cu») United States 2) Patent Application Publication co) Pub. No.: US 2020/0317909 A1 oy ow 2 ey @y (66) (0) 6) ASPIN et al. CURABLE RESIN COMPOSITION AND FIBER REINFORCED RESIN MATRIX COMPOSITE MATERIAL Applicant: Cytee Industries Ine, Princeton, NJ ws) Ian ASPIN, Derbyshire (GB); Nieolas DREUILLES, Nottingham (C2); Jonathan MEEGAN, Chester (GB) Appl. Nox 167183,434 PCT Filed: Oct. 5, 2018 PCTNo: — PET/US2018/054662 $371 XI), (2) Date: Related US. Application Data Provisional application No, 62/569,856, filed on Oct. 9, 2017 Publication Classification CosL 63/00 (2006.01) cuss 5/24 (2006.01) ‘US 2020031790941 (43) Pub. Date: Oct. 8, 2020 m0 11/10 200501) ‘B20B 116 (2006.01), B29¢ 7032 (200501), (2) US.¢ ce CaBL 63/00 (2013.01), Cosy 524 (2013.01), 8298 11/10 (2013.01), B29K 2063/00 (2013.01); B29C 7022 (2013.01) COBY 3363/00 (2013.01), COSI 2487/00 (2013.01); B29B 11/16 (301301) on ABs RACT A curable resin composition contains @ curable resin that ‘comprises at least one non-aromatie epoxy compound, at least one non-aromiatic oxelane compound, or & mixture thereof, one or more curing agents selected trom Lewis scid:Lewis base complexes, and a cure accelerating amount fof one or more anhydride compounds, A method aeceler jing the cure of a curable resin composition, comprising adding a cure eeelerating amount of one or more anhydride ‘compounds 10 a curable resin composition comprising. @ ‘crahle resin that Comprises at Teast ane non-aromaic epoxy ‘compound of non-ansmatie oxetane compound and a coring ‘get that comprises one or more Lewis acid-base com plexes. The composition and method are useful in making liber reinforced resin matrix composite atices‘US 2020/0317909 AL 2020 Sheet 1 of 4 Oct. Patent Application Publication Frienaun (9,) eimesedway eo saues ——— zp aduerg -—— {Semues --— {educa —— old anos (Bin) MO} BH‘US 2020/0317909 AL Oct. 8, 2020 Sheet 2 of 4 Patent Application Publication salesman (9,) emeeduiay, oz og on oo or oF Zod enw (Bina) 05384,Patent Application Publication Oct. 8, 2020 Sheet 3 of 4. US 2020/0317909 AI “Temperature ((C) (Gin) wots 22H FIG.3Patent Application Publication Oct. 8, 2020 Sheet 4 of 4 US 2020/0317909 AL 7250 i : 260 150 S § Ee 5 B 3 8 3 3 8 3 3 35 ao. (Gina) mola eo 2US 2020/0317909 AI (CURABLE RESIN COMPOSITION AND. IBER REINFORCED RESIN MATRIX ‘COMPOSITE MATERIAL FIELD OF THE INVENTION [0001] This invention reltes to a curable resin, fiber reinforced resin mattix composite materials comprising ‘hers and the curable resin, and fiber reinforce resin mateix ‘composite articles made thereby. BACKGROUND OF THE INVENTION [0002] | Carbon and/or glass reinforced carbon fiber com posite materials are used in high performance applications, ‘eg. in sorospace and automotive applications, where light= weight high performance are required 10003] The automotive industry has wsed flber reinforced ‘composites (FRC) for parts of automobiles, especially high performance cars, and trucks for many years, The Use of high spoed manufacturing technologies allows carbon fiber reinforced plastic (CFRP) composite materials to move into serial production vehicles. One such tecanique is rapid cure press moulding, The substrates used in this process could be from prepreg or from filament wound materials. ln the later, ‘ows of carbon fiber, ether pre-impregnated with resin of more commonly; impregnated in-line, are wound around & rotating mandzel, As the winding head is moved back and {ont long the mandrel i allows a variety of woven articles with numerous interlocking angles to be constructed. The removal of the fiber reinforced resin matrix composite ‘material from the mandeel ereates rectangular “blak” that ‘can be used as the substrates for rapid press curing in a similar way to prepreg materials SUMMARY OF THE INVENTION 10004} na frst aspect, the preseat inventions dinete to 2 curable a curable resin composition, comprising {1005}, (@) a curable resin tht comprises at least one ‘on-aomtic epoxy compound a est one naam exctane compound, oF a mixture there, 10006} (6) one or more curing agents selected from Lewis ack:Lewis base complenes and 0007], () a cure accelerating amount of one or more ankydride compounds {00108} none embodiment of the resin composition, the at least one non-aromatie epoxy compound comprise at lest ‘one epoxide gmoup per moleesle of such compound the at Jeast one non-aromatic oxetane compound comprise at east ‘one oxetano group per molec of such compound, the one ‘or more andre compounds each comprise at least one anhydride group per molecule of such compounds and the resin composition comprises [0009] a amour ofthe one or more curing agents elf tive to provide a ratio of Irom 1:25 t0 1:2, preferably fom 1:20 15, of molar equivalents of Lewis acid ewis base complex &© molar oivalents of epoxide groups, oxetano froups, oF mixture of soch groups, snd 10010) an amount of the one oF more anhydride com- pounds effective to provide arti of up t6 I: prefebiy From 1:20 0 1, of molar equivalents of ankydeide groups to molar equivalents ofthe Lewis sci eis base complex ‘component ofthe resin composition Oct. 8, 2020 [0011] In another embodiment, the curable resin compo= sition comprises 0012] (a) a curable resin comprising at least one non- ‘roma epoxy compotnd that comprises atleast one ‘epoxide group per molecule of such compound, at least ‘one non-aramati oxetane compound that comprises at Teast one oxetano group per molecule of such com- pound, ora mixture of fueh compounds, [0013] () one oF more curing agents selected from Lewis acid-Lewis base complexes, in an amount of fiom 1 10 20 parts by weight ofthe one or more curing ‘agents per 100 parts by weight of the resin composition, and 10014] (@) one oF more anhydride compounds, each ‘comprising at least one anhydride group per molecule ‘of such compound, in a cure accelerating amount of fess than 0.5 molar equivalents of anhydride groups per molar eguvalets of eponde groups, etre rps [015] In another embodiment, the anbydide compound Js an anhydride polymer or oligomer having a molecular ‘Weight of greater than or equal to about $00 mole and having one or more anhydeide functional group per mol- ecule. [0016] Ina second aspect, the present invention is directed to a method accelemting the ete of a curable resin com- position, comprising adding a cure accelerating amount of ‘one oF more anhydride compounds to curable resin com- position comprising a curable resin that comprises at least fone non-aromatie epoxy compound, at least one non-are- ‘matie oxetane compound, ora mixture thereof, and a curing ‘agent that comprises one or more Lewis acid-Lewis base womplexes. [0017] The accelerated cure makes to possible to fully ‘ure the resin composition ofthe present invention ata lower temperature, typically a temperature of greater than or equal {0 60° C., more typically of from 100° C. to 180° C., and even more typically of from 120° C. to 160°C. fora shorter time period, typically a time period of less than or equal t0 20 minutes, more typically of from 1 1015 minutes, and even ‘more typically of fom 1 minute to 10 minutes, wither ‘requiring a post cure, compared to analogous resin compo- sitions that Taek either the one or more Levis aeid-Lewis base complexes or the one or more aaliydride compounds [0018] Ina third aspect, the present invention is directed to a method for toughening a cured resin composition, comprising adding. @ cure accelerating amount of one oF ‘mon’ polsmeric anhydride compounds a curable resin composition comprising a curable resin that comprises at Jeast one non-aromatic epoxy compound, atleast one non- aromatic exetane compaund, or mixture thereot, and @ fcuring agent that comprises one or more Lewis acid-base ‘complexes, inthe substantial absence of anyother polymeric toughening agent [0019] The curable resin composition is capable of being rpdly cured at moderate temperature. In one embodiment the resin composition exhibits a high degree of cure con: version, as measured by DSC (residual enthalpy), of typ cally greater than or equal to 85%, more typically greater ‘an or equal to 90%, and even more typically greater than ‘or equal to 95%, and high glass transition temperature, as measured by DMA (storage modulus transition), typically ‘greater than or equal o 210° C., more typically greater than fr equal to 215° C., and even more typically greater than or equal to 220° C., well as good mechanical strength, ater curing at a temperature of greater than or equal to 60° C.,US 2020/0317909 AI more typically of from 100° €. to 180°C, and even more typically of from 120° C. to 160°C, fora time period of less than or equal to 20 minutes, more typically of from I 10 1S minutes, and even more typically of from 1 minute to 10 minutes. BRIEF DESCRIPTION OF THE DRAWINGS 10020] FIG. 1 shows a plot of heat fow (Wig) versus temperature, as measured by differential scanning calorim- 10021} FIG. 2 shows a plot of heat flow (Ws temipenitie, as ensued by differential scanning calor. ‘ety ding curing of the resin compositions of Examples 1, 5.6.7, Solthe present invention axl Comparative Example a 10022] FIG. 3 shows a plot of heat flow (Wa) versus temperature, ss measure by diferetal seaming calori- ‘ey during curing of he resin composition of Example 9 of the present invention and Comparative Example C3 10023] FIG. 4 shows a plot of Wig) versus temperature, as measured by dllerential scanning calorimetry ding curing ‘of the resin compositions of Examples I and 12 of the present invention DETAILED DESCRIPTION OF INVENTION AND PREFERRED EMBODIMENTS, 10024] As used herein in reference to an onuanie com pound, the term “aliphatic” means that the organic com ound has a straight or branched chain stricture and lacks ny aryl or alicyclic ring moiety, wherein the chains com- prise carbon atoms joined by respective single, double, or triple bonds and may optionally be interrupted by one or more heteroatoms, typically selected from oxygen, nitrogen, ‘and sulfur heteroatoms, and the carbon atom members of the ‘chains may each opdionally be substituted with one oF more ‘organic groups that lack aay’ aryl or alicyclic cing moiety. typically selected fom alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkeyalky, haloalkyl 10025] As used hervin, the teem “acyl” means a monova- Jeat organic radical consisting of a carbon atom bearing an ‘organic substituent group, typically an alkyl, alkenyl or aryl _roup, and an oxygen atom connected to the earbon atom Ry ' double bond. 10026] As used herein in reference to an onganie com und, the term “alieyelie" means that the compound com prises one or more aon-aromatic ing moieties and lacks any fnyl ring moiety, wherein the members of the one or more rnon-aromaic ring moieties comprise carbon atoms, each of the one oF more non-aromatie ring moieties may optionally be interrupted by one or more heteroatoms, typically selected from oxygen, nitrogen, and sulfur heteroatoms, and the earbon atom miembers of the one or more nom-aromatic ring moieties may each optionally be substituted with one or ‘more non-aryl onganie groups, ypically selected from alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkoxyalkyl, haloalkyl [0027] As used herein, the term “alkenyl” means an unsaturated steaight, branched, oF eyctie hydrocarbon radi cal, more typically’ an unsaturated straight, branched, oF feyelic (Cy-C,,) hydrocarbon radical, that contains one oF ‘more carhos-carbon double bonds, such as, for example ‘ethenyl, n-propenyl,iso-propenyl, and eyelopentenyl Oct. 8, 2020 [0028] As used herein, the term “alkoxy” means a sate ‘ited straight or branched alkyl ether radical more typically a (C-Cy) allyl ether radical, such 3s, for example, methoxy. ethoxy, n-propoxy, isopropoxy, n-butoxy, tert Dutoxy,See-butoxy, n-pentoxy, and nonony, [0029] As used herein, the tem “alkoxyalky?” means an alkyl radial that is substitnted with one oF more alkoxy substituents, more typically a (Cy-C,,) alkyloxy (Cy-C,) alkyl radical, such as methoxymeth, and ethoxybuty [0030] As used herein, the term “alky” means a monova- Tent steaight or branched saturated hyoearbon radical, sore typically, a monovalent strsight or branched saturated (C.C.,) hydrocarbon radical, such as, for example, met], ethyl, a-propyl, isopropyl, n-butyl, isobutyl, tert-butyl exyl, noctyl, and nehexadey [034] "As used herein, che term “alkylene” means a biva- Jent acyclic saturated hydrocarbon radical, including meth- ylene, polyethylene, and alkyl substituted polymethylene ‘dials, such as, for example, dimethylene, tetramethylene, and 2-medhyltimethylene [0032] As used herein, the teem “alkynyl” refers 10 an ‘unsaturated straight or branched hydrocarbon radical, more typically an unsaturuted stright or branched (C.-C,3) hydrocarbon radical that has one or more carbon-carbon teple bonds per radial such as, for example, ehynyl and propargy! [033] As used hervia in reference 10 an organic com- pound or radical, the term “anhyclide” is a compound or radical that has two aeyl groups bonded tothe same oxygen atom wherein the respective carbon atoms of the two acyl groups may be Finked to form a eyelic structure, such as, for ‘example, maleic anhydride, succinic anhydride, phthalic anhydride [0034] As used herein, the term “aralkyl” means an alkyl ‘group substituted with one or more aryl groups, more ‘ypieally a (C,-C,q) alkyl substituted with one or more (CCya) aryl substitoents, such as, for example, pheaylm- ety, phenethyl, and triphenytmethyl [0038] As used herein in reference to an organic com- pound, the term “aromatic” means that the organic com: pound that comprises one or more one aryl moieties, which nay each optionally be interrupted by one or more heteroa- toms, typically selected from oxygen, nitrogen, and sulfur heteroatoms, and one of more ofthe carbon atoms of one oF ‘more one aryl moieties may optionally be substituted with fone of more orwanic groups, typically selected fom alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkoxyalkyl, haloalkyl, aryl, alkary, aralkyl [0036] As used herein, the term “aryl” means eyeic, ‘coplanar 5- or 6-membered organi group having a delocal- Jed, conjugated = systom, with a numberof electrons that is equal to 4n¢2, where n is O ora positive integer, including ‘compounds sshere each of the ring members is @ carbon ftom, such as henzene, compounds Where ane or more ofthe ring members isa heteroatom, typically selected from oxy zen, nitrogen and sulfur atoms, such as furan, pyridine, Jmidazole, and thiophene, and fused ring systems, such as ‘naphthalene, aracene, and fluorene, wherein one or more ‘of the ring earbons may be substituted with one or more ‘organic groups, typically selected from alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkoxyalkyl, haloalkyl, ary, alkaryl, halo groups, such as, for example, phenyl, methyl. phenyl, trimethy!phenyl, nonyiphenyl, chlorophenyl, or ‘eiehioromethylphenylUS 2020/0317909 AI 10037] As used herein, the terminology “(CC reference 10 an omganie group, wherein n and mi are cac tegers, indicates that the group may contain From n carbon. ‘toms Io m carhon atoms per group. 10038) The terms “cure” and “curing” as used herein may include polymerizing and/or cross-linking of the cursble resin composition. 10039] As used herein, the term “curing agent” means @ ‘compound or complex that is capable of dissociating 10 provide one or more species capable of initiating polymer- zation ofthe curable resin component of the curable resin ‘composition ofthe present invention, [0040] As used herein, the term “cycloalkenyl” refers 10 ‘yelic (C,-C,) alkenyl radical having a single eyeli ring ‘and at least carbon-carbon double bond between ring car bons, whieh can be optionally substituted with from I 10 3 alkyl groups, such a, for example, eyelopent-3enyl, eyelo- hex-2-enyl, and eyelooct--eny1 [0041] As used herein, the term “cycloalkyl” means saturated (C.-C) hydrocarbon radical that incades one oF more eyelic alkyl rings, such as, for example, cyclopentyl ‘eyelooetyl, and adamantanyl [0042] "As used herein, “epoxide group” means a vicinal epoxy BrOup, ie. a, 2-epoxy group. 10043] As used herein, the tem “ber” has its ordinary ‘meaning as known o those skilled inthe art and may include ‘one or more fibrous materials adapted forthe reinforcement ‘of eomposites, which may take the form of any of particles, Fakes, whiskers, shoe fibers, continuous fibers, sheets, plies, nd combinations thereo {0044} As used herein, the terminology “fiber pre-form” means assembly of fibers, layers of fibers, fabri oF layers of fabric pls configured to receive a liquid curable resin ‘composition in a resin infusion proces. [0045] As used herein, the tem “halo” means chlor, ‘uoro, bromo, or iodo, more typically chlor. 10046) As used herein, the term “haloalky!” means an alkyl radical that is substituted with one o¢ more halo substituents, such as chloroethy! and trichloromethy 10047] As used herein, the term “hydroxyalky!" means an alkyl radical, more typically a (C,-C,,) alkyl radical, that is substituted with ane or mare hydroxs] groups, such as for ‘example, hydroxymethyl, hydroxyethyl, hydroxypropyl, ‘and hydroxydecyl [0048] As used herein, the term “Lewis acid: ewis base ‘complex means a molecule formed by bonding of a Lewis, such as, BEs, ZaC1;, SaCl,, FeCly, and AICI, YOC, BCl,, AIF, with’ Lewis base, such’ 36 an aliphatic oF ‘aromatic amine, avetonitele, diethyetherate, tetaydro- furan, acetone, ethyl acetate, dimethyl acetamide, totahy- “drthiophene, timethylpbosphine, triphenylpbosphine with ‘out the simultaneous loss ofa leaving group. 10049] As used herein, the term “non-aromatic epoxy “compound” means & non-aromatie compound thal eomprises atest on, more pally test 1, epoxide oop pe 10050] As used herein “non-aromatie oxetane compound” cans # non-aromatic compound that comprises at least anc ‘and in some embodiments, Wo, oxetano group per mole cet [0051] As referred to herein, a “non-crimp fabric” or SNCF" means a fabric comprising of two or more plies of Oct. 8, 2020 wiizetional fibers the fibers of Kate, braided, discontinuous bonded chopped fiber mat. {0082} _Asused herein, “oxyalkylene” means bivalent cal comprising a alkylene radical hati subsite foxy group, sch as, for example, oxymetilene, and ox) imthylene {0083} As used herein, the tenn “preprew” means a fiber reinforcement chat Is been pre-impregate, fully or par “aly with curable resin composition ora fabric made fom ‘woven tows of bos that have been preimpregnated with resin climb resin composition (0084) "Thecurable resin composition ofthe present iven- tion compises at least one non-aomatc epoxy compound, a least one non-aromatie cXelane compound, or a tke thereat In one embodiment, the eesin composition com: prises at least one non-aromatie epoxy compound. In one Embodiment, the resin composition comprises atleast one son-aromaticoxetane compound. In one embodiment, the resin composition comprises. at least one nonatomsatic epoxy compound ad a least one non-arnatie oxetane compound {0085} "Suitable alicyclic epoxy compounds inludeaiey- Clie compounds having 860 oF more epoxide BrOUpS per ‘molecule, including know compouns suchas, for example, bis2.3-epony-cyelopentyDether. copolymers of bisQS-cpoxy-eyclopentyeter with ethylene glob dieyelopentadiene diopoxie, 4-viny! cyclohexenedonie, Ssteponseyelohexylmethy, 3.tepoxyeyelohexane car toxglte 1-2.8.9-iepony limonene (limonene dioxide, 34 cpoxy-Srmetiyheyclohexylmetiyl, 3hepoxy-Gmetyley- clohexane carboxylate, Wis epoxy rethyleyelohexylmethyDadipate, 2-(7-xabicyell 4.1.0] hept-3-Ispito[ 3 ioxane-5.9-(7}oxabicyebo[ 410] heptane), diepoxides of alpleyelopenteay! ether, 1. qelohexadione depoxide, 1, yelohexanemethanol Gglydeal cher, bs0 4-cpoxyeyelohexyinetyl)opae Sskspoxy-G-methyleyclohenane carbonate, dglyeil 1.2-eyelobexane cirboxylte. 3.4-opoxseyelohexyimethy] metho, }(oxiran-2y)-Toxabicyelo[4LOjbepane Ds2 8 RB op bw wm a ee 1. A curable resin composition, comprising: (8) a curable resin that comprises at least one non aromatic epoxy compound, a least one non-aromatic foxetane compound, or 2 mixture thereof, said: com= pounds bearing an amount of molar equivalents of epoxide groups, axctano groups, or a mixture thereof, (6) an amount of one or more curing agents selected from Leis avid-Lewis base complexes, in rato of from 1:25 to 1:2, preferably fiom 1:20 to 15, molar equiva lenis of Lewis acid:Lewis base complex to molar equivalents of epoxide groups, oxetano groups, or ‘mixture thereof, and (©) an amount of a cure secelerating amount of one oF ‘more anhydride compounds, in a ratio of up t0 1: preferably trom 1:20 to Tl, of molar equivalents of fnkydride groups to molar equivalents of the Lewis Aacid:Lewis base complex component of the resin com positon, 2, The resin composition of claim 1, wherein the ress ‘composition exhibits a cure conversion of greater than oF ‘equal to 85% and a glass transition temperature of greater than or equal © 210° C. after curing at tempersture of Irom 100° C. to 180°C. fora time period of Tess than or equal to 20 minutes. 3. The composition of claim 1, wherein the composito ‘comprises, based on 100 pbw ofthe resin composition, fom 50 0 80 pbw of one of more nom-aromatie epoxy com- Pounds and optionally, an aggregate amount af up to 30 phw ‘of one or more aromatic epoxy compounds andor monoe= oxide compounds 4. The composition of claim 1, wherein the anhydride ‘compound is an anhydride polymer or oligomer having 3 molecular weight of greater than or equal to about 500 ‘pole and having one or more anhydride Functional group per molecule. '5, The composition of claim 1, wherein the resin compo: sition exhibits an initial cure rate ata temperature of from 100° C. to 180° C,, further comprising. an amount of an nitrogen base compound, preferably selected from imidazole ‘componnds and teriary amine compounds, effetive to slow the intial cure mite 6. A curable liber rinforoed resin matrix composite material, comprising fibers impregnated with the curable resin composition according to claim 1. 7A fiber reinforced resin matrix composite article, made by curing the article of claim 6 8. A method for making a curable esi impregnated fber material, comprising impregnating fibers with a cumble resin composition according to claim 12 Oct. 8, 2020 9. The method of claim 8, wherein the curable res ‘composition furher comprises one or more thermoplas polymers that are soluble in the resia composition in aa famouat effective w increase the viseosty of the resin ‘composition to greater than or equal to 500 Poise, wherein the viseosiy of the resin composition inthe absence of the thermoplastic polymer is Tess than or equal to 50 Poise, ‘wherein the step af impregnating the fibers comprises: blending the thermoplastic polymer with the components ‘ofthe curable resin composition other than the Lewis ‘acid:Lewis base and anhydride components, a 3 tem- perature of trom 30° C. to 150° C., adding the Lewis acieL ewis base and anbydride compo- nents to the blended thermoplastic polymer and resin ‘composition, ata temperature of fom about 40° C. 0 70° €. to form the curable resin composition, ‘extruding the cursble resin composition, and ‘impregnating fibers with the curable resin composition by ‘onlating fibers with the extruded curable resin com position 10, A method for making a fiber reinforced resin matrix composite article, comprising stacking Wo or more layers oF ‘the curable resin composition impregnated fibers of claim 9 and eating the stacked layer to a temperature of frm 100 (Coto 180° C. fora time period of les than or equal to 20 minutes to cure the curable resin composition and thereby ‘orm the fiber reinfored resin matrix composite anicle. 1 The method of elsim 8, wherein when the resin, curing agent, and eure accelerator are initially combined, the eur fahle resin composition exhibits a viscosity of less than oF ‘equal to 50 Poise at 40° C, comprising: ‘impregnating tows of fibers with the curable resin com: position, and ‘winding the curable resin composition-impregnated fiber ‘ows around a mandee! to forma filament wound fiber reinforced resin matrix composite material, and allowing the filament wound fiber reinforced resin mtx ‘composite material to react at room temperature for from 4 t0 7 hours, so thatthe curable resin composition exhibits a viscosity of from $0,000 to 300,000 Poise and removing the lament wound fbr reinforced resin matrix ‘composite material from the mandrel 12, A method for making a fiber reinforced resin matrix composite ariele, comprising press molding the filament ‘wound fiber reinforeed resin matrix composite material of claim 10 at temperature of from 100° C10 180! C. for a time period of less than or equal to 20 minutes to shape the filament wound fiber reinforced resin matrix composite ‘material and cur the curable esin componition aad thereby orm fiber reinforeed resin matrix composite article. 13. The method of claim 8, wherein when te resin, curing agent, ane cure accelerator are initially combined, the eu able resin composition exhibis a viscosity of less than or ‘equal to 50 Poise, comprising impregnating a ber preform ‘vith the curable resin composition in a mold. 14, A method for making a fiber reinforced resin matrix ‘composite article, comprising eating the curable resin com position impregnated fiber preform of elaim 15 to a tem- perature of from 100! C. to 80°C. fora time period of less than or equal to 20 minutes to cure the curable resin ‘composition and thereby form fiber reinforced resin matrix composite article,US 2020/0317909 AI 1B 15, A method accelerating the cure of a curable resi ‘composition, comprising adding a cure accelerating amount ‘of one of more anhydride compounds to a curable resin, ‘composition comprising a curable resia that comprises al Jeast one non-aromatie epoxy eompound, a last one non- ‘aromatic oxetane compound, oF a mixture thereof and a ‘curing agent that comprises one or more Lewis acid-base ‘complexes 16, A method toughening a resin composition, comprising adding a cure accelerating amount of one or more polymeric anhydride compounds 10 a curable resin composition that ‘comprises « curable resin that comprises at lest one non= ‘aromatic epoxy compound, at leat one non-aromatie oxet- lane compotind, ofa mixture thereof, and a curing agent that ‘comprises one or more Lewis acid-base complexes, ia the subst swhirei the resin composi tion exhibits, after curing ata temperature of from 100° C. to 180" C, for a time period of lest than or equal w 20 minutes fracture toughness of greater than or equal to 0:3 Pum", as measured by notched impuet esting according © ASTM D-5045.99, 18, A curable resin composition, comprising (2) a curable resi, comprising at least one non-aromatic ‘epoxy compound that comprises at least one eponide ‘group per molecule of such compound, at least one ‘non-aromatie oxetane compound that comprises at least ‘one oxetana group per molecule of such compound, of ‘a mixture of such compounds, (©) one oF more curing agents selected from Lewis acid:Lewis base complexes, in an amount of from 1 to 20 parts by weight ofthe one or more curing agents per 100 pars by weight ofthe resin composition, and Oct. 8, 2020 re anhydride compounds, each comprising at mnlydride group per molecule of sich come Pound, in a cure accelerating amount of fess than 0.5 Imolar equivalents of anbyeride groups per’ molar ‘equivalents of epoxide groups, oxctane groups, or ‘mixture thereof 19,.4 curable resin composition, comprising: () a curable resin that comprises at least one non ‘arontatie epoxy compound, a least one non-aromatie ‘oxotane compound, or a mixture there, () ove oF more curing agents selected’ from Lewis ‘acid:Lewis base complenes, and (c)a.cure acelerating amount of one or more anhydride polymer or oligomer having a molecular weight of {reater than or equal to about 0 gimole and having fone oF more anliydrde fitional group per molecu 20. The curable resin composition of claim 19, wher thea lest one non-aromatie epoxy compound comprises at Teast one epoxide group per molecule of such com- pound, the at least one mon-aromatie oxetane com ‘ound comprises at Teast one oxetano group pee mol- ‘cule of such compound, the one or more anhydride polymer or oligomer each comprise at least one any dide group per molecule of such compounds and the resin composition comprises: the one oF more curing agents is present in an amount ‘of from | 10 20 parts by weight ofthe one or more ‘curing agents per 100 parts by weight of the resin ‘composition, and the one or more anhydride polymer or oligomer is present ina cure accelerating amount of Tes than 0.5 ‘molar equivalents of anhydride groups per molar ‘equivalents of epoxide groups, oxetane groups, oF mixture thereof