyimides: thermoplastic polyimides, derived from a condensation reaction between anhydrides or anhydride derivatives and diam- ines, and crosslinked polyimide, derived from an addition reaction between unsaturated groups ‘of preformed imide monomer or oligomer. The imide monomers or oligomers are also devived from the typical condensation reaction to form the imide group, but polymer formation stems from the addition reaction. or completeness, the chemistry of both types and process conditions to fabricate articles re described in this ariel. [Bismaleimides are not reviewed in this article. (See the article “Bismaleimide Resins” inthis Volume.) Properties and Applications ‘The specific advantages and disadvantages of ‘wo types of polyimides are summarized in Table 1. These are generalized conclusions regarding ‘each type, because there ae exceptions, which depend on chemical structure. ‘The condensation polyimides, which are li car long-chtin thermoplastic polymers, have high melt viscosity, thereby requiring high pros- sures and temperatures for neat resin molding or composite processing. However, the highly aro- ‘matic nature of these systems coupled with lex- ‘ble groups, such as ether, hexofluorosopropyli- dene, of ‘methylene within the backbone structure, yields materials with good toughness, ‘excellent thermal snd thermooxidative stability, and moderate to high glass transition tempera: tures (7) ‘The dddition-type polyimides, derived from preformed oligomers, undergo thermal cross Tinking or chain extension to form a thermoset. ‘The oligomer molecular weight controls the pro- cessability, the degree of crosslinking or chain extension, and the T,, However, because no vol- ates are’ released during processing, and the oligomers have a melt or softening region where the viscosity is relatively low near the tempera- ture region where the addition reaction occurs, moderate to low pressure is required during pro. cessing to consolidate the part being fabricated, Polyimides are finding wide applications be- ‘cause of their unusual properties. The polyim- ides derived from aromatie dianhyérides and ar ‘matic diamines containing stable flexible units inthe backbone exhibit: 4 High ermal and thermo-oxidative saiiy upto 400°C 750") ‘Excellent mechanical properies, bot troom temperature and elevated temperatures ‘Film and fiber forming ability © Exoelent adhesive properties, both at room temperature and elevated temperature ‘+ Nonflmmabiity—will not suppor combus- tion Table 1 General attributes of condensation (thermoplastic) and addition-type (cross- linked) polyimides ie ‘ean Condensation (rncpnas) Themoransfopacesbly) “Madeat to gh ps eansionenpertrs (7) Vass lowed cng ‘raph igh eure eu proce Excl ema nd ero-iaive salty Prose rw inked Herr, Nove in processing Addon ype rosin) Le epcty Poo ema se hemo-xive ably Fluorine-containing polyimides exhibit the properties listed previously, as well as low di- tleetric constant. Polyimides containing func- Iale2_ Applian opines by mas, a =. See a aa a Eos ies =e a rd Bett sviches oo Fo er ea nn Solna Seirecyarn (Gs poten ‘sop Malay eppsions Naming Table 3 Applications of high-temperature polyonide composites in arrat engines lag cegins Sao vanes Seed in cio) Bishings Garcons nace) ‘hn ig aria vne aan ‘Seat siete ow ree Exelspeerbo hv sad mo Beas 106 / Constituent Materials onal oe pendant groups inthe backbone ofthe Since te mi-1980s the appiaion areas for ie oe Pee applications Polyimide products Lona en eePoafand Giamine exhibit high-temperature polyimides have continually are wed i 8 es, ‘of applications, such a somatic, iby ed previously: es well grown, Thus is Bens f the ailty ovary the soatigs, GS, or matrices, bes, as selective gas permeability erin suctre therchy tailoring te proper- fms, foams, moldings, membrane, awit COs, . lulline displays, and insulation. A lst of general saratoga by indy seen a Tble2 se apteons of ighemperatre ply SRSa feta tse a abe 3 Clay o 8 it rye Hy RT to or ROH. + HAIN HQEEO —satles Developmental hightemperature Bee] to see aa palin res ik oe 4 en aoe _ ae ie ely (omic sai) = DAA 38 a — we-s07e = sae low Lf sr OT oy Sk ve PORES opus at seme |. - _ AX sf he spurs, Aevsoan 1 _ solvent PMMDAIAINE PDMDAJA:NHs 2» nai Te g8 Me B In momar Ba en DD imide BTDA/BABNINE wo Fig. 1 conc! racton or ondnstonpbiiesSer cr be NE OME mers ame sroMBBAT 2877 a cD ives 8 Table 4 Commercial polyimide materi ar ams os — Be Oeem = _ Sor Hotere 3 ere Pate BONE a3 ‘DuPont Teton “Veapel composites ‘DuPet Tiibon Composites ‘BIDAJAPEINE. 2 Daf: ernie re es iss) ED Meosyses RONEN TE ene Ce an ee a ‘avin: K3 (pee, powder) Cyt Fiberie ADATMEZINE SS rLCLr ne Seen er ones ren ein oe i felted, Sree ra te ey eM So ers octane. sci coe eo _ SSAe iam momen — S Sa ee aon ae TE ae MEM | Seefiptennte eeneatcs reale ee eres in a Sac eagle ee wees — io soi cro cae _ _ Sees retire tae _ _ tte 5 tate - Ee nw me say ter aAPR 22-8 (amino rvnis neko Fiese APRN gered cits croum | mma aap as ‘Raton Aeonmis 208 See aac on, pe SEM em eg Eeyalnts fel tfc aoe a rien bmn ect arene on ans gem ae Sara mmmoed tee ae _— ise pasar aruiee) _. sn Hef bch a ea eras ssa ytd ‘PETS oni onde) — a — masons Se ee coe esa a _ _ eee ee aca ERE omy nig herby RSE a te ee ee “ova Fe Si pron nOME UApaneniomnpn bat Soe nay ese MIDMGAF e-ganniem sepia, sat, DARTON, 22 Rr hotccnpmiie PB, phn LARCSt oan poms) Ine. ne Tee 779 ros poste) Tie 27 tan, ome) Table 6 Thermal properties of pol Polyimide Resins / 107 ‘sore semper Poser tepertae eatepuccre ——_tperore_ “Toermaplanie pigmies = dram 8 et 5539) mw 0 * ee ) imi er a2) 0 ao iso Bs ‘nis IA Ret 3-02) ae an mtr ‘Avis 3B ha 2-2) Bs oe Bf awe a 3) as SoMa mo serious) mom mais oT é aioe Serr ers) a a8 aul * ' re TARCSI Reta) a 3m Sm mo ‘her 10 et 5) ho 40m isto Syn 1 Serie (Re 6) bo 0 goo eo ‘Aonon New Te), = 0 mS oS ‘roar (ee). "omen cs mo sama ue Sod ste cae jo ao] ek he opon HR 8) 3 ao im ae Pn P2505 (Re 0) = 0 4s ae Py PL s10 Ret 8) ww 3st Sis an ymin 2500 (Rel 2) so kth ms ‘Amoco Uae 212 (Ret 50) Bs So i] ‘epee S) so |] mie Teton 205 et 52) a oS ms GT 27as-sepaKeopARe 6) = 9 gta HD ae BIDAMTPER et (7) ho S05 ste BEDAVTPER tet 19) bo Sims mo ie POMDNAAIEIAMDA) Reta = 2104190 Bie ros tke pies ‘imate 300 0 a ‘imi RB 55) Se et Ot ates ar 6-6) Mo oe mat 6 & we ism TARC RP et 2) mo Soe mo mm 5 so m0 om ‘ABR U0 ha 8-5) mm 0a 7, : Ss m 36 at Sipe 10 Re eo) so 0 Sieg tetoo a0 2 a om OMe a Pers et 3,16). mm m 3 MD 2 fe AGRI le 67-9) me att +6 By wo ete earatso et) pu «0 Bs i os St IDA (et 2,26) ao mo o = @ om om ar PE Ute 500 (Re 5) mo uD mo ae SPDAp-FDANE (Re) So ee it #8 me an ‘the range of applications forthe polyimide is a ‘200d indication ofthe ability to modify molec ‘lar structure for specific properties. Hundreds of research polyimide materials have been syn- thesized over the years, but only a few are com- ‘mercially available atthe present time. However, ‘many research polyimides are available fom specialty chemical houses. partial lis of avail- able polyimides and their sources is shown in ‘Tables 4 and 5. The glass transition temperatures and upper temperature capabilities ofthe wo types of pol- yyimides ae listed in Table 6, The thermal prop- eis ofthe polyimides depend on the presence of flexible units, such as ether, isopropylidene, methylene, hexafuoroisopropylidene, and car bbonyl in the backbone of the polymer chain, or Dulky side groups pendant tothe backbone struc ture, These groups can also affect solubility. Dis ruption of regularity by the copolymerization of ‘wo dianhydrides with two diamines also affects solubility. ‘An important consideration inthe selection of «polyimide for a composite application is resin Toughness. An interesting corelation of resin toughness versus estimated cost is shown in Ti- ble 7. The polyether imide (PED) Ultem has the ‘most favorable toughness/eost corelation. As with all polyimides, this property must be bal= anced between other properties, such as process ability, 7, temperature capability, and meckan- {cal props. ‘A’summary of the thermo-oxidative stability of several polyimides at 316°C (600°F) and 371 °C (100 F) is given in Tables 8,9, and 10. The data clearly show that the fluorinated aromatic polyimides possess the highest thermo-oxidative stability ‘A comparison of common physical and me- ‘chanical properties of polyimides is provided in ‘Table 1 Chemistry of Condensation-Type Polyimides ‘These material, discovered in 1908 by TM. Bogert and RR. Renshaw (Ref 75) and made practical by WM. Edwards and IM, Robertson ‘Table 7_ Relationship of resin toughness to cost Gouscos sepia msn etn ope = ae a pee “a0 0 0 “a0 ‘eam oR isco io & 0 i APE T0850) 00 to iso to uw ut = 2 = is 5 Uhea =) 000 Mo 5 é ier (eine ci hen (0) in ey ct nS. Tn rae ite wit ink in sce Sure RE 108 / Constituent Materials (Ref 76, are derived from polyamic acids by tier evel or thermal treatment over a tem perature range fom room temperature to 370°C {700 7) The polyanic acids are produced by & ‘ets of stp growth reantions at rom tempera ture from a dianhydride or dianhydride de tive anda diamine. The general reaction for pole Ynide fomation is iustated in Fig. 1. The ferictures of several commercially available thermoplastic polyimies are shown ia Fig. 2. Synthesis (Genera). Themoplsticposin- ides are prepared in dimaylactamide (DMAC) co Nomethy pyrolidinone (NMP) by dissolving the appropriate diamine in the solvent at room temperate under nivogen. The dianhydride is seid asa solid ora slry in the solvent while Sting over a period of one-alf hour. The r= fection is allowed to continue from 6 t0 24h hile siving under ambient conditions, depend- ing on the Telatve reactivities ofthe diamines sand dianhydride. The polyamide acid solution thus produced can be sampled for detemnination of ine viscosity or analyzed by gel perme- ation_chromatography (GPO) for molecular ‘eight or analyzed by ober methods a required. “The polyamide acid soluon ean be usd to pre= pare polyamide acid or polyimide powder, hia fms, suppored adhesive tape, and to impreg- ‘ate nirecdonal carbon fiber, carbon loth, or ‘ther befloth substrate ‘Altematively, thermoplastic polyimides can also be prepare by disolvng the alkyl ester {anes ethyl, o isopropy) ofthe dianhydride in ethanol at room temperate followed bythe son ofthe aromatic alanine. This polyimide ‘recusor solution can also be used to prepare povider, thin ns, supported adhesive ape, and Jimpregnated carbon iter, carbon clth, other Apecoth substrate. The polyamide acid canbe converted the polyimide by thermal methods or by chemical methods, described subsequent Processing of Polyamide Acid Precursor Solution to Polyimide. The polyamide acid so- Tation canbe converted thermally insolation the polyimide by: the addition of a sufiiest «quantity of toldene or o-xylene, followed by Sseotzopie distillation of water in a DeanStark trap overnight by refluxing the polyamide aid solution containing 1 10 2 wt isoquinoline eat lyst (based on solvent for 6h: or by the adi tion of ten-fold excess of aco anytside with pridine of wiethylamine catalyst at a 4t0 1 bight ao, followed by beating a 100°C (210 for 3h “The polyamie acid solution can also be pre- pared in mresolsolvetinsiead of DMAC or NMP at room temperature and converted. the polyimide by relaxing st 200 °C (390 °F) with oF without a caulyst (1 © 2 wi isoquinoline based on m-creol for 4h The polyimide pow ders isolated os described in the folowing par amps 'NMP or DMAC polyamie acid solution is added while siting vigorously to « methanol ‘eater (50:0) solution. ‘The peecipiated po- Iyamic acid powder is fered and washed agsin in methanol and water, then died at 125 °C for 24 him a vacuum, or at 200°C (390 °F) for 4h in vacuum. The polyamic acid powder is con- verted to polyimide in an oven at 150 °C (300 °F for 1h + 250°C (480 F) for 1h + 275°C (23°F) for 1h ‘Alcohol solutions of the diester and diamine ‘composition are concentrated to solvent-free °C (140 °F for 2h. The polyamic acid powder is converted thermally to polyimide powder at 150°C (300 °F) for 1h + 250 °C (480 °F) for Dh + 275°C (525 °F) for th Preparation of Polyimide Films from Ther- ‘moplastic Polyamic Acid Precursors. Ceatr- faged NMP or DMAC solutions ofthe polyamic cide are caston a clean glass plate and heated polyamic acid powder in a vacuum oven at 60, ‘Table 8 Thermo-oxidative stability of high-temperature polymers at 316 °C (600 °F) (air flow, 100 m/min, oF 6 in./min) Pee coma petce 9 oe mae a seat @ 13 ae se 107 2279. o 2 at si 13 Paras ° <7 uA aa ss ws sto. 8 ooo as 92 Lancet ° at 88 wes 2 C0 ro oe mw 10 o Ss ino ti. ar ‘» ms. ea Py Saetas ® 10 a $3 Poe30 ° 2 i an9 io Pae.30 ® 3 to ios iso See o toe a See o 30 So eR 708 ® 200 ‘Te avo derbi.) 3164 an HLA + 30 ISTHE 0) 2H -C IS VA OTE (HOTA. (9216 Sanit stern Gsecon nas secon asec ae mit Motes Oe 1 esc ep Sect Som Cans Ca 50m (nm Sm i Sa ed Helicase arseanon Oa cmomie SORT FH comman Duce HIE TS Table 9 Thermo-oxidative stability of polyimides at 370 °C (700 °F, 1 atm (air-crculating, oven) Tie ar mabe a) esate coneetpeian Bb toe soho ving ® Teese w GPK 1, Avis Neomed) o ts 33 io, Srepa Gem ® to 4 non Set ® so 16 Paears0 ° Fn Psa ° 45 astm Sse) 280 @ in 26) ® ty 6 ® oot ers in nom (SR. 98, 7 ar ate) Capt BPD SF OA BH Sess A Sr ie‘ sytn nc ooo pany Mg CCB) Con onc rR ‘Sefamsnan ise (ory nt 30°C (0A +31 O00 “Sh oe mapas fe MEISE CD TT St Sn ash Smee Ra 1h) Ses a Fa rae 1 'C GN It eA at SODA posed 71 ‘iu eh Fie ecw ape eg den, dh Some Ra, 7 TE ides at 371 °C (700 °F), 4 atm (airflow, 100 Table 10 Thermo-oxidative stability of poly ‘em?/min, or 6 in."/min) Dimi @ 1st 230436 10 ms eR PDA co) @ ua it Sun tas 2 SEPA @ 1 bas So io rt uueirso ® fy Ts i Potett30 ® 3a ie Pats ® so aa ‘APR"W0B ‘9 os tas a is ‘Seea @ ir 30 o a ‘See eats on Cn tn i FDA 3B DASE PDA, AER TOE 165 DP + ‘Soren aes s esc cm rye cue mone eka ies tore 91 8 + MOCO TE SEBEL Cal pce fr AE HS Elo IPH ATED aA eae Re a 80°C (175 °F) ina vacuum for 1h. The tack free film is then cured at 100 °C (210 °F), 200, °C (390 F), and 300°C (570 *F) for 1h at each temperature, The film i removed from the glass surface by immersion into warm water. Alter- natively, an alcoho solution af the polyami€ acid precursor is centrifuged, and then the solution is cast on a clean glass plate using a doctor blade, ‘The film solution is placed in a chamber undee flowing nitrogen at room temperature for 4b tO become a tack-free film, and cured according 0 the schedule described previously. Chemistry of Addition-Type Polyimides General suuctures of several types of addli- tion-type polyimides are shown in Fig. 3, Spe- cific structures of the more common materials are shown in Fig. 4. Generally, these materials are low-molecular- weight imide oligomers con- ‘aining unsaturated end caps, capable of forming an addition-type reaction. In some cases, these unsaturated groups ean also be located as pen- ‘dant groups inthe backbone ofthe oligomer unit. Phenylethynyl-Containing Imide Oligomers Sine 1985, consideble efforts have been nade inthe area of phenyltyny containing inde aligomers were th phony thyny group nb laa at chain ends (Ret 17-89), per dant the main cain (Ret 84,85) ell pendant and terminal (Re 13,18, 86-90) 0 the fain cia, shown schematically in Fig. 5: Of the many penpetiynyend

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