us) United States ‘US 2020008750841 2) Patent Application Publication co) Pub. No.: US 2020/0087508 A1 AGRAWAL et al. (4) CATALYST -FREE CURABLE EPOXY COMPOSITIONS (71) Applicant: SABIC GLOBAL TECHNOLOGI B.V,, Bergen Op Zoom (NL) (72) Inventors: Mukesh AGRAWAL, Bangalore (IN): NI IL K.E. VERGHES Maastricht (NL) (21) Appl. Now 61543,005 Filed: Aug. 16, 2019 G0) Foreign Application Priority Data Sep. 13, 2018 ey 181942483 Publication Classification (1) Incr. COL 63/08 cose 59/82 COB 63706 cos 59724 case 59282 (2006.01) (2006.01) (2006.01) (2005.01), (2006.01) (43) Pub. Date Mar. 19, 2020 (62) USC cP COBL, 63/04 (2013.01), CBG 59/4223 (2013.01): Cos $932 (2013.01): Co8G 59/245 (2013.01); COBL 63/06 (2013.01) on ABSTRACT A curable epoxy composition, comprising: 100 parts by ‘Weight of an epoxy resin composition comprising one oF fore epoxy resins, cach independently having an epoxy. equivalent cast 2; 30 t0 208 pats by weight of fn aromatic dianhydride euring agent of formula (1) in Tis—O. (0), 80. 80, GHz, wherein y_is ian ioteger from 1 10 5 or & baldgetted derivative thereof, or O-ZO— wherein Z is an aromatic C,y monocyclic or polycyclic moiety ‘optionally substituted with 1 0 GC. alkyl groups, | to & toms, o # combination compising t least one of sing, wherein the composition does not contin a catalystUS 2020/0087508 AI FREE CURABLE EPOXY ‘COMPOSITIONS. BACKGROUND 10001] Thermoset polymers are use in a wide varity of ‘consumer and industrial products including protective coat ings, adhesives, electonic laminates (uch as those used ia the fabrication of printed circuit boards), flooring and pav- ing, glass fiber-reinforced pipes, and automotive parts (sueh ‘Tea springs, pumps, and electrical components). Ther- moset epoxies are commonly derived fom thermosetting ‘epoxy resins that are polymerized in the presence of 3 ceoveactive curing agent (aso referred to in the art a6 3 hardener) and a catalytic curing agent (also referred to in the ant as a cure accelerator or a catalyst) to alle! a cured thermoset polymer, [0002] "Anhydride curing agents ean be used to provide ‘cured epoxies having higher heat properties, better electrical properties, longer pot life, and lower shrinkage. Aromatic ‘anhydrides ae a class of anhydride curing agents that provide high density crosslinking to the cuted thermoset ‘epoxy, which can further enhance the high heat properties, However, curing epoxy formulations that include dianhy- rides offen requires the use ofa curing catalyst in conjunc tion with high temperatures (eg., 200° C.) for extended periods oftime (eg. 24 hours) The use of curing eatalysts ‘can deteriorate the properties of the resulting cured epoxy product, and increase both the complexity and cost of the ‘curing process. 10003] Accordingly, there remains a need for curable ‘epoxy compositions suitable for manufecturing thermoset (Cured) epoxy resins for high heat applications. More par ticularly, there remains a need for curable epoxy’ eomposi- tions that can be cured in the absence of a curing catalyst BRIPP DESCRIPTION 10004) According to an aspect, a curable epoxy composi- tion comprises 100 pars by weight of an epoxy resin ‘composition comprising one of more epoxy resins, each independently having an epoxy equivalent weight of at last 2; 30 to 200 parts by weight of an aromatic dianhydride ‘curing agent of formula (1) w 8 ° swhersin Tis 0—, —S—,—C(0)—,—$0,, 80, ‘Gilg wherein ys an integer fom 1 10 3 oF a balgtated derivative thereof, or -O—Z--O—wherin ie an aromatic Cy, monocyclic ot polycyclic moiety ptionallysubstiied wilh fo 6C, alkyl groupe, 1 to 8 Talogen atoms, ora combination cotprsing alts! one of ihe foregoing, wherein the composiion docs ot coatia @ catalyst [0005] According to another aspect, a method for the franufactre of the curable epoxy composition comprises ‘outocting the epory resin Sompostion sad ibe aromatic Mar. 19, 2020 anhydride curing agent ata temperature of 130 10 200" preferably 140 to 190° C., more prelerably 150 to 180° {o provide the curable epoxy composition. [0006] In an aspect, a thermoset epoxy composition com- rising a cured product of the curable epoxy composition is provided [0007] According to stil another aspect, a method for the ‘manufacture of a thermoset epoxy composition comprises ‘curing the curable epoxy composition, wherein the curing is performed without a catalyst; preferably wherein the curing Of the curable epoxy compesition comprises compression ‘molding, injection molding, wansfer molding, puliewsion, resin eating, ora combination comprising atleast one ofthe Toregoing, {0008} Tn an aspect, an article comprising the thermoset epoxy composition is provided. [0009] The above described and other features are exem- plified by the following detailed description DETAILED DESCRIPTION [0010] ‘This disclosure relates 10 a eatalyst-free curable ‘epoxy composition including an epoxy resin and an aromatic anhydride a curing agent. The inventors have discovered tat an aromatic dianhydride, for example bisphenol-A anhydride (BPA-DA), ean be a useful curing agent for ‘making high heat cured epoxies in the absence ofa catalyst. ‘The curable epoxy composition including the aromatic dian- hydride as an epoxy curing agent can provide @ cured thermoset prodict having good! high heat resistance proper- ties, sueh asa plas transition temperature that can be preater than 210" C. Moreover, the curing time and heat of polym- ezaiion when using the curable epoxy composition may be Jess than those of other eurable epoxy compositions that do ‘not include the aromatic dianhydride curing agent, The disclosed curable epaxy composition and the coresponding ‘eued thermoset product can be used in a varoty of high heat Applications incliding but not limite to adhesives, coatings, epoxy tooling compositions, potting compositions, and liber-reinforced composites, [O11] - The curable epoxy composition inckades 100 parts by weight of an epoxy resin compestion comprising one oF sone epoxy rests, cach independently having an epoxy ‘equivalent weight of atleast 2;anel 30 to 200 parts by weight of an atomistic disnbydride curing agent, The curable epoxy ‘composition does not contain catalyst or accelerator [0012] In particular embodiments, the stoichiometric ratio between the aromatic dianhydride curing agent and the epoxy resin composition is 01:1 0 20:1, preferably 04:1 10 12:1, more preferably 0.6:1 to :1. The stoichiometric ratio is the molar rato of anhydride functionalities in the dian- hydride curing agent to the epoxy functionalities in the epoxy resin composition. The stoichiometric ratio is also selerned to herein as the anhydride to epoxy (A/E) ratio. [0013] In some embodiments, the curable epoxy compo- sition includes 50 to 150, preferably 60 to 140, more preferably 80 to 120 parts by weight of the aromatic dian- hydride curing agent, based on the total parts by weight of the epoxy resin composition and the aromatic dianhydride curing agent. [0014] The epoxy resin composition can be a bisphenol A epoxy resin, a tglycidy!-substitutod epoxy rosin, a tetragly- cidyl-substituted epoxy resin, a bisphenol F epoxy resin, @ phenol novolak epoxy resin, a resol novolak epoxy resin, 2 eyeloaliphatic dialyeidyl ester epoxy resin, a cycloaliphaticUS 2020/0087508 AI ‘epoxy resin comprising a ring epoxy group, an epoxy es containing a spiro-ring, a hydantoin epoxy resin, o ‘combination comprising a least one of the foregoing. In an ‘embodiment, the epoxy resins bisphenol-A diglyeidyl ether (BPA-DGE), [0015] The aromatic dianhydride ean be ofthe formula (1) oOrao bonds of the -O— or the OZ -O- group are in the 33, 3.4 43 or the 4.4 postions 10016] | Fxemplary groups Z.inelude groups of formula (2) a ‘wherein RY and R® are each independently the same of “different, nd are a halogen atom ora monovalent C,. alkyl ‘aroup, for example: p and q are each independently iategers ‘0F0 0-4; eis Oto 4 and X° isa bridging proup connecting the hydroxy-subsituted aromatic groups, were the bridging roup and the hydroxy substituent of each C, arylene group ate disposed ortho, meta, or pars (specially para) 0 each ‘ther onthe C, arylene group. The bridging group X" can be a single bond, O-, S$, SO), SOs. C(O}; oF Cs organic bridging group. The C15 ‘organic bridging group can be cyclic or acyelic, aromatic oF ron-aromitie, and ean furher comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur. silicon, or plhospborous. The C,..» organic group ean be disposed sich thatthe C anylene groups contcted thereto are each connected to 8 ‘common alkylene carbon or to different earbons of the Cy congue bridging group. A specific example of @ g0up isa divalent group of formula (3a) or (35) >: ow Mar. 19, 2020 continued OO wherein Qis O-, SCO), $0, $0. “PIR\—0)— wherein Ris aC, 5 alkyl or Cy aryl, oF CH, — swherein y is at integer from Ita” S of @ halogenated derivative thereof Gioeluding a peefluoroalky- Jene group). In some embodiments. Q is 22-isopropylidene, [0017] In some embodiments, T is O20, prof cembly wherein Z is derived from bisphenol A (ie. Z is 2.2-(4-phenylene)sopropylidene). Musirative examples of ‘aromatic dianhy rides inchide 3,3-is[4-34-diearbonyphe- oxy)phenyl}propane dianhydride; 44-bis(3,4-dicarboxy- phenoxyxlipheny! ether dianhydride; 44-bis(3.4-dicar boxyphenoxy)dipheny! sulfide dianhydride; 44bis(3.4- icarboxyphenoxy benzophenone dianhydride; 44-bis(3- ‘carboxyphenoxy Miphenyl sl fone dianhydride; 2,2-bis(4- (@.3licarboxyphenoxy}phenylIpropane dianhydride, 4.4 bis(2.3-dicarboxyphenoxy diphenyl ether dianhydride; 4. bis(23-dicarboxyphenoxy)iphenyl sulfide dianhydride: 44-bis(2.3-dicarboxyphenoxy benzophenone dianhydride: 44-bis(2.3-dicarboxyphenoxy diphenyl sulfone dianhy- rides” 44(23-dicarbonyphenoxy)-4-3 4-dicarboxyphe- noxyxliphenyl-2,2-propane dianhydride; 4-(23-dicarboxy- phenoxy)-#-(3.4-ciearboxyphenoxy dipheny ther anhydride; 4-2,3-dicarboxyphenoxy)-4-,4-dicarboxy- phonoxy)dipheny! sulfide dianhydride; 4-(23-diearboxy- ‘henoxy)-4'(3.4-diearboxyphenoxy benzophenone diany- ride: and, 4(2,3-dicarboxyphenoxy)-443.4- sicarboxyphenoxyiphenyl sulfone dianhydride [018] In some embodiments, Uke curable epoxy compo- sition includes an additive composition. The additive com- tion ean include a particulate filler a Hhrous filer, a reinforcing material, n antioxidant, a eat stabilizer ight stabilizer, a ultraviolet light stbilizer, a ultraviolet light hsorbing compound, «near infrared lightabsorbing com pound, an infrared light-absorbing compound, a plasticizer, a lubricant, a release agent, antistatic agent, an antilog ‘gent, an antimicrobial agent, a colorant, «surface elect ‘additive, a radiation stabilizer, a Rame retardant, flame retardant synergsts such as antimony pentoxide, an anti-drip agent, a fragrance, an adhesion promoter, a flow enhancer, 2 coating additive, a polymer differnt from the thermoset polymer, ar a combination comprising atleast one of the foregoing. Ina preferred embodiment, the additive compo- sition comprises a fame retardant, a particulate fille, a ‘ibeous filer, an adhesion promoter, a flow enhancer, coating additive, a colonint, o @ combination comprising st Teast one of the Torepoing, [0019] In particular embodiments, the additive composi- tion includes a paniculate filler. The particulate filler can include alumina powder, hydrated alumina powder, quartz powder or fused quartz powder, glass fibers, earbon fibers, ‘ora combination comprising at least one ofthe foregoing. In ‘one embodiment, the curable composition futher eomprises fibrous substzate (woven or non-woven) such as lass, ‘quartz, polyester, polyimide, polypropylene, cellulose, car bon fibers and carbon fibrils, aylon or acrylic fibers, pref- cembly a glass substrate, that can he impregnated with the ‘rable composition (ie. prepress) omUS 2020/0087508 AI [0020] In some embodiments, the curable composition Jurkier comprises a poly(phenylene ether) copolymer. The poly(phenylene ether) copolymer is ideally suited as a Feacive component inthe curse composition because iis bifunctional, with two reactive phenolic grovps. In some ‘embodiments, the curable epoxy composition can fare ‘comprise 1 to 100 parts by weight of the poly(phenylene ether) copolymer. [0021] |The curable epoxy composition does not include » Catalyst. AS used herein, “catalyst” means @ catalyst come pound that initiates polymerization of epoxide groups oF ocelerates the reaction of curing agents with epoxide troupe, and ean encompass various terms such as curing accelerators, hardening accelerators, curing catalysts, and ‘curing promoters. Catalyst compounds include, but are a0 Timited to, henzoriazoles triazines; piperazines such as “amingethyfpiperazine, N-(-aminopropy piperazine, ofthe like; imidazoles such a I-methylimidazole, 2-methylii- i hydrocarbons, C,_allglalkanoates, ‘Cy alkyl nites, C, «dial sulfoxide of a combination compesing atleast one of the foregoing. Examples of C, ketones Include acetone, methyl ethyl Ketone, methyi isobutyl Ketone, and combinations comprising at least one of the foregoing. Fxamples of Cas NiN-dalkylamides include dimethyliomamie, dimetivlacctamie, Nenethy-2-pye rolidane, and combinations comprising at least one ofthe foregoing: Example of C,,. dialky ethers include tetahy~ drofiran dioxane, and combinations comprising at Teast one Of the foregoing. The Cg dilkyl ether can optionally Turterincads one or mote ether oxygen atoms within the alkyl groups and one or more hydroxy substituents on the alkyl groups, for example the Ce dialkyl ether can be cihslene glycol menometiyl ete The aromatic hydrocar ton solvent con be an etiplnically unsaturated solvent Examples of... aromatic hydrocarbons sacle beazene, tohvee, xylene, styrene, ivnylbenzenes, and combina. ‘ions comprising af lest one of the foregoing. Examples of Coal! alkanoates ince methyl acta, ey est snot] propionate, es propionate and combinations con Prising tIeast one ofthe foregoing. Examples of C. . alkyl Eyanides include aeetoitle, peopiontile, butyeonitie fn combinations comprising a least ane of the foregoing Tramps of C.-C, callsh sulfoxides include dimethyl sulfoxide, methyl ethyl sulfoxide, diets! sulfoxide, and ombinations comprising atleast one ofthe Foreing. In Some embodiments the solvent comprises stone, methyl eds! ketone, N-methy)2-pymoidone, toluene, ora combi- ation comprising atleast one ofthe foregoing. In il other embodiment the solvent ean be a halogenated solvent sich fm methylene chloride, chloroform, I.,1-tichlonosthane. chlorobenzene, ofthe ike {0024] In anther aspot, disclose isa thermoset epoxy composition that inehides a cured product of the curable poy composition. The cured prot othe erable epoxy composition can be obtained as provided hein {0025] The thermoset epoxy composition including the ced composition ca exhibit ningle glass transition temperature (T,) ste as single T, greater than or equal to 170" C. preferably grester than of ual (0 180" C. more preferably greater than or equal 10 200° C. The giss transition temperature can be determined sing, dynamic ‘mechanical anaysis (DMA), Alternatively, canbe deter ‘mined wing diferent scanning ealorimetn’ (DSC) with a heating rate of 10° C/minute o 20° C minute (0026) The resulting themnoset epoxy composition afer uring canbe clear anor transparent The themnoset epoxy composition icloding the eure composition ean exhibit light ransmission of greatec than 50%, preferably greater than 70%, more preferably greater that 90%. The light transmission can be determined on ® 2 millimeter (mm) plac according to ASTM D1003. As ws rei, “liaht {ransmission” means ansmission of Visible ight ina wave- length rion of 380 fo 750 nanometers (a). {0027} Ina prefered embodiment, the themnoset epoxy composition as « glass ansiton temperature of greater than or equal to 170°. prefebly greater than or eal 180° C, more preferably greater than or equal to 200°C as determined by dynamic mechanical soalsis; and light transmission of greater than 50%, preferably grater than Too, more preferably arester than AP, as. determin aecotiag to ASTM D1G03 on a 2 mam plagueUS 2020/0087508 AI 10028] The thermoset epoxy composition ean be manu- Jiacured by curing the curable epoxy composition. There is ro paticular Himitation on the method by which the com Position may be cured, The composition may be cured, for ‘example, by thermal curing or radiation curing. Combinae tions of themmal curing and radiation curing can also be use. ‘When thermal curing is used, the heating temperature ean be fm 80 t0 300° C., preferably 120 to 240° C. The heating period can he from 1 minute to 1 hours, preferably | minute to 6 hours, more preferably 3 hours to 5 hours. The curing process can be staged to produce a partially cured and often luck-free resin, which then is fully cured by heating for Jonger periods or temperatures within the aforementioned ranges. Radiation cui can be performed using ultraviolet Fight or electron beams. 10029] In paricular embodiments, the curable epoxy com Position can be cured by compression molding, injection ‘molding, transfer molding, pultruion, resin casting, or & ‘combination comprising al least one of the foregoing, Ia Some embodiments, the curable epoxy composition ean be «disposed i, for example injected into, mold and then cured ‘130 49 260° C, in the mold, The curing tine ean be from, T to 15 hours i the mold, Various molded articles or ‘components can be prepared in this manner, ineluding those ‘described herei 10030] |The thermoset epoxy composition can exhibit good ‘duetilty, good fracture toughness, unnotched Tod impact sireagth, and good tensile elongation, [0031] "The thermoset epoxy composition can exhibit ‘increased char formation on pyrolysis. 10032] The thermoset epoxy composition ean exhibit low ‘moisture absomption, 10033] The thermoset epoxy ‘decreased shrinkage upon curing, 10034) The thermoset epoxy composition can exhibit decreased dielectric properties 10035] The disclosed curable epoxy compositions and thermoset epoxy compositions can be used ia @ variety of applications and articles, inclading any applications where ‘conventional epoxides are currently used. Exemplary uses tnd applications include coatings such as protective coal- ings, sealants, weather resistant costings, seratel resistant ‘outings, and electrical insulative coatings; adhesives; bind ers; ules; composite materials such as those using earbon. fiber and fiberglass reinforcements. When utilized as 2 ‘coating, the disclosed compounds and compositions ean be ‘deposited ona surface of a variety of underlying substrates, For example, the compositions eat he deposited on a surface ‘of metals, plastics, glass, fiber sizings, cemmics, ston, ‘wood, or any combination thereof. The disclosed composi- tions can be used as a coating on a surface of a metal ‘container, such as those commonly used for packaging and ‘containment in the paint and surface covering induscies, [a ome instances the coated metal is aluminum of stet 10036] Articles that can be prepared using the disclosed ‘curable epoxy compositions and thermoset epoxy compost tions include, for example, electrical components, and com puter components, Other articles include, for example, com- Ponents of transport, including bicyele, motoreyclo, ‘automotive, arceil, and watereraft exterior and interior ‘components. In some embodiments the ante isin the form ‘of in the form of a composite, foam, a fer. a layer, 3 ‘coating. an encapsulant, an adhesive, « sealant. 8 compo- nent, a prepreg, a easing, or a combination comprising at wition can exbibit Mar. 19, 2020 least one of the foregoing. In cerain embodiments, the isclosed curable epoxy compositions are used for the production of composite materials for use inthe aerospace industry. The curable epoxy compositions can be used in Torming composites used for printed circuit boards, Methods ‘of forming composites for use in printed circuit boards are known inthe art and ae deseribed in, for example, US. Pa. No. 5,622,588 to Weber, US. Pat. No. ,582,872 w Prinz, and US, Pat. No, 7,655,278 to Braidsood [0037] Additional applications include, for example, acid bath containers; neutralization tanks; airralt components bridge heams: bridge deckings; electrolytic cells; exhaust stacks; scrubbers: sporting equipment; stair eases: walk- ways; automobile exterior panels suc as hoods and trunk ids hoor pans; ar scoops; pipes and duets, including heater ducts; industrial fan, fan housings, and blowers; industrial mixers; boat hulls and decks; marine terminal fenders les ‘and coatings; building panels; business machine housings: ‘rays, including cable Lays; eonerete modifiers; dishwasher and refiigerator parts; electrical encapsulants, electrical pan- els; tanks, including electromfining tanks, water soflener tanks uel tanks, andl various filament-wound tanks and tank Jinings: furniture; garage doors; gratings: protective body sear, luggage: outdoor motor vehicles; pressure tanks: Print circuit boards; optical waveguides; radomes; ra ‘ngs railroad parts such a tank cas; hopper ear covers car ors truck bed liners; satellite dishes: signs; solar energy panels; telephone switchgear housings: tractor pats: trans- ormer covers tick parts such as fenders, hoods, bodies, cabs, and beds; insulation for rotating machines including ground insulation, tum insulation, and phase separation Jnsulation; commutators; core insulation and cords and Jacing tape; drive shaft couplings; propeller blades: missile ‘components; rocket motor eases; wing sections; sucker rods; fuselage sections: wing skin and firings; engine nacelles cargo doors; tennis racquets; golf elub shafts; fishing rods; skis and ski poles; bicycle parts; transverse leaf springs: ‘pumps, such as automotive smog pumps: electrical compo: ents, embedding, and tooling, such as electrical cable joimts, wire windings and densely packed nulti-element ‘assemblies; sealing of eleciromechanieal devices: battery ‘eases; resistors; fses and thermal cui? devices; coatings ‘or printed Wiring boards; casting items such as capacitors, transformers, erankease heaters: small molded electronic parts including coils, capacitors, resistors, and semieondue- tors; asa replacement for stel in chemical processing, polp and. paper, power generation, and wastewater teatmeat; serubbing towers; pultruded pars for structural applications, including structural members, gratings, and safely rails ‘swimming pools, swimming poo! slides, hot-ibs, and sau- fas; drive shafs for under the hood applications: dey toner resins for copying machines; marine tooling and composites: ‘eat shields; submarine hulls; prototype generation; devel ‘opment of experimental models; laminated trim; drilling fixtures; bonding jigs: inspeetion fiatures industrial metal forming lies; aircraft stretch block and hammer forms; vacuum molding tools; fring, including Nooring for pro- duction and assembly areas, clean rooms, machine shops, ‘control rooms, laboratories, parking garages, freezers, cool- ers, and outdoor leading’ docks: electrically conductive ‘composition for antistatic applications: for decorative Mloor- jing: expansion joins for bridges; injectable mortars for patch and repair of cracks in structural concrete; grouting forUS 2020/0087508 AI tie; machinery rls metal dowels; bolts and posts; repair of cil and fuel storage tanks, and numerous ote applications [0038] Methods of forming a composite can_ include Impregnating a reinforcing structure with a curable epoxy ‘composition; patially curing the curable epoxy composition to form a prepreg; and laminating one or a plurality of prepregs. The lamination can include disposing an addi- tional layer, eg., an elevtically conductive layer or un adhesive or bond ply on aside ofa prepreg before lamina- tion, The lamination ean include disposing an additional layer, eg, an electrically conductive layer or an adhesive or bond ply on a side of a prepreg before lamination, [0039] Reinforcing structures suitable for prepreg forma- tion are known in the ar. Suitable reinforcing structures inchide reinforcing fabrics. Reinforcing fabrics inclide those having complex architectures, including two or three- dimensional braided, knitted, woven, and filament wound, ‘The curable epoxy composition is capable of permesting such complex reinforcing sirvctures, The reinforcing strue- ture can comprise fibers of materials known for the rein- oreement of plastics material, for example fibers of carbon, lass, meal, and aromatie polyamides, Suitable reinforcing Structures are described, for example, in Anonymous (Hex- ‘cel Corporation), "Prepreg Technology”, March 2008, Pubs lication No. FGU 017b: Anonymous (Hexcel Corporation). “Advanced Fibre Reinlorced Matrix Products for Direct Processes", June 2008, Publication No, ITA 272: and Bob Griliths, "Farnborough Airshow Report 2006%, Compos= itesWorld.com, September 2006. The weight nnd thickness ‘of the reinforcing structure are ehosen aecoeding to the intended use of the composite using criteria well known t0 those skilled in the production of fiber reinforced resin ‘composites, The reinforced sieuetie can contain various finishes suitable forthe epoxy mateix. 10040] The method of forming the composite can com- prise partially curing the curable epoxy composition ater the reinforcing structure has been impregnated with it Partial curing is curing suficent to reduce or eliminate the wetness and tackiness ofthe curable composition But not so _aeat as to fly eure the composition, The resin ina prepreg 's customarily inthe partially curd state, and those skilled Jn the thermoset arts, and particularly the reinforced com- posit arts, understand the concept of partial curing and how to determine conditions to partially cure a resin without undue experimentation, References herein to properties of the “cured epony composition” refer toa composition tha is substantially flly cured. For example, the resin in lami- rate formed from prepregs is typically substantially fully ‘cured. One skilled in the thermoset ans ean determine Whether a sample is parially cured of substantially fully ‘cured without undue experimentation. For example, one can analyze a sample by differential scanning calorimetry (DSC) to look for an exotherm indicative of additional curing ‘occurring during the analysis. A sample that is partially ‘cored will exhibit an exothem, A sample tht is substantially {lly cured will exhibit litle or no exotherm. Partial curing ‘ean be effected by subjecting the curable-composit pregnated reinforcing strictire to a temperature of 133 10 140° C. for 410 10 minutes [0041] Commercial-scale methods of forming composites are known in the art, and the curable epoxy compositions ‘described herein are readily adaptable to existing processes and equipment. For example, prepregs are often produced on teeaters. The main components of a treater include feeder Mar. 19, 2020 rollers, a resin impregnation tank, a tater oven, and reesiver voles. The reinforcing stwcture (E-pan, for example) is usally rolled into large spook. The spool is ‘hen pt on the fede oles that tums a slowly allot the reinforcing structure. The reinforcing structure then moves ‘brough the resin imprewuation nk, which comuns the curable composition. The varnish impregntes the reinfore dng structure. After emerging fom the tk, the coated reinforcing strocture moves upward though the vertical teeter oven, which typically ata temperate of 175 t0 200" Cad the solvent of te varnish is boiled sway. The ‘resin begins o polymerize at this tine. When the composite comes ot ofthe ower ssufclnty cured so that te web Js not wet or tack. The eure proves, however, is stopped shoe of completion so that additonal ering can oecur When laminate is made. The web then rolls The prepeeg. ona receiver rol {0042} While the shove-describod coring methods rely on {hema curing, it is abo possible to effect curing with ‘adation, including ulravilet light and clecion beams Combinations of theamal curing and radiation curing ean ako be wd [0043] Processes useful for preparing the ales and ‘oterialsinelado those generally know tothe art forthe pcessing of themosting resins. Sich processes have Seon described in the iterture asin, for example, Ege oer! Materials Handbook, Volume 1, Composites, ASM International Metals Pk, Obio, copyright 1987 Cyril A Dosa Senior Ed, pp 105-168 and 497-533, and “Povesters and Their Appistions” by Bjorksen Research Laborao- ‘es, Johan Byorksten (pres) Ten Tovey (Ch. Lit Ass), Batty Harker (Ad- Ass) Tames Henning (Ad. Ass), Rein: hold Publishing Corporation, N.Y, 1956, Provessing tech- igs ince resin transfer voldingsshoct molding: bulk ‘mokling:pultsion; injection molding, inluting reaction dnjecton tolling (RIM); atmospheric presure molding (APM); casting, eluting centipal and state easing fpen mold casing: lamination inching wt or dy lay-up fn spray layup: also included se contaet molding, elude fing cylindrical contact molding: compression molding ‘eluding vacuum ssisted resin wansfer molding and chemi cally ssisted resin transfer molding: matched eo! molding fuelave euring: them cueing in ar: vacuum hogging: Puluusion: Sceman's Composite Resin Infsion Manutae~ ng Processing (SCRIMP); open. molding, continous combiaation of resin and glass, and lament winding, including eylindial filament winding In certain embod ‘nls, an ail ean be prepared rom the disclosed curable compositions via resin transfer moling process (0044) ‘Thi disclosure sft stead by the fallow ing examples, which are non-limiting EXAMPLES [045] Materials used in the examples are deseribed in ‘Table 1 TABLE 1 Conponeot Dein Sou fag No. 167553 BPA-DA —Daptenl A danbvsde, CAS Reg. Na. SAICUS 2020/0087508 AI TABLE 1-continued Conponent _Deripion = MTHPA Tahoma ibalc pine, TCI Chemical CAS Rep No. same MUHA Hewne-t nepali snide, Sinai CAS Reg No. ABB NMA Mell Snbomene2.-dewbontic Sig Adich {CxS Rep No. 8138218 PMDA sida, CAS Ret. No, Signa Ach Sample Preparation Example 1 [0046] | BPA-DGE is heated at 160° C. and combined with BPA-DA at an anhydride to epoxy (A/E) ratio of 08:1 by Weight, A homogenous and transparent regetion mixture is forded. The reaction mixture was poured into preheated ‘mold (130° C.) and then eured in the mold st 220° C. for 1 hour to provide a rigid and clear casting. Example 2 [0047] The same procedure as Example 1 was followed, ‘except the curing time was 3 hours. Example 3 [0048] The same procedure as Example 1 was followed, ‘except the euring time was 5 hours. Example 4 [0049] The same procedure as Example 1 was followed, ‘except the curing time was 7 hours Example 5 10050] The same procedure as Example 1 was followed, ‘except the euring time was 15 hours Comparative Example 1 [0081] | BPA-DGE was combined with MHHPA at 23° C. ‘with an AVE ratio of 08:1 by weight. The reaction mixture was heated a 90° C. and then poured into « prebeated mold (130° C,) and cured in the mold at 220° C. for 1 hour. No rigid epoxy resin was afforded. Comparative Example 2 10082] The same procedure as Comparative Example 1 ‘was used, excep the curing time as 15 hours. No rigid epoxy resin was afforded, Comparative Example 3 10083] The same procedure as Comparative Fxample 1 ‘vas used, except the curing agent was MTFIPA. No rigid epoxy resin was afforded Compsrative Example 4 10084] The same procedure as Comparative Example 3 ‘was used, excep the curing time as 15 hours. No rigid epoxy resin was afforded, Mar. 19, 2020 Comparative Example 5 [055] The same procedure as Comparative Example 1 was used, exeept the curing agent was NMA, No rigid epoxy resin was afforded ‘Comparative Pxample 6 [0056] The same procedure as Comparative Example § vwas used, except the curing time was’ 1S hours. No rigid epoxy resin ss allorded Comparative Example 7 [0057] BPA-DGP is heated at 160° C. and combined with PMDA at an AE ratio of O.8:1 by weight. The resulting ‘mixture had light yellow color and a substantial amount of the PMDA remained undissolved with stirring. The eaction mixture was poured into a mold preheated at 130° C., and ‘thea cured in the mold at 220°C. for | hour to provides rigid ‘and cured resin having undissolved particles of PMDA ‘istrbuted therein, Comparative Example 8 [0058] The same procedure as Comparative Example 7 ‘vas used, except the curing time was 15 hours. The resulting product was a rigid and cured resin having undissolved particles of PMDA distributed thereia Sample Analysis [0059] The glass transition temperature (T,) was deter ined by dynamic mechanical analysis “ony using an RDA Ill DMA fom Rheometrie Scientific. Sample bars were prepared (40 mm length, 4mm wid, and 6 mm ‘hiokness) and analyzed at 40 6 300° C. with a temperatare ramp of 3°C. per minute and at frequeney of 6.283 radians per second. Evaluation [0060] Table 2 shows the curing agent, catalyst, curing ‘ime (hours) rigidity, and clarity for Examples 1 to 5 and Comparative Examples Ito 8, Rigidity and clarity are the ualitative propedies of the cured sample eae 8 fs e pee eo 8 a oe eee a oS Commumive HPA Ne 1s No ON os = Comumnive NMA Ne 1 No ON Come PDA Ne 1 Ye xUS 2020/0087508 AI ‘TABLE 2-continued Cosng Agent Cae Tee) Rigiy Clty ‘Conparave PDA es Exile ® [0061] As shown in Table 2, BPA-DGE can be cured 10 provide clear and rigid castings using BPA-DA.as the curing ‘agent without the necessity of an added catalyst. Curing times of 1 to 15 hours were effective in Examples 1 to 5. {0062} In contrast, anhydride curing agents such as MHHDPA, MTHPA, and NMA in Comparative Examples 1-6 ‘were ineffective in curing BPA-DGE and failed to provide ‘lear and rigid eesins tnder same curing. conditions. To ‘Comparative Examples 7 and 8 the dianhydride curing ‘agent PMDA provided a rigid, cured resin without sufficient clarity and having a significant amount of undissolved PMDA particles embedded into the cured resi, [0063] "Table 3 shows the curing time (hr and, (°C. for Examples 1 to 5 TABLES Exanplet r 2 Example 3 4 Exanple¢ } Exanple$ 8 10068] As shown in Table 3, Examples 1 to 5 had glass transition temperatures of greater than 210” C. The glass transition temperature was found to increake asa function of ‘curing time, 0065] The results show that the aromatic dianhydride ‘curing agent BPA-DA can be used to provide high tempera ture, rigid, and clear epoxy resins in the absence of any added catalyst, Cured epoxide resins having similar prop- ‘erties were not obtained in the absence of an added catalyst Jor the anhydride curing agents MHHPA, MTHPA, NMA, ‘and PMDA. 10066] This disclosure futher encompasses the following aspects. 10067] Aspect 1: A curable epoxy composition, compris- Jing: 100 parts by weight of an epoxy resin composition ‘comprising one or more epoxy resins, eh independently having an epoxy equivalent weight of atleast 2; 30 10 200 parts by weight of an aromatic dianhydride curing agent of ormula (1) wherein Tis 0, S$, C(O), $0, 80, “GH, — wherein y is an integer from 1 to 5 or @ halogenated derivative thereof, or —O—Z-O— wherein Z Mar. 19, 2020 is an aromatic C.24 momocyelic or polyeyelic: moiety optionally substituted with 1 10 6 C,,, alkyl groups, | © 8 halogen atoms, of a combination comprising at leis one of the foregoing, Wherein the composition does not contain a catalyst [0068] "Aspect 2: The curable epoxy composition aevord- ing to Aspect 1, wherein a stoichiometric ratio between the ‘aromatic diankydrde curing agent and the epoxy resin ‘composition is 0.1:1 to 2.01, preferably 0.41 t01.2:1, more preferably 06:1 10 1:1 [069] Aspect 3: The curable epoxy composition aevord- ing to Aspect I or Aspect 2, Wherein the epoxy resin composition comprises a bisphenol A epoxy resin, a trighy- cidylsubstiuted epoxy resin, a tetralyeidyl substituted epoxy resin, a bisphenol F epoxy resin, a phenol novalak epoxy resin, a cresol novolak epoxy resin, & cycloaliphatic diglyeidyl ester epoxy resin, a eycloaliphatic epoxy resin ‘comprising ring epoxy group, an epoxy resin containing & spine-ring. a hydantoin epoxy resin, or a combination com- prising atleast one of the foregoing, [0070] Aspect 4: The curable epoxy composition accord: ng to any one or more of the preceding Aspects, wherein T js -O— ora group of the formula 0-2-0 wherein Z.is of formula (2) rein R° and RY are each independently the same or dierent, and area halogen stom ora monovalent C9 alkyl group, X° is a single bond, —O-, —S_, S(O), S(O), C(O), oF a C, 4 organic bridging group, and p, d, and e are each independently integers of 0 10 4 [0071] "Aspect S: The curable epoxy composition aeeord- ing to Aspect 4, wherein Z is a divalent group of formla Ga) or Gb) -O-O- wherein Qis O-, S ow oy C(O), $0, $0 PUR'(—O)_ wherein R’ is Cs alkyl or Cas aryl oF GH, wherein y is an ioteger from 1 to. oF a haalogenited derivative thereof, preferably wherein Q is 2,2:sopropylidene. [0072] Aspect 6: The curable epoxy composition aeeord- ing t0 any one or more of the preceding Aspects, furher ‘comprising an adltve composition; preferably wherein the additive composition comprises a particulate filler, a fibrous iller, an antoxidaat, a heat stabilizer, a light stabilizer, a ‘ltraviolet light stabilizer, a ultrvioletlight-absorbing com pound, a neat infrared lght-absorbing compound, anUS 2020/0087508 AI rod liahabsorbing compound, plasticizer, @Wbviant, @ release agent, state agent, am antiefow agent. an antic Imjrobial agent, a colorant a suriee eet alive, @ ‘olltion subilizer a Mame retardant an an-dip eat, & Fragrance, an adhesion promote, fw enhance, coating ‘addtve,a polymer dilleen rom the thermoset polymer. oF 4 combination comprising at least one of the foregoing: tore preferably wherein the additive composition com- prises lame retardant a particle ile, fibrous fileran Suicsion promoter, «flow enhancer, coating alive, 3 folorant, Ora combination comprising atleast one ofthe Toregoing 10073} "Aspect 7: A method for the manufacture of the ‘curable epoxy composition aeording to any one oF more of the proceling Aspects. the method comprising contacting the epoxy resin composition and the aromatic danhyeride ‘curing agent ata tempertire of 130 to 200? C, preferably 140 to 190°C, more preferably 150 10 180° Ct provide the curable epoxy composition. {0074} Aspect © The mothod of Aspect 7, wherein the reaction mixture contains no solvent or reactive dient solvent [0075] Aspect: dhemmose epoxy composition comprise 4 cared product of the ctmable epoxy composition acconting to any one or more of Aspect If 6 {0075} "Aspect 10: The themosct epoxy” composition scconing aeording to Aspect 9, which ar curing has at least one of a last transition temperate of pear than ‘or equal 0 170° C, preferably grater thn or eal 1 180° C. more prefenbiy greater than or eis! © 200" C., as ‘dcermined by dynamic mechanical analysis: and a Hight teansmision of greater than 50%, profembly greater than OM, more preferably greater than 9%, as determined acconting to ASTM D1Q03 of 2 mm plague. 10077) Aspect 11: A method for the manuiacure of a thermoset epoxy composition, the metho comprising: cur ing the ewable epoxy composition of any one oF more of Aspects Ito 6, eherin the curing is performed without a ‘east, preferably wherein the curing ofthe curable epoxy ‘composition comprises compression molding, injection tmolding, trimer molding, plrosion, resin casting, oF ‘combiastion comprising at Hast one ofthe foregoing 1078] Aspect 12: The method of Aspect 13, wherein the ‘ring comprises dispasing the curable epoxy composition ito a mold, and curing te epoxy resin composition at 150 to 260° C. for to 15 hours inthe mo 10079] Aspect 13: An aricle comprising the thermoset ‘pony componiton of Aspect 9 oe Aspect 10 [080] Aspect 14: The ale of Aspect 13, wherdia the articles in the form of inthe form ofa compost, foam, aibr, layer, a coating an encapsulant, an adhesive, Sealant, component, prepreg, #eesng, or 4 combinotion ‘comprising at east one ofthe foregoing [0081] The compositions, methods, ad ances ean ater natively comprise, consist ol or eosin essen a, ay appropriate materials, steps, oF components herein die Closed. The compositions, methods, and articles ean adi tionally, or alternatively, be frmlated so ast be devoid, of substantially fie, of any moteals (or specie), eps, of ‘components, that ae otherwise not necessary to the achiove- ment of the function or objectives of the compositions methods, and articles. {0082} "All inges disclosed herein are inclusive of the ‘endpoint and the endpoints ae independently combinable Mar. 19, 2020 with each other (ep, ranges of “up to 25 wt %, or, more specially. $to 25 wt %", is inclusive ofthe endpoints and all intermediate values ofthe ranges of “S wt % 10 25 wt 9%,” fe.) Disclosure of narrower range or more specific sup in addition to a broader range is not a disclaimer oft broader ringe or lager group. The singular forms "a" and “the” include plural referents unless the context clearly Sictates otherwise 0083] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly ‘understood by one ofl in the art to which this application belongs. All cited patents, patent applications, and other references are ineomporated herein by reference in their entirety. However, if a tem in the present application contracts or confics with a term in the incorporated reference, the term from the present application takes pre- cedence over the conilieting term from the incorporated reference. [0084] Compounds ate described using standard nomen- lature, For example, any position not substituted by any indicated group is understood to have its valeney filed by a bond as indicated, oc a hydrogen atom, A dash (*") that is ‘not between two letters or symbols js used to indicate a point of attachment for a substivent. For example, CHO is attached through carbon of the carbonyl group. [0085] The term “hydrocarbyl” refers to a monovalent soup containing carbon and hydrogen. Hydrocarbyl can be alkyl. eycloalky|, alkenyl, cycloalkenyl, aryl, alkylary, oF ‘arylalkyl as detined below. ‘The term “hydrocarbylene” ‘elers to a divalent group containing carbon and hydrogen. Hydrocarbylene can be alkylene, eycloalkylene, arylene, alkylarylese, or arylalkylene as delined below. The term “alkyl” meas branched or straight chain, unsaturated aliphatic hydrocarbon group, e., methyl, ethyl, n-propyl, inpropyl, n-butyl, s-butyl, ebutyl, a-penty,s-pentyl, and n- and s-hexyl “Allenyl” means a stright or branched chain, ‘monovalent hyirocarbon group having atleast one carbon. carbon double bond (eg. etbenyl (HC—CH,)) “Alkoxy" ‘means an alkyl group that is linked via an oxygen (ie, alky/-O—), for example methoxy, ethoxy, and see-butyloxy ‘arups. “Alkylene™ means a straight oF branched ehain, Sslurted, divalent alipbatie hydrocarbon group (exe. meth ylene (—CH—) or, propylene (—{CH,},—)). “Cyeoalky- Tene means divalent evelie alkylene group, —C,Hoy_.— ‘wherein x is the number of hydrogens replaced by eyeiiza- tion(s), “Cyeloatkeny” means @ monovalent group having fone or more rings and one or more carbon-carbon double bonds in the ing, witercin all ing members are carbon (e. ceyelopenteny] and eyelohexeny!). "Ary1” means an aromatic hydrocarbon group containing the specified number of ear bon atoms, such as phenyl, trepone, indany, or naphthyl “Arylene”’ means a divalent aryl group. “Alkylarylene” ‘means en arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group. “Amino” means a radical ofthe formula —NRR’ eit R and RY are independently hydrogen of 4 Cy-Cyy hnydrocarby}, for example a Cy-Cay alkyl group oF & Cy-C 3, aryl group. “Halogen” or “halogen atom” means fluorine, chlorine, bromine, or iodine atom. The prefix “halo” means ‘8 group or compound including one more ofa fro, chloro, bromo, or iodo substituent. A combination of different halo groups (¢2., bromo and fluor), oF only chloro groups ean be present. The prefix “beter” means thatthe compotind or soup includes at least one ring member that sa hetercatUS 2020/0087508 AI (ez, 1,2, oF heteroatoms), wherein the heteroatom(s) is ‘each independently N, O, 8, Si, or P. The suffix “oxy” Jndcates thatthe open valence of the group is on an oxygen ‘tom and the sul “io” indicates tht the open valence of the group is om a sulfur stom, 10086] Unless substituents are otherwise specifically indi- ‘cated, each of the foregoing groups can be unsubstituted oF substituted, provided that the substinon does not sigaili- cantly adversely affect synthesis, stability, or use of the ‘compound. “Substituted” means thatthe compound, up, ‘or atom is substituted with atleast one (eg, 1,2, 3, 08 4) substituents instead of hydrogen, where each substituent is independently nitro. (—NO.), eyano (—CN), hydroxy (O1), halogen, thiol (SED, thioeyano (SCN), Cy, alkyl, C «alkenyl, C,-« alkynyl C, haloalkyl Cy. alkoxy, Cy haloalkoxy, C,.,:eyeloalkyt, C,. cycloalkenyl, Cy. aryl Cys arylalijlene (eg., bonzy)), C,..2 alkylarylone (ea, tolyD, Cy» heteracycloalkyl, C,.. heteroaryl Cy 5 alkyl sulfonyl (2'SC-O}maliyl, C,..5 arylsulfony ("S (O}e-aryb, oF tsyl (CH,C,H,8O,—), provided that the ronal valence of the substituted slom is not excoeded. Whea a compound or group is substituted, the indicated umber of carbon atoms is the umber of carbo atoms ia the compound or group, excluding those of any substituents 10087] While particular embodiments have boca described, altematives, modifications, variations, improve- mens, and substantial equivalents thar are or may be pres- ‘ently unforeseen may arise 1 applicants or others skilled in theart. Accordingly, the appends claims as ied aad as they may be amended are intended to embrace all such alterna- tives, modifications variations, improvements, and substan- tial equivalents. 1. A cursble epoxy composition, comprising 100 parts by weight of an epoxy resin composition ‘comprises an epoxy resin that is a bisphenol A epoxy rosin, Uriglyeidl-substtuted epoxy resin, a wtragly- cidyl-substituted epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a eresol novolak epoxy resin, a cycloaliphatic digiyeidyl ester epoxy resin, a cycloaliphatic epoxy resin comprising a ring {epoxy group, hydantoin epoxy resi ora combination thereol: 30 to 200 parts by weight of an aromatic dianhydride ceuring agent of formula (1) whan Tis 0,8, $0, 0-2-0. SHES 2B an emai Cy mie psi ininy optus oe Cys eas ‘Plaga stone at “hone component ua 2 The canile spony compost seg tein 1 winetns sionals mie basen toma da hydride curing agent and the epoxy resin composition is O:1 to 20:1 Mar. 19, 2020 3. The curable epoxy cor wherein the epoxy resin composi A-epony resi ‘4. The curable epoxy composition according to clam I wherein T is —O— or a group of the formula —O—Z. (O- wherein Z is of formula (2) wherein RY and R” are each independently the same or different, and are a halogen atom or @ monovalent C,.¢ alkyl rou, X"isa ingle bond, —O. 2 C(O}, ora €, nd 1g, and e are each independently integers of Oto 4 5. The curable epoxy composition according to claim 4 wherein Z is a divalent group of formula Ga) or 3b) -O-O- wherein Q is —O-, —S—, —C(O)-, —S0,-, SO (RO) whercin R*isaC, alkyl or Cog aryl or —CyHy— wherein isan integer from 1 fo 5 of a halogenated derivative thereat. 6. The curable epoxy composition avcording to claim 1, further comprising an additive composition. 7. (canceled) 8. (canceled) 9. canceled) 10. The curable epoxy composition according to claim 1, ‘wherein a cured product ofthe curable epoxy composition bas at least one of: ‘glass transition temperature of greater than or equal 10 170° C,, as determined by dynamic mechanical analy sis; and light transmission of greater than 50%, as determined accoring to ASTM D1003 on a 2 mm plaque. 11, A method for the manafocture of thermoset epoxy composition, the method comprising: ccontaeting the epoxy resin composition and the aromatic dianhydride curing agent at a temperature of 130 200) C. to provide the curable epoxy composition of claim 1; snd curing the curable epoxy’ composition 12. The method of claim I wherein the curing comprises isposing the curable epoxy composition into a mold, and tering the curable epoxy composition at 15D to 260° C. for To TS bours in the mold —S-, $0). 80) 5 organic bridging group,US 2020/0087508 AI 13. An article comprising a cured product of the curable ‘epoxy composition according to claims 1. 14, The article of claim 1, wherein the article isin the form of a composite, a foam, fiber, a layer, a coating, an ‘encapsolant, an adhesive, a sealant, a component, a peepreg, ‘8 casing, or @ combination thersof. 15, The method according 10 claim 1, wherein the ‘curable epoxy composition contains no solvent or reactive slluent 16, The metiod according to claim 11, wherein the epoxy resin composition and the aromatic dianhydride curing agent ate contacted without a solvent or a reactive diluent 17. The method aevoding fo claim 11, wherein the curing Js performed without a catalyst. 18, The method acconting to claim 11, wherein a method {or the curing ofthe curable epoxy composition is compres- sion molding, injection molding, transfer molding, pute sion, resin casting, or a combination thereo, Mar. 19, 2020 19. The method avcording. to claim 1, wherein the ‘emperature ofthe contacting ofthe epoxy resin composition and the aromatic dianhydride is 140 0 190° C: 120, The method according to claim 11, wherein a cured product of the cumble epoxy composition has a glass {runsition temperate of greser than or equal 0 180° C..as dlermined by dynamic mechanieal analysis, 21. The curable epoxy composition aevording to claim 1, comprising 50 to 130 parts by. weight of the aromatic anhydride curing agent 22. The curable epoxy composition acording to claim 1, ‘wherein the epoxy resin composition dees not comprise a ‘pony resin containing a spiro-cig. 23. The curable epoxy composition cording to claim 1, ‘wherein the curable epoxy composition does not comprise 3 benzotrazolea triazine, a piperazine, an imidazole, a eyelic famidine, N.N-cimethylaminopyridine, a sulfamidate, a Ciao alkylamine, a totr(C,.., alkyDguanidine, a trary amine or salt thereof, a urea, # sulfonamide, or a sulfone