(12) Patent Application Publication (10) Pub. No.: US 2009/024.0003 A1 Burns Et Al

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US 2009.024.0003A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/024.0003 A1 Burns et al. (43) Pub. Date: Sep. 24, 2009

(54) ADDUCTS AND CURABLE COMPOSITIONS Publication Classification USING SAME (51) Int. Cl. (75) Inventors: Barry N. Burns, Killiney (IE); Ray O Zee. CR P. Tully, Slane (IE); Jonathan P. ( .01) Wigham, Rathfarnham (IE) COSL 83/04 (2006.01) s CSG 18/00 (2006.01) iOS orless (52) U.S. Cl...... 525/410; 528/28: 528/65; 525/452 One Henkel Way Rocky Hill, CT 06067 (US) (57) ABSTRACT (73) Assignee: Loctite (R&D) Limited, Tallaght The ppresent invention relates to adducts useful for improvinp 9. (IE) the toughness and curable compositions using such toughen ing adducts. In a particular aspect, the present invention (21) Appl. No.: 12/051,871 relates to inventive toughening9. 9. adducts and curable compop sitions having improved fracture toughness using those (22) Filed: Mar. 20, 2008 toughening adducts. US 2009/024.0003 A1 Sep. 24, 2009

ADDUCTS AND CURABLE COMPOSITIONS include improved impact resistance especially at low tem USING SAME perature, and adhesion to Substrate Surfaces. 0011. The inventive adducts may be represented by com BACKGROUND OF THE INVENTION pounds within general formula I. 0001 1. Field of the Invention 0002 The present invention relates to adducts useful for improving toughness, and curable compositions using Such adducts. The inventive adducts may improve toughness. Such x. N.N1 N. as in terms of impact resistance, and/or adhesion in curable compositions using those adducts. Y Y 0003 2. Brief Description of Related Technology 0004 Toughness generally is the ability of a material to absorb energy and undergo large permanent set without rup where R is selected from backbones of polyethers, perfluori ture. For many engineering adhesive applications, toughness nated polyethers, polyesters, perfluorinated polyesters, poly is often the deciding factor. Plastics, because of their inherent dimethylsiloxanes or hydroxy terminated polybutadienes; brittleness, have heretofore been modified in a variety of ways 0012 R and Q are independent from one another and are in efforts to improve the toughness thereof. Epoxy resins, for selected from alkylene, arylene, alkyleneoxy or aryleneoxy; example, which form a versatile glassy network when cured, exhibit excellent resistance to corrosion and solvents, good 0013 X is selected from O, NH, S, S=O, and O—S—O: adhesion, reasonably high glass transition temperatures (T) 0014 Y is selected from O or S; and and adequate electrical properties. Unfortunately, however, 00.15 n is 1-4. the poor fracture toughness of epoxy resins oftentimes limits 0016 R thus may be selected from polyethers, such as the usefulness thereof in many commercial applications. polypropylene glycol (“PPG') and polyTHF, perfluorinated 0005. The impact strength, as well as other physical prop polyethers (“PFP), JEFFAMINE type backbones (as more erties of crosslinked epoxy resins, is controlled by the chemi fully described below), polydimethylsiloxane (“PDMS) cal structure and molecular weight of the epoxy resin, weight ratio of the epoxy resin to the hardener, by any added fillers, backbones (again, as more fully described below), LP3 type and by the conditions used to cure the formulation. Unfortu backbones (as more fully described below), and hydroxy nately, crosslinked, glassy epoxy resins with a relatively high terminated polybutadiene (“HPBD") backbones. glass transition temperature (“T”) (>100° C.) are brittle in 0017. In order to improve low temperature fracture tough nature. The poor impact strength of high glass transition ness performance properties, while conferring improved epoxy resins limits their usage as structural materials and use adhesion on Substrates, such as steel, the inventive adducts in or as composites. should also have a low Tg value, such as below room tem 0006 Conventional toughening agents (e.g., carboxyl ter perature, desirably -20° C. and more desirably -40°C. or minated butadiene nitrile rubbers, “CTBN') are frequently lower. In addition, other physical properties of the adduct may unsuitable as additives in formulations where low tempera contribute to Such low temperature performance. Such as ture crash impact performance is desired. compatibility with the thermoset matrix and solubility param 0007. In addition, U.S. Pat. No. 5.278,257 (Mulhaupt) and eters generally. To that end, the level of PDMS in R of the International Patent Publication No. WO 2005/007766 A1 adduct, for instance, may be adjusted if desired within the describe the preparation of a rubber modified epoxy compo range of about 5 to about 95%, such as about 20 to about 80%, sition containing a phenol-capped polyurethane pre-polymer desirably about 20% by weight of R in the adduct, to provide as a toughening agent. The so-described toughening agents the adduct with the desirable Tg, particularly for improving are believed to be the basis of the BETAMATE-brand product wedge impact performance and improved adhesion. To the offering from Dow Automotive. extent that R in the adduct is composed of a second (or third) 0008. The low temperature performance properties of backbone, the remaining portion of R may be a non-silicon such BETAMATE-brand products could stand improvement. containing segment, such as one derived from a polypropy In addition, consumers would benefit from the offering of lene glycol, of course bearing appropriate functionalization. additional adducts and products using Such adducts having 0018. Adducts within general formula I may be useful as different or more desirable physical property performance. additives in one part thermosetting resin compositions, so as 0009. Accordingly, there is a need for inventive adducts to improve physical properties, such as tensile peel strength that are effective for improving the toughness of adhesive values, tensile shear strength values and wedge impact prop formulations, especially in formulations requiring good low erties. temperature performance, and which formulations are based on thermosets such as epoxy, episulfides and/or benzox azines. DETAILED DESCRIPTION OF THE INVENTION 0019. As noted above, the present invention provides SUMMARY OF THE INVENTION inventive adducts which are useful for improving the perfor 0010. In accordance with the present invention, there are mance properties of thermosetting resinformulations, such as provided inventive adducts which are useful for improving those based on epoxy, episulfide, benzoxazine and combina the performance properties of thermosetting resin formula tions thereof. tions, such as those based on epoxy, episulfide, benzoxazine 0020. The inventive adducts may be represented by com and combinations thereof. The performance properties pounds within general formula I. US 2009/024.0003 A1 Sep. 24, 2009

0031. The JEFFAMINET series are trifunctional amine products based on propylene oxide and may be represented by x. N. N. N1 (OCH2CH). NH CH Y Y A(OCH2CH), -NH2 where R is selected from backbones of polyethers, perfluori nated polyethers, polyesters, perfluorinated polyesters, poly CH dimethylsiloxanes or hydroxy terminated polybutadienes; (OCH2CH), -NH2 0021) R' and Q are independent from one another and are CH3 selected from alkylene, arylene, alkyleneoxy or aryleneoxy; 0022 X is selected from O, NH, S, S=O, and O—S—O: where x, y and Z are set forth below in Table A. 0023 Y is selected from O or S; and 0024 n is 1-4. TABLE A 0025 RandR' are each independently selected from poly Approx. Mole ethers, such as PPG and polyTHF, PFP, JEFFAMINE type JEFFAMINE Initiator (A) MOI. Wit PO backbones, PDMS backbones, LP-3 type backbones, and T403 Trimethylolpropane 440 S-6 hydroxy terminated polybutadiene (“HPBD) backbones. T-3 OOO Glycerine 3,000 50 0026. With reference to the building blocks used to pre TSOOO Glycerine 5,000 85 pare the inventive adducts, the linkage represented by “R” may be formed from polyethers functionalized with one or more of hydroxy, mercapto and amino groups. Such poly 0032 More specifically, the JEFFAMINE T403 product ethers may originate from commercially available starting is a trifunctional amine and may be represented by materials, for instance the amine-functionalized polyethers sold under the JEFFAMINE tradename, the mercapto-func tionalized polythioethers sold under the LP-3 tradename and/ CH-OCHCH(CH)-NH or the hydroxy-functionalized polyethers sold under the trade CHCHCCH3-(OCH2CH(CH3)ly-NH. designation, PPG. 0027. Each of these building blocks are available commer CH-OCHCH(CH), -NH cially, or can be prepared, in a variety of molecular weights. where x+y+Z is 5.3 (CAS Registry No. 39423-51-3). With the different molecular weights, physical property 0033. The JEFFAMINEED series are polyether diamine changes can be imported into the inventive adduct to tailor the based products and may be represented by adduct for the specific end use application for which it is intended. 0028 Amine-functionalized polyethers include oxyethyl HN-CHCH-OCHCH-OCHCH-OCHCH-NH ene diamines, oxyethylene triamines, polyoxyethylene diamines, polyoxyethylene triamines, oxypropylene CH CH CH CH diamines, oxypropylene triamines, polyoxypropylene diamines, polyoxypropylene triamines, dimethylene glycol where a, b and c are set forth below in Table B. dipropyl amine and/or derivatives and adducts thereof, and combinations thereof. TABLE B 0029 Commercially available examples of such polyether Approx. Value Approx. amine-based hardeners—amine-functionalized polyethers— include those from BASF Corporation, Mt. Olive, N.J., under JEFFAMINE b 8 - C MOI. Wit the trade designation 4,7,10 TTD, and Huntsman Corpora ED-600 8.5 2.5 600 tion, Houston, Tex., under the JEFFAMINE tradename, such ED-900 15.5 2.5 900 as JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE ED-2001 40.5 2.5 2,000 D-2000, JEFFAMINE T403, JEFFAMINE ED-600, JEF FAMINE ED-900, JEFFAMINE ED-2001, JEFFAMINE 0034. As the mercapto-functionalized polythioethers, EDR-148, JEFFAMINE XTJ-509, JEFFAMINE T-3000, JEFFAMINE T-5000, and combinations thereof. many materials may be used. For instance, polysulfides of the 0030. The JEFFAMINED series are diamine based prod general formulae may be used ucts and may be represented by HS-(R-SS)-R-SH and H2NCHCH (OCH2CH2 NH HS-(R-SS)-CH-CH-CH2-(SS-R)-SH CH3 CH3 (SS-R)-SH (CAS Registry NO. 904610-0) where R is an alkyl ether, Such as —(CH2). O—CH2—O— where x is about 2.6 (for JEFFAMINED-230), 5.6 (for JEF (CH) , and a--b+c n. FAMINE D-400) and 33.1 (for JEFFAMINE D-2000), 0035. A particularly desirable material is known as respectively. THIOKOL LP-3, available commercially from Rohm and US 2009/024.0003 A1 Sep. 24, 2009

Haas Company, Philadelphia, Pa., where n is 6 and about 2 or polyamine compounds), or a polyisocyanate prepolymer mole percent branching exists. LP-3 is also reported to have a derived from a prepolymer polyamine. Such as a prepolymer molecular weight of about 1,000. polyetheramine. 0036) Another particularly desirable material is available 0044) A variety of diisocyanates are useful for reaction in commercially from Akcros Chemicals, Manchester, Great this regard and the choice of any particular one will be left to Britain under the tradename THIOPLAST, such as G1 (n is those persons of ordinary skill in the art, likely to be dictated 19-21, 1.8-2 percent thiol content, and a 3.300-3,700 molecu lar weight), G4 (n is less than 7, less than 5.9 percent thiol in part by the commercial availability and in part by the end content, and less than 1,100 molecular weight), G12 (n is use properties desired. 23-26, 1.5-1.7 percent thiol content, and a 3.900-4,400 0045 Useful diisocyanates include ethylene diisocyanate, molecular weight), G21 (n is 12-15, 2.5-3.1 percent thiol trimethylene diisocyanate, tetramethylene diisocyanate, pen content, and a 2,100-2,600 molecular weight), G22 (n is tamethylene diisocyanate, hexamethylene diisocyanate, hep 14-18, 2.1-2.7 percent thiol content, and a 2,400-3,100 tamethylene diisocyanate, octamethylene diisocyanate, deca molecular weight), G112 (n is 23-25, 1.5-1.7 percent thiol methylene diisocyanate, dodecamethylene diisocyanate, content, and a 3.900–4,300 molecular weight), and G 131 (nis tetradecamethylene diisocyanate, hexadecamethylene diiso 30-38, 1.5-1.7 percent thiol content, and a 5,000-6,500 cyanate, octadecamethylene diisocyanate, eicosamethylene molecular weight). The THIOPLAST materials are reported diisocyanate, cyclohexamethylene diisocyanate, cyclo to be prepared from the polycondensation of bis-(2-chloro penthalene diisocyanate, or cyclohepthalene diisocyanate, or ethyl) formal with alkali polysulfide. bis-cyclohexalene, cyclohexylmethylene diisocyanate, tet 0037 (Meth)acrylate-functionalized polydimethyl silox ramethylxylylene diisocyanate, phenyl diisocyanate, toluene anes of various molecular weights may be used as the build diisocyanate (Such as 2,4-diisocyanatotoluene and 2,6-diiso ing block for this portion of the adduct, as well. cyanatotoluene), 4,4'-diphenyl diisocyanate, 4,4'-diphe 0038 Commercial sources for such (meth)acrylate-func nylene methane diisocyanate, dianisidine diisocyanate, 1.5- tionalized polydimethyl siloxanes include Genesee Silicone, naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, Gelest Silicone and Wacker Silicones. For instance, meth p-phenylene diisocyanate, 4,4'-dicyclo-hexylmethane diiso acryloxypropyl terminated PDMS Imolecular weight 900 cyanate, 1,3-bis-(isocyanatomethyl)cyclohexane, cyclohexy 1200 is available from Gelest under the trade designation lene diisocyanate, tetrachlorophenylene diisocyanate, 2,6-di DMS-R11, methacryloxymethyl terminated PDMS Imolecu ethyl-p-phenylenediisocyanate, 3,5-diethyl-4,4'- lar weight ~1360 is available from Wacker under the trade designation SLM 446016-15 VP 3-acryloxy-2-hydroxypro diisocyanatodiphenyl-methane, tetramethylene diisocyanate, pyl terminated PDMSmolecular weight 1000-1250) is avail hexamethylene diisocyanate, ethylene diisocyanate, cyclo able from Gelest under the trade designation DMS-U22, acry hexylene diisocyanate, nonamethylene diisocyanate, octa loxy terminated ethylene oxide PDMS Imolecular weight decamethylene diisocyanate, 2-chloropropane diisocyanate, 1500-1600 is available from Gelest under the trade designa 2,2'-diethylether diisocyanate, 3-(dimethylamine) pentane tion DBE-U12 and from Goldschmidt under the trade desig diisocyanate, tetrachlorophenylene diisocyanate-1,4,3-hep nation TEGOV-Si 2250 molecular weight -2500. tane diisocyanate and transvinylene diisocyanate. 0039 Again, the different molecular weights of this seg 0046 Additional examples of suitable isocyanates are ure ment impact desirable physical properties of the adduct, so thanized 4,4'-diisocyanatodiphenylmethane, carbodiim that the resulting adduct may be more or less suitable for a idized 4,4'-diisocyanatodiphenylmethane, the adduct formed variety of end use applications. from diisocyanatotoluene and trimethylolpropane, the trimer 0040. A polyalkylene glycol, Such as polypropylene gly formed from diisocyanatotoluene, diisocyanato-m-xylylene, col available commercial from Aldrich Chemical Co., N,N'-di-(4-methyl-3-isocyanatophenyl)-urea, mixed trimer molecular weight ~10,000 may also be used as a building ization products of diisocyanatotoluene and 1,6-diisocyana block of the inventive adduct. Here, too, different molecular tohexamethylene, 1,6-diisocyanatohexane, 3.5.5-trimethyl weights of this segment impact desirable physical properties 1-isocyano-3-isocyanatomethylcyclohexane (isophorene of the adduct, so that the resulting adduct may be more or less diisocyanate), N,N',N'-tri-(6-isocyanatohexyl)-biuret, 2.2, Suitable for a variety of end use applications. 4-trimethyl-1,6-diisocyanatohexane, 1-methyl-2,4-diisocy 0041. These materials may be used as building blocks anatocyclohexane, diisocyanate, 4,4'-diisocyanatodicyclo individually or they may be used in various combinations. The intended end use application will suggest to those of hexylmethane, trimeric isophorene, diisocyanate, trimeric ordinary skill in the art whether to choose one or the other or hexane diisocyanate and methyl 2,6-diisocyanatohexanoate. a combination to provide the physical property set beneficial 0047. As noted above, chain lengtheners may be used as to that end use application. well, examples of which include diols and polyols, such as 0042. Thus, for instance in order to prepare the inventive 1,4-butanediol. 1,1,1-trimethylolpropane or hydroquinone adduct with polyurethane segments, a polyol. Such as trim 2-hydroxyethyl ether, or diamines, such as diaminoethane, ethylol propane, would be reacted under mildly elevated tem 1,6-diaminohexane, piperazine, 2,5-dimethylpiperazine, perature conditions with an isocyanate, desirably a polyiso 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'- cyanate, such as hexamethylene diisocyanate, in the presence diaminocyclohexylmethane, 1,4-diaminocyclohexane and of the building block(s) of the R segments. 1.2-propylenediamine, or hydrazine, amino acid hydrazides, 0043 Isocyanates suitable for use in this adduct building hydrazides of semicarbazidocarboxylic acids, bis-hydrazides reaction include polyisocyanates. Such as a diisocyanate (for and bis-semicarbazides. instance an aliphatic, cycloaliphatic, aromatic or araliphatic 0048. The inventive adducts can be readily prepared in a one) or triisocyanate, or, if desirable, in combination with variety of ways, some of which are discussed in the Examples chain lengtheners (short-chain polyhydroxyl, polysulfhydryl section below.

US 2009/024.0003 A1 Sep. 24, 2009

0050 Structures 7-13 below are examples of A-B-A Block be used as precursors to form Adducts 14-20. Of course copolymers that are hydroxyl or amine functional. These structures can be used in combination with Adducts 14-20 as structures can be used in combination with Adducts 1-6 or can well.

7 Me Me Me

Me Me X. Me

where x is 0-40, m is 0-1, n is 1-50, and p is 1-4.

HOC C OH 2 Me y H HN-CHCH-(O-CHCH)-NH Sin Si N-(CHCH-O)-CHCH-NH | Yo Me CH CH CH CH Me / O O

where n is 0-40 and X is 2-50.

9 O O Me y HN-CHCH-(O-CHCH)-N "No Si -(CH2CH-O)-CHCH-NH M Me CH3 CH3 CH3 CH3 e O O

where n is 1-40 and X is 2-50.

Me OH OH Me H Si O O NH-CHCH-(O-CHCH), -N O O Sin nu1N1 N O Me H3C H3C Me

H N-(CHCH-O).-CHCH-NH N^- CH CH

where n is 1-40 and X is 2-50.

11 Me Me H Si N-1N HN-Ichi-o-HCH-N O "no Me N-(CH, H-O-CHCH-NH. H3C H3C Me /, O CH3 CH3

where n is 1-40 and X is 2-50. US 2009/024.0003 A1 Sep. 24, 2009

12 lsO usO ... ( \| is-cis-to-rich- N-(CH, NH O-(CH) —o – CH CH Me (, Me O l --see- N-(CH2CH-O).H CHCH-NH CH CH where n is 1-40 and X is 2-50.

CN where n is 1-40, m is 3-10, X is 0-10, Y is 0-10, Z is 0-2, R is an alkyl or a cycloalkyl radical and p is 1-4. 0051. Or, in each of structures 7-13, the terminal hydroxyl/ amine groups may be reacted with an isocyanate-containing compound and thereafter with a polythiol Such as, for example, 3,6-dioxa-1,8-octane dithiol to form a thiol-func tionalized adduct, as shown below in Adducts 14-20.

14 O O --0Ye / e–o \ Ye (CH2)(OCH2CH)mO-(CO(CH2)5O)-CO(CH2)5O-CONH 1.NH-(CH)-NH --> Me Me Me X.

O SH

N1)-N-1 N-1 no-1N1 p where x is 0-40, m is 0-1, n is 1-50 and p is 1-4.

15 CO2H O M Me e ls S Si N-(CHCH-O).-CHCH-N N Si H H No Me CH3 CH3 O Me O

where n is 1-40 and X is 2-50. US 2009/024.0003 A1 Sep. 24, 2009

16 O O Me Me l NH SN Si N-(CH2CH-O)-CHCH-N N Si H H No Me CH3 CH3 O Me O

2 where n is 1-40 and X is 2-50.

17 O

M e Me OH ls Si Si nu-1N1O O N-(CHCH-O), -CHCH-NH NH No Me CH CH Me O in-r-soS O O

where n is 1-40 and X is 2-50.

18 O M e Me l 1. Si Su-1N1 NH-(CHCH-O).-CHCH-NH N no-h1.Me CH3 CH3 Me O

H N r S n-1N1N-1 O NSH O 2 where n is 1-40 and X is 2-50.

19 O O O Me Me \ ||Si-(CH2)-O ul NH-(CH2)NH ls NH-(CH2CH-O).-CHCH-NH - N - No Me CH CH US 2009/024.0003 A1 Sep. 24, 2009

-continued Hs N-1N1\-1'N's O where n is 1-40 and X is 2-50. Me y-cis-( O lsO Yo Me HN (CH2)6-N Me H N-R-(CH),NHCO-CH-H)-(CH-CH=CH-CHJCONH CN O H -R-NH ls N H NS-S-N- O p where n is 1-40, m is 3-10, X is 0-10, Y is 0-10, Z is 0-2, R is PGA-X and PGA-C from the Sherwin-Williams Co. And of an alkyl or a cycloalkyl radical and p is 1-4. course combinations of the different epoxy resins are also 0052. As noted above, the thermosetting resin formula desirable for use herein. tions include as athermosetting resin one or more of an epoxy, 0054 Representative episulfide monomers for use herein an episulfide and a benzoxazine. Representative epoxy mono are the thirane counterparts to the epoxy monomers noted in mers contemplated for use herein the preparation of invention the preceding paragraphs. toughening agents include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 4-vinyl-1-cyclohexene diep 0055 Representative benzoxazine monomers for use oxide, butanediol diglycidyl ether, neopentylglycol digly herein include those embraced by the following structure: cidyl ether, 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohex BOZ-A anecarboxylate, limonene diepoxide, hexanediol diglycidyl R ether, trimethylolpropane triglycidyl ether, aniline diglycidyl ether, diglycidyl ether of propylene glycol, cyanuric acid N triglycidyl ether, ortho-phthalic acid diglycidyl ether, digly cidyl ester of linoleic dimer acid, dicyclopentadiene diep oxide, diglycidyl ether of tetrachloro bisphenol A, 1,1,1-tris (p-hydroxyphenyl)ethane glycidyl ether, tetra glycidyl ether of tetrskis(4-hydroxyphenyl)ethane, epoxy phenol novolac resins, epoxy cresol novolac resins, tetraglycidyl-4,4'-diami nodiphenylmethane, and the like. 0053 Among the commercially available epoxy resins where o is 1-4, X is selected from a direct bond (when o is 2), suitable for use herein are polyglycidyl derivatives of phe alkyl (when o is 1), alkylene (when o is 2-4), carbonyl (when nolic compounds, Such as those available under the trade o is 2), thiol (when o is 1), thioether (when o is 2), sulfoxide names EPON 828, EPON 1001, EPON 1009, and EPON (when o is 2), and sulfone (when o is 2), R is selected from 1031, from Shell Chemical Co.; DER 331, DER 332, DER hydrogen, alkyl, alkenyl and aryl, and R is selected from 334, and DER 542 from Dow Chemical Co.: GY285 from hydrogen, halogen, alkyl and alkenyl. Ciba Specialty Chemicals, Tarrytown, N.Y.; and BREN-S 0056 Alternatively, the benzoxazine may be embraced by from Nippon Kayaku, Japan. Other Suitable epoxy resins the following structure: include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, BOZ-B the latter of which are available commercially under the 9-y tradenames DEN 431, DEN 438, and DEN 439 from Dow Y Chemical Company. Cresol analogs are also available com R.C N mercially ECN 1235, ECN 1273, and ECN 1299 from Ciba \ / Specialty Chemicals. SU-8 is a bisphenol A-type epoxy p novolac available from Resolution. Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also use where p is 2, Y is selected from biphenyl (when p is 2), ful in this invention, commercially available resins of which diphenyl methane (when p is 2), diphenyl isopropane (when p include GLYAMINE 135, GLYAMINE 125, and is 2), diphenyl sulfide (when p is 2), diphenylsulfoxide(when GLYAMINE 115 from F.I.C. Corporation; ARALDITE p is 2), diphenyl Sulfone (when p is 2), and diphenylketone MY-720, ARALDITE MY-721, ARALDITE 0500, and (when p is 2), and R is selected from hydrogen, halogen, ARALDITE 0510 from Ciba Specialty Chemicals and alkyl and alkenyl. US 2009/024.0003 A1 Sep. 24, 2009

0057 More specifically, within structure BOZ-A the ben 0.058 Though not embraced by benzoxazine structures Zoxazine may be embraced by the following structure BOZ BOZ-A or BOZ-B, additional benzoxazines are within the following structures: BOZ-C

BOZ-H R2 M N SR)-O-V 1. / x \ y - 2 R4/7 ) O A. where X is selected from a direct bond, CH, C(CH), C=O. ( \ Ž, S, S=O and O—S—O, R and R are the same or different N and are selected from hydrogen, alkyl, Such as methyl, ethyl, / propyls and butyls, alkenyl, such as allyl, and aryland Ra are R the same or different and are selected from hydrogen or alkenyl. Such as allyl. Representative benzoxazines within BOZ-I structure BOZ-C include: R BOZ-D / 2 R4 N o / "Y| N / \, :) ( t / R BOZ-E

BOZ-J

BOZ-F

BOZ-G

where R. RandR areas defined above, and R is defined as where R, R2 and Ra are as defined above. R. R. or R. US 2009/024.0003 A1 Sep. 24, 2009 10

0059 Specific examples of these benzoxazines include: -continued BOZ-K BOZ-P CH ( O-HO y C) - CH BOZ-Q CH BOZ-L | N 21 K H N CH3 O O O C O H ) CH N H / BOZ-M

BOZ-R (O- O / CH3 ) N

BOZ-N

N 0060. The benzoxazine component may include the com H bination of multifunctional benzoxazines and monofunc tional benzoxazines, or may be the combination of one or O C O) functionalmore multifunctional benzoxazines. benzoxazines or one or more mono H 0061 Examples of monofunctional benzoxazines may be embraced by the following structure:

y o N N where R is alkyl, Such as methyl, ethyl, propyls and butyls, or CH2 aryl with or without substitution on one, some or all of the available substitutable sites, and R is selected from hydro gen, halogen, alkyl and alkenyl. US 2009/024.0003 A1 Sep. 24, 2009 11

0062 For instance, monofunctional benzoxazines may be Pat. No. (Schreiber), U.S. Pat. No. 5,021,484 (Schreiber), embraced by the structure U.S. Pat. No. 5,200,452 (Schreiber) and U.S. Pat. No. 5,443, 911 (Schreiber). 0.066 Benzoxazine polymerization can be self-initiated BOZ-T under elevated temperature conditions and also by inclusion of cationic initiators, such as Lewis acids, and other known cationic initiators, such as metal halides; organometallic derivatives; metallophorphyrin compounds such as alumi num phthalocyanine chloride; methyl tosylate, methyl tri flate, and triflic acid; and oxyhalides. Likewise, basic mate rials, such as imidizaoles, may be used to initiate polymerization. 0067. The epoxy, episulfide and/or benzoxazine should be present in the inventive composition in an amount in the range of about 10 to about 90 percent by weight, such as about 25 to where in this case R is selected from alkyl, alkenyl, each of about 75 percent by weight, desirably about 35 to about 65 which being optionally substituted or interupted by one or percent by weight, based on the total weight of the composi more O, N, S, C=O, COO, and NHC=O, and aryl; m is 0-4: tion. and R-Rs are independently selected from hydrogen, alkyl, 0068. As noted above, the composition may include as the alkenyl, each of which being optionally substituted or inter thermoset component any epoxy, episulfide or benzoxazine, upted by one or more O, N, S, C=O, COOH, and NHC=O, at least a portion of which is a multifunctional monomer. and aryl. Ordinarily, the multifunctional monomer used in the compo 0063 Specific examples of such a monofunctional ben sition should be included in amount within the range of about Zoxazine are: 20 weight percent to about 100 weight percent of the compo sition. BOZ-U 0069. A monofunctional monomer, if present, should ordinarily be used as a reactive diluent, or crosslink density modifier. In the event such a monofunctional monomer is included as a portion of the composition, Such resin should be 1N employed in an amount of up to about 20 weight percent, based on the composition. 21 0070 Typically, the composition including the inventive adduct have about 40 to about 95 weight percent of the ther N X moset component, about 5 to about 50 weight percent of the o R inventive adduct, and about 0.2 to about 10 weight percent of the curative. where R is as defined above; or 0071. As employed herein, the term "curing agent” or 'curative' refers to polymerization promoters, co-curing agents, catalysts, initiators or other additives designed to par BOZ-V ticipate in or promote curing of the thermosetting resin for 1a1n 4 mulation. With respect to epoxy containing thermosetting resin formulations, such curing agents include polymeriza tion promoters and catalysts such as, for example, anhy drides, amines, imidazoles, amides, thiols, carboxylic acids, phenols, dicyandiamide, urea, hydrazine, hydrazide, amino formaldehyde resins, melamine-formaldehyde resins, amine boron trihalide complexes, quaternary ammonium salts, qua 0064. Many benzoxazines are presently available com ternary phosphonium salts, tri-aryl Sulfonium salts, di-aryl mercially from several Sources, including Hexcion; Georgia iodonium salts, diazonium salts, and the like, as well as com Pacific Resins, Inc.; and Shikoku Chemicals Corporation, binations of any two or more thereof, optionally also includ Chiba, Japan, the last of which offers among others B.-a, B-m, ing a transition metal complex. Presently preferred curing F-a, C-a, Pd and F-a benzoxazine resins. agents and catalysts for epoxy composition include anhy 0065. If desired, however, instead of using commercially drides, amines, imidazoles, and the like. available sources, the benzoxazine may typically be prepared 0072. As readily recognized by those of skill in the art, by reacting a phenolic compound, Such as a bisphenol A, curing agents contemplated for use in the practice of the bisphenol F. bisphenol S or thiodiphenol, with an aldehyde present invention will vary with the reactive functionality(ies) and an alkyl or arylamine. U.S. Pat. No. 5,543,516, hereby present, the presence of optional co-reactant(s), and the like. expressly incorporated herein by reference, describes a Typically, the quantity of curing agent will fall in the range of method of forming benzoxazines, where the reaction time can about 1 weight percent up to about 50 weight percent of the vary from a few minutes to a few hours, depending on reactant composition, with presently preferred amounts of curing concentration, reactivity and temperature. See also Burke et agent falling in the range of about 5 weight percent up to al., J. Org. Chem., 30(10), 3423 (1965); see generally U.S. about 40 weight percent of the composition. US 2009/024.0003 A1 Sep. 24, 2009

0073. Initiators include hydroxy functionalized com core, hard shell, soft shell, hard shell). In one embodiment of pounds such as, for example, alkylene glycols. Preferred the invention, the rubber particles used are comprised of a alkylene glycols include ethylene glycols and propylene gly core and at least two concentric shells having different chemi cols. cal compositions and/or properties. Either the core or the shell 0074 Fillers contemplated for optional use in the practice or both the core and the shell may be crosslinked (e.g., toni of the present invention include, for example, aluminum cally or covalently). The shell may be grafted onto the core. nitride, boron nitride, silicon carbide, diamond, graphite, The polymer comprising the shell may bear one or more beryllium oxide, magnesia, silicas, such as fumed silica or different types of functional groups (e.g., epoxy groups) that fused silica, alumina, perfluorinated hydrocarbon polymers are capable of interacting with other components of the com (i.e., TEFLON), thermoplastic polymers, thermoplastic elas positions of the present invention. tomers, mica, glass powder and the like. Preferably, the par ticle size of these fillers will be about 20 microns. If alumi 0080 Typically, the core will comprise from about 50 to num nitride is used as a filler, it is preferred that it be about 95 weight percent of the rubber particles while the shell passivated via an adherent, conformal coating (e.g., silica, or will comprise from about 5 to about 50 weight percent of the the like). Some of those fillers may impart properties to the rubber particles. adhesive formulation Such as, for example, reduced thermal I0081 Preferably, the rubber particles are relatively small expansion of the cured adhesive, reduced dielectric constant, in size. For example, the average particle size may be from improved toughness, increased hydrophobicity, and the like. about 0.03 to about 2 microns or from about 0.05 to about 1 0075 Flexibilizers (also called plasticizers) contemplated micron. The rubber particles may have an average diameter of for optional use in the practice of the present invention less than about 500 nm, such as less than about 200 nm. For include branched polyalkanes or polysiloxanes that lower the example, the core-shell rubber particles may have an average T of the formulation. Such flexibilizers include, for example, diameter within the range of from about 25 to about 200 nm. polyethers, polyesters, polythiols, polysulfides, and the like. I0082 Methods of preparing rubber particles having a Ifused, flexibilizers typically are present in the range of about core-shell structure are well-known in the art and are 0.5 weight percent up to about 30 weight percent of the described, for example, in U.S. Pat. Nos. 4,419,496, 4,778, composition. 851, 5,981,659, 6,111,015, 6,147,142 and 6,180,693, each of 0076 Dyes and/or pigments may be used in the practice of which being incorporated herein by reference in its entirety. the present invention. When present, Such dyes and pigments I0083) Rubber particles having a core-shell structure may are typically present in the range of about 0.5 weight percent be prepared as a masterbatch where the rubber particles are up to about 5 weight percent based on the composition. dispersed in one or more epoxy resins such as a diglycidyl 0077 Rubber particles, especially rubber particles that ether of bisphenol A. For example, the rubber particles typi have relatively small average particle size (e.g., less than cally are prepared as aqueous dispersions or emulsions. Such about 500 nm or less than about 200 nm), may also be dispersions or emulsions may be combined with the desired included in the compositions of the present invention. The epoxy resin or mixture of epoxy resins and the water and other rubber particles may or may not have a shell common to volatile substances removed by distillation or the like. One known core-shell structures. method of preparing Such masterbatches is described in more 0078. In the case of rubber particles having a core-shell detail in International Patent Publication No. WO 2004/ structure, such particles generally have a core comprised of a 108825, incorporated herein by reference in its entirety. For polymeric material having elastomeric or rubbery properties example, an aqueous latex of rubber particles may be brought (i.e., a glass transition temperature less than about 0°C., e.g., into contact with an organic medium having partial Solubility less than about -30°C.) surrounded by a shell comprised of a in water and then with another organic medium having lower non-elastomeric polymeric material (i.e., a thermoplastic or partial Solubility in water than the first organic medium to thermoset/crosslinked polymer having a glass transition tem separate the water and to provide a dispersion of the rubber perature greater than ambient temperatures, e.g., greater than particles in the second organic medium. This dispersion may about 50° C.). For example, the core may be comprised of a then be mixed with the desired epoxy resin(s) and volatile diene homopolymer or copolymer (for example, a homopoly substances removed by distillation or the like to provide the mer of butadiene or isoprene, a copolymer of butadiene or masterbatch. isoprene with one or more ethylenically unsaturated mono merS Such as vinyl aromatic monomers, (meth)acrylonitrile, I0084 Particularly suitable dispersions of rubber particles (meth)acrylates, or the like) while the shell may be comprised having a core-shell structure in an epoxy resin matrix are of a polymer or copolymer of one or more monomers such as available from Kaneka Corporation. (meth)acrylates (e.g., methyl methacrylate), vinyl aromatic I0085 For instance, the core may beformed predominantly monomers (e.g., Styrene), vinyl cyanides (e.g., acrylonitrile), from feed stocks of polybutadiene, polyacrylate, polybutadi unsaturated acids and anhydrides (e.g., acrylic acid), (meth) enefacrylonitrile mixture, polyols and/or polysiloxanes or acrylamides, and the like having a suitably high glass transi any other monomers that give a low glass transition tempera tion temperature. Other rubbery polymers may also be suit ture. The outer shells may be formed predominantly from ably be used for the core, including polybutylacrylate or feed stocks of polymethylmethacrylate, polystyrene or poly polysiloxane elastomer (e.g., polydimethylsiloxane, particu vinyl chloride or any other monomers that give a higher glass larly crosslinked polydimethylsiloxane). transition temperature. 007.9 The rubber particle may be comprised of more than I0086. The core shell rubbers may have a particle size in the two layers (e.g., a central core of one rubbery material may be range of 0.07 to 10 um, such as 0.1 to 5um. surrounded by a second core of a different rubbery material or I0087. The core shell rubber made in this way are may be the rubbery core may be surrounded by two shells of different dispersed in an epoxy matrix or a phenolic matrix. Examples composition or the rubber particle may have the structure soft of epoxy matrices include the diglycidyl ethers of bisphenol US 2009/024.0003 A1 Sep. 24, 2009

A, F or S, or biphenol, novalac epoxies, and cycloaliphatic epoxies, and cycloaliphatic epoxies. Examples of phenolic epoxies. Examples of phenolic resins include bisphenol-A resins include bisphenol-A based phenoxies. based phenoxies. 0096. The rubber particles may be present in the epoxy or 0088. The core shell rubber dispersion may be present in phenolic matrix in an amount in the range of about 5 to about the epoxy or phenolic matrix in an amount in the range of 50 weight percent and as about 15 to about 40 weight percent. about 5 to about 50% by weight, with about 15 to about 25% 0097. Typically, the composition may contain in the range by weight being desirable based on viscosity considerations. of about 5 to about 35 weight percent, and as about 15 to about 0089. When used in the inventive compositions, these core 30 weight percent rubber particles. shell rubbers allow for toughening to occur in the composi 0.098 Combinations of different rubber particles may tion and oftentimes in a predictable manner in terms of advantageously be used in the present invention. The rubber temperature neutrality toward cure—because of the Substan particles may differ, for example, in particle size, the glass tial uniform dispersion, which is ordinarily observed in the transition temperatures of their respective materials, whether, core shell rubbers as they are offered for sale commercially. to what extent and by what the materials are functionalized, 0090. Many of the core-shell rubber structures available and whether and how their surfaces are treated. from Kaneka are believed to have a core made from a copoly 0099. A portion of the rubber particles may be supplied to mer of (meth)acrylate-butadiene-styrene, where the butadi the adhesive composition in the form of a masterbatch, where ene is the primary component in the phase separated particles, the particles are stably dispersed in an epoxy resin matrix and dispersed in epoxy resins. Other commercially available mas another portion may be supplied to the adhesive composition terbatches of core-shell rubber particles dispersed in epoxy in the form of a dry powder (i.e., without any epoxy resin or resins include GENIOPERL M23A (a dispersion of 30 other matrix material). For example, the adhesive composi weight percent core-shell particles in an aromatic epoxy resin tion may be prepared using both a first type of rubberparticles based-on bisphenol A diglycidyl ether; the core-shell par in dry powder form having an average particle diameter of ticles have an average diameter of ca. 100 nm and contain a from about 0.1 to about 0.5 p and a second type of rubber crosslinked silicone elastomer core onto which an epoxy particles stably dispersed in a matrix of liquid bisphenol A functional acrylate copolymer has been grafted; the silicone diglycidyl ether at a concentration of from about 5 to about 50 elastomer core represents about 65 weight percent of the percent by weight having an average particle diameter of core-shell particle), available from Wacker Chemie GmbH. from about 25 to about 200 nm. The weight ratio of first type: second type rubber particles may be from about 1.5:1 to 0091. In the case of those rubber particles that do not have about 0.3:1, for example. such a shell, the rubber particles may be based on the core of 0100. The chemical composition of the rubber particles Such structures. may be essentially uniform throughout each particle. How 0092 Preferably, the rubber particles are relatively small ever, the outer surface of the particle may be modified by in size. For example, the average particle size may be from reaction with a coupling agent, oxidizing agent or the like so about 0.03 to about 2 um or from about 0.05 to about 1 lum. In as to enhance the ability to disperse the rubber particles in the certain embodiments of the invention, the rubber particles adhesive composition (e.g., reduce agglomeration of the rub have an average diameter of less than about 500 nm. In other ber particles, reduce the tendency of the rubber particles to embodiments, the average particle size is less than about 200 settle out of the adhesive composition). Modification of the nm. For example, the rubber particles may have an average rubber particle surface may also enhance the adhesion of the diameter within the range of from about 25 to about 200 nm epoxy resin matrix to the rubber particles when the adhesive or from about 50 to about 150 nm. is cured. The rubber particles may alternatively be irradiated 0093. The rubber particles generally are comprised of a So as to change the extent of crosslinking of the polymer(s) polymeric material having elastomeric or rubbery properties constituting the rubber particles in different regions of the (i.e., a glass transition temperature less than about 0°C., e.g., particle. For example, the rubber particles may be treated with less than about -30°C.). For example, the rubber particles gamma radiation Such that the rubber is more highly may be comprised of a diene homopolymer or copolymer (for crosslinked near the surface of the particle than in the center example, a homopolymer ofbutadiene or isoprene, a copoly of the particle. mer of butadiene or isoprene with one or more ethylenically 0101 Rubber particles that are suitable for use in the unsaturated monomers such as vinyl aromatic monomers, present invention are available from commercial sources. For (meth)acrylonitrile, (meth)acrylates, or the like) and polysi example, rubber particles supplied by Eliokem, Inc. may be loxanes. The rubber particles may contain functional groups used, such as NEP RO401 and NEP R401S (both based on Such as carboxylate groups, hydroxyl groups or the like and acrylonitrile/butadiene copolymer); NEP R0501 (based on may have a linear, branched, crosslinked, random copolymer carboxylated acrylonitrile/butadiene copolymer; CAS No. or block copolymer structure. 9010-81-5); NEP RO601A -(based on hydroxy-terminated 0094 For instance, the rubber particles may be formed polydimethylsiloxane: CAS No. 70131-67-8); and NEP predominantly from feed stocks of dienes such as butadiene, R0701 and NEP 0701S (based on butadiene/styrene/2-vi (meth)acrylates, ethylenically unsaturated nitriles such as nylpyridine copolymer; CAS No. 25053-48-9). acrylonitrile, and/or any other monomers that when polymer 0102 Rubber particles that have been treated with a reac ized or copolymerized yield a polymer or copolymer having tive gas or other reagent to modify the outer Surfaces of the a low glass transition temperature. particles by, for instance, creating polar groups (e.g., 0095. The rubber particles may be used in a dry form or hydroxyl groups, carboxylic acid groups) on the particle Sur may be dispersed in a matrix, Such as an epoxy matrix or a face, are also suitable for use in the present invention. Illus phenolic matrix. The matrix material preferably is liquid at trative reactive gases include, for example, oZone, Cl, FO, room temperature. Examples of epoxy matrices include the SOs, and oxidative gases. Methods of surface modifying rub diglycidyl ethers of bisphenol A, For S, or bisphenol, novalac ber particles using Such reagents are known in the art and are US 2009/024.0003 A1 Sep. 24, 2009

described, for example, in U.S. Pat. Nos. 5,382,635: 5,506, aliphatic, cycloaliphatic or aromatic group, each of which 283:5,693,714; and 5,969,053, each of which is incorporated may be optionally further substituted in any position with herein by reference in its entirety. Suitable surface modified one or more, of C-C alkyl, OH, halogen (F, Br, Cl, or I), rubber particles are also available from commercial sources, phenyl, a C-C alkylphenyl, a C-C alkenylphenyl, or such as the rubbers sold under the tradename VISTAMER by OR, where R is phenyl, a carboxylic group, carbonyl, oran Exousia Corporation. aromatic group and R is optionally Substituted with C-C (0103) Where the rubber particles are initially provided in alkyl, OH, or halogen; or nitro, nitrile, or halogen. dry form, it may be advantageous to ensure that Such particles are well dispersed in the adhesive composition prior to curing 0114 Examples of useful solid organic acids are phenols, the adhesive composition. That is, agglomerates of the rubber quinones, carboxylic acids and enolisable materials. An particles are preferably broken up so as to provide discrete example of an enolisable material is barbituric acid. The term individual rubber particles, which may be accomplished by 'acid' includes polymeric acids including polycarboxylic intimate and thorough mixing of the dry rubber particles with acids and polyphenols. other components of the adhesive composition. For example, 0115 The solid organic acids should be substantially dry rubber particles may be blended with epoxy resin and insoluble in the thermosetting resin formulation attempera milled or melt compounded for a length of time effective to tures in the range of about 5°C. to about 35°C., such as about essentially completely disperse the rubber particles and break 15° C. to about 30° C. up any agglomerations of the rubber particles. 0116. The solid organic acid should be present in an 0104 Solid organic acids are useful in the thermosetting amount of about 0.1 to 25 parts by weight per 100 parts of the resin formulation to improve viscosity stability. These solid organic acids include compounds having acid functional thermosetting resin in the thermosetting resin formulation. groups, as well as compounds which have an acidic proton or 0117 The solid organic acid should have a degree of have an acid nature, for example enolisable materials. insolubility Such that it can act as a reservoir permitting only 0105. The term “aliphatic' as used in connection with the sufficient acid to solubilise thereby neutralising any soluble Solid organic acid refers to C-Cao Suitably C-Co straight or curative and/or a reaction product of the thiol-capped adduct branched chain alkenyl, alkyl, or alkynyl which may or may and the curative. The Solid organic acid which is Substantially not be interrupted or substituted by one or more heteroatoms insoluble, remains so in effective amounts at temperatures such as O, N or S. below the elevated activation temperatures necessary to ini 0106 The term "cycloaliphatic” as used herein refers to tiate cure of the composition. The temperatures below the cyclised aliphatic C-Clo, Suitably C-C groups and activation temperature referred to include temperatures at or includes those interrupted by one or more heteroatoms Such about room temperature. In other words, an amount of the as O, N, or S. Solid organic acid remains in the solid form, the amount being 0107 The term “aromatic” refers to C-C suitably effective to stabilise the composition. Thus cure initiating C-Clso aromatic groups including heterocyclic aromatic species present in the composition are neutralised by the groups containing one or more of the heteroatoms, O, N, or S. solubilised acid, on a continuing basis. Of course, depending and fused ring systems containing one or more of these aro on the particular acid and hardener the stabilisation time may matic groups fused together. vary. Those skilled in the art will readily understand how to 0108. The term “carboxylic acid' includes acids having vary that time as desired by making appropriate choices of the one or more carboxylic groups, and if two or more are present, particular components and using Suitable amounts thereof. one or more may be optionally esterified, the ester group 0118. The solid organic acids should have a pKa less than Suitably comprising a C-Co alkyl group Suitably a C-C, the pKa of the thiol-capped adduct. Typically, the thiol alkyl group. capped adducts have pKas within the range of about 8-12. 0109 The term "quinone' includes compounds having Desirable acids are those having a pKa less than or equal to one or more quinone groups and the terms aliphatic, about 12.0, desirably less than or equal to about 10.0, and cycloaliphatic and aromatic when used to describe quinones often less than or equal to about 9.0. Such as less than or equal are used to refer to quinones to which aliphatic, cycloaliphatic to about 7.5. Where a combination of two or more solid and aromatic groups or combinations of these groups are organic acids is used the pKa of the combination should be attached by direct bonding or ring fusion. less than or equal to about 12.0. Ordinarily, at least one of the 0110. The term “phenol includes compounds having one acids in the Solid organic acid component has a pKa less than or more phenolic groups and the terms aliphatic, that of the thiol-capped adduct, i.e. less than or equal to about cycloaliphatic and aromatic when used-to describe phenols is 12.0, and suitably less than or equal to about 10.0 and often used to refer to phenols to which aliphatic, cycloaliphatic and less than or equal to about 9.0 such as less than or equal to aromatic groups or combinations of these groups are attached about 7.5. by direct bonding or ring fusion. 0119 When present, the solid organic acid may react pref 0111. The term “enolisable' includes compounds having erentially with the soluble latent hardener until the acid con one or more enolisable functional groups. centration has been exhausted, at which time the latent hard 0112. The term "derivatives’ refers to substitutions at one ener may react with the thiol-capped adduct in the ore more positions (including directly on a heteroatom) with thermosetting resin formulation to commence cure of the one or more of the following: composition. The Solid organic acid component remains Sub 0113 C-C alkoxy, C-C alkyl, C-C alkenyl, a car stantially insoluble in the composition so that Solid organic bonyl group, a thiocarbonyl group Such as a —C=S group, acid is present in an amount effective to stabilise the Theo a carboxylic group, a C-C alkyl group further containing logical properties of the composition. Some Theological sta up to three Natoms, phenyl, C-C alkylphenyl, or C-C bilisation may be imparted by the neutralisation of the soluble alkenylphenyl; OR, NR, SR, or SSR, where R is phenyl, an latent hardener by the Solid organic acid. US 2009/024.0003 A1 Sep. 24, 2009

0120. The solid organic acid desirably has a mean particle size in the range about 0.1 to about 500 microns suitably about 5 to about 100 microns, and desirably about 10 to about 50 microns. 0121 The solid organic acid may be selected from car boxylic acids of the general formula: RCOH, where R is trans-CH=CHCOH, -CH=CHCOR where R is CHI, —CHC(OR)(COR")CHCOR" where R' is H, C-Co alkyl, or Ar; R" is H. C-C alkyl, or Ar; R" is H, C-Co alkyl, or Art, C-C alkyl, -(CH2)COH n is 1-9. where R. R. R. and R are independently H, alkyl, -(CHR),COHR is Hor OH, n is 1 or 21, -CH(OR)R"R" haloalkyl, alkenyl, ORR is H, alkyl, Ar., Ph, or Bn CN, Ph, or is H, alkyl, R"—C-C alkyl, or Ph. —CH=CH-Ar, or Ar 0.124 Phenols of the general formula below are also suit CH3 able for use herein. OH OH

OH CH O CH3 CH CO2H

where R is H or OH: R is H, alkyl, haloalkyl such as CX where X is F, Br, Cl, or II, alkenyl, Cl, F, Br, I, CN, OH, OR -CH where R is alkyl, Ph, Bn, or Arl, NO, C(=O)R where R is alkyl, Ph, Bn, or Ar), CHO, COR where R is H, alkyl, Ph. 0122. Other suitable solid organic acids are benzoic acids Bn, or Arl, or PhOH: R is H. alkyl, haloalkyl, alkenyl, OH, of the general formula: OR where R is alkyl, Ph, Bn, or Arl, Ph, Bn, —CHAr, CN, F, Cl, Br, or I; R is H, alkyl, haloalkyl such as CX where X is F, Br, Cl, or II, alkenyl, NO, C(=O)R where R is alkyl, COH Ph, Bn, or Arl, CHO, COR where R is alkyl, Ph, Bn, or Ar), OH, OR where R is alkyl, Ph, Bn, or Arl, Ar, Bn, Ph, C(R) PhOH where R is Me or H, C(R), Arwhere R is Me or H O

where R is H, alkyl, haloalkyl such as CX where X is F, Cl, Br, or II, alkenyl, OH, OR where R is alkyl, Ph, Bn, or Ar. O OH O OH S S Ar—COH, -S. S. Ar. —SR (where R is H. alkyl, haloalkyl, Ph, Bn, or Ar), Ph, Bn, Ar., COR where R is where R and R, are independently H, alkyl, haloalkyl, alk H, alkyl, Ph, Bn, or Ar), C(=O) R where R is H, alkyl, Ph. enyl, OH, or OR where R is alkyl, Ph, Bn, or Ar; R is H. Bn, or Ar), or NO; R is H, alkyl, haloalkyl such as CX alkyl, haloalkyl, alkenyl, OH, OR where R is alkyl, Ph, Bn, where X is F, Cl, Br, or II, alkenyl, Ph, Bn, Ar, OH, OR or Ar), F, Cl, Br, I, CN, Ph, Bn, or —CHAr; Rs is H, alkyl, where R is alkyl, Ph, Bn, or Arl, -CHAr, NO, C(=O)R haloalkyl such as CX, where X is F, Br, Cl, or II, alkenyl, F, where R is C-C alkyl, Ph, Bn, or Ar), CHO, COR where Cl, Br, I, CN, OH, ORR is alkyl, Ph, Bn, or Ar), NO, R is H. alkyl, haloalkyl, Ph, Bn, or Ar), or R is H, alkyl, C(=O)R where R is alkyl, Ph, Bn, or Ar), CHO, CO, R haloalkyl such as CX where X is F, Cl, Br, or II, alkenyl, OH, where R is H, alkyl, Ph, Bn, or Ar), or PhOH, provided that OR where R is alkyl, Ph, Bn, or Ar), Ph, Bn, Ar, alkyl, CHO, a compound of general Formula IV is chosen to have at least C(=O)R where R is alkyl, Ph, Bn, or Arl, COR where R is one phenolic group present. H, alkyl, Ph, Bn, or Aror NO; R is H, alkyl, haloalkyl such 0.125 Enolisable materials such as those compounds of as CX where X is F, Cl, Br, or II, alkenyl, OH, OR where R the general formula below are also suitable for use herein. is alkyl, Ph, Bn, or Arl, NO, C(=O)R where R is alkyl, Ph. Bn, or Ar), CHO, COR where R is H, alkyl, Ph, Bn, or Ar), O O Ph, Bn, or Ar; Rs is H, alkyl, haloalkyl such as CX where X is F, Cl, Br, or II, alkenyl, OH, OR where R is alkyl, Ph, Bn, or Ar), Ph, Bn, Ar. CHO, C(=O)R (where R is alkyl, Ph, Bn, ---, or Arl, COR where R is H, alkyl, Ph, Bn, or Ar), or NO. 0123. Quinones of the general formula below are also where R or R are NRC(=O)NR'R'" where R is H, alkyl, suitable for use herein. Ph, or Ar; R" is H, alkyl, Ph, or Ar; and R" is H, alkyl, Ph, or US 2009/024.0003 A1 Sep. 24, 2009

Ar), or OR where R is H, alkyl, Ph, or Ar; X is (CH), C(R) where R is alkyl, Ph, Ar, or CN, O, S, NR where R is H, -continued alkyl, Ph, or Ar), and n is 1-10. 0126 The enolisable material of the preceding paragraph 3,4-dihydroxy cinnamic acid may be selected from compounds of the general formula Quinone Derivatives Enolisable Acids below: 2,3-dicyanohydroquinone barbituric acid tetrahydroxy-p-benzoquinone parabanic acid phenylboronic acid 5-phenyl Meldrum's acid Meldrum's acid

0.134 Conditions suitable to cure the inventive composi tions include exposing the compositions to a temperature of at least about 120° C. but less than about 190° C. for about 0.5 up to about 60 minutes, such as 30 minutes at 180° C. where (a) X=XNH, R—H, R=O, n=1; or 0127 (b) X—X—NH, R=O, n is Zero so that the cyclic 0.135 More specifically, the inventive adducts may also be structure has a five membered ring; or used as latent curatives for the thermosetting resin, if they I0128 (c) X=X=O, R—H, R=(CH), n=1; or contain a thiol and/or amine functional group or if they are 0129 (d) X=X—O, R—Ph, R=(CH), n=1. reacted to become functionalized with Such a group. In addi 0130. In the general formulae above for the solid organic tion, they may be used to prepare compositions capable of acids, Arrepresents Substituted phenyl, Substituted or unsub curing attemperatures lower than those set forth above. Such stituted bicyclic or multicyclic aromatic compounds, e.g., as at about 100° C. naphthalene, substituted naphthalene, and the like and Ph is 0.136 The inventive compositions may also be formulated phenyl. Bn is a substituted or unsubstituted benzyl group. as one part compositions or two part compositions, as desired. Alkyl may be straight chained or branched C-C alkyl, In a one part composition, it may be desirable to grind the suitably C-C alkyl. Haloalkyl should be interpreted as an inventive adduct to a uniform particle size. Such as by cryo alkyl Substituted one or more times by one or more halogens. genic grinding techniques, to ensure a dispersable particle Alkenyl may be straight chain or branched C-C alkenyl, size. In a two part composition, the inventive adduct may be Suitably C-Coalkenyl. solubilized in one of the parts. 0131 The solid organic acid may for example be selected 0.137 The present invention provides methods for adhe from 4-nitroguaiacol. 3,4,5-trimethoxy benzoic acid, sively attaching a first article to a second article. Such meth hexachlorophene, 3,5-dinitrosalicylic acid, 4.5,7-trihydroxy ods include flavanone, 2.2-dithiosalicylic acid, phloroglucinol, fumaric 0.138 (a) applying an inventive composition to a first acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxy benzoic article, acid, trolox, pamoic acid, ascorbic acid, salicylic acid, citric 0.139 (b) bringing together the first article and a second acid, 3,4-dihydroxy cinnamic acid, 2,3-dicyanohydro article into intimate contact to form an assembly, where the quinone, barbituric acid, tetrahydroxy-p-benzoquinone, first article and the second article are separated only by the parabanic acid, phenyl boronic acid, 5-phenyl Meldrum's adhesive composition applied in step (a), and thereafter, acid and Meldrum's acid. 0140 (c) subjecting the assembly to conditions suitable to 0132) Of these acids those which display a greater stabi cure the composition. lising effect are barbituric acid, Trolox, and fumaric acid with 0.141. In accordance with yet another embodiment of the barbituric acid displaying a better stabilising effect. A number present invention, there are provided assemblies produced by of solid organic acids which are set out below, and for ease of these methods. discussion herein only, have been classified into four different 0142. The invention will now be illustrated by way of the groups. following examples. EXAMPLES OF SOLID ORGANIC ACIDS EXAMPLES 0133) Example 1 General Preparation of Polyurethane Type Adducts Phenolic Functional Groups Carboxylic Functional Groups 1-6 4-nitroguaiacol 3,4,5-trimethoxybenzoic acid hexachlorophene 3,5-dinitrosalicylic acid 0143. One equivalent of a functionalized polyether or 4,5,7-trihydroxyflavanone 2,2-dithiosalicylic acid phloroglucinol fumaric acid polydimethyl siloxane backbone material (such as one termi 3,4-dihydroxybenzoic acid nated at each end with one of hydroxyl, amino, mercapto or 3,4,5-trihydroxybenzoic acid carboxyl) is reacted with 2 equivalents of a diisocyanate (e.g., Trolox (6-hydroxy-2,5,7,8- hexamethylene diisocyanate or isophorone diisocyanate) by tetramethylchroman-2 carboxylic acid) pamoic acid bringing into contact the two materials with or without the ascorbic acid presence of a chain extender, such as trimethylol propane, Salicylic acid under appropriate catalysis at a temperature between 20 and citric acid 100° C., particularly between 60 and 80°C., under an inert atmosphere. The reaction is maintained until the isocyanate US 2009/024.0003 A1 Sep. 24, 2009

content reaches a value indicative of complete reaction and copolymeris reacted with 2 equivalents of a diisocyanate (e.g. the formation of an isocyanate terminated polyurethane hexamethylene or isophorone diisocyanate) by bringing into adduct. contact the two materials with or without the presence of a 0144. The above isocyanate terminated polyurethane chain extender, Such as trimethylol propane, under appropri adduct is used as an intermediate to be capped by reaction of ate catalysis at a temperature between 20 and 100° C., par the terminal isocyanate functional groups with a mercaptain ticularly between 60 and 80°C., under an inert atmosphere. capping agent, such as 3,6-dioxa-1,8-octane dithiol. The reaction is maintained until the isocyanate content 0145. In this manner Adducts 1-6 may be synthesised. reaches a value indicative of complete reaction and the for 0146 In the case of Adduct 5 a blend of a hydroxy func mation of an isocyanate-terminated polyurethane adduct. tionalised polyether and a hydroxy terminated polydimethyl 0157. The above isocyanates-terminated polyurethane siloxane are reacted in the presence of a trimethylol propane adduct is used as an intermediate to be capped by reaction of chain extender with the appropriate equivalents of diisocyan the terminal isocyanate functional groups with a mercaptain ate. The terminal isocyanate groups are then capped with an capping agent, such as 3,6-dioxa-1,8-octane dithiol. appropriate mercaptain capping agent, such as 3,6-dioxa-1.8- 0158. In this manner Adducts 14-20 may be synthesised. octane dithiol. Example 2 Example 3 Preparation of A-B-A Block Copolymer Type 0159. The following versions of Adduct 1 were prepared Adducts 7-13 in accordance with the procedure outlined in Example 1, using various hydroxyl functional polyether backbone mate 0147 Here, A-B-A block copolymer type materials of rials of different molecular weights and with or without a structures 7-13 are prepared and are Subsequently reacted as chain extender Such as trimethylol propane. in Example 1 above to prepare Adducts 14-20. 0148 More specifically, the A-B-A block copolymer materials are prepared by reacting an appropriate amount Adduct 1 a (two equivalents for example) of a suitable Block A material 0160 Polytetrahydrofuran with a molecular weight of Such as an amine functional polyether, a e-caprolactone, oran 2000 under the tradename TERATHANE 2000 200g, 0.1 amine terminated rubber such as a Hycar rubber material with mol. 1,6-diisocyanato hexane (34.47 g., 0.205 mol and tri one equivalent of a functionalised polyether or polydimethyl methylol propane 2.5g, 0.018 mol were mixed with heating siloxane Block B material such as one terminated with (meth) to a temperature of 65° C. under an inert atmosphere in a acrylate groups, or anhydride groups. Alternately, the Block reactor vessel equipped with a mechanical stirrer and a ther B material may be first reacted with a diisocyanate to forman mometer. On dissolution of the trimethylol propane, a cata isocyanate functional pre-polymer which is then reacted with lytic amount of dibutyl tin dilaurate was added to the stirring the appropriate Block A material. mixture to initiate reaction, evidence of which was observed 0149 Suitable A-B-A Block copolymer materials include by a rise in temperature. The mixture was allowed to continue the reaction products of: to stir for a period of time of 1 hour. When the temperature 0150 amino/mercapto/hydroxy terminated Block B receded to a temperature of 80° C., 1,2-bis(2-mercaptoet material with a lactone Such as caprolactone structure hoxy)ethane 38.28 g., 0.209 mol was added as a single 7, aliquot and the mixture stirred for a further period of time of 0151 an anhydride terminated Block B material with 1.5 hours and then cooled to room temperature to afford the one or more equivalents of an amine/mercapto/hydroxy Adduct la as a high viscosity resin. terminated Block A material structure 8. 0152 Structure 8 may also be subjected to appropriate Adduct lb heat treatment to effect ring closure to form the corre sponding imide structure structure 9. 0.161. Using the same procedure as described in connec 0153 an amine- or mercapto-containing polyether tion with the formation of Adduct 1a, except that the polytet material by Michael addition reaction of one or more rahydrofuran used here had a molecular weight of 650 ITER equivalents of a, for example, a JEFFAMINE onto an ATHANE 650 was employed to form Adduct 1b. acrylate structure 10 or methacrylate structure 11 terminated Block B material. Adduct lic 0154 a hydroxy- or carboxyl-containing Block B mate rial with a diisocyanate under appropriate catalysis con 0162. Using the same procedure as described in connec ditions, and capping the terminal isocyanate groups with tion with the formation of Adduct 1 a, except that no trimethy a hydroxy- or amino-terminated polyether, such as a lol propane was added to form Adduct 1c. JEFFAMINE structure 12, oranamino terminated rub ber such as a HYCAR rubber material structure 13. Adduct 1d 0155 The Block A and B materials in proper stoichiomet 0163. Using the same procedure as described in connec ric amounts are heated to an appropriate temperature for a tion with the formation of Adduct 1b, except that no trimethy period of time, such as 1 to 24 hours, depending on the nature lol propane was added to form Adduct 1d. and identity of the reactants, to form the A-B-A block copoly mer materials of structures 7-13. Adduct le 0156 The A-B-A Block copolymer materials of structures 7-13 are then reacted as in Example 1 i.e. one equivalent of an 0164. Using the same procedure as described in connec appropriate amine/hydroxyl terminated A-B-A Block tion with the formation of Adduct 1 a, except that TER US 2009/024.0003 A1 Sep. 24, 2009

ATHANE 2000 was replaced by polypropylene glycol with a molecular weight of 2000 to form Adduct le. TABLE 3

Adduct lif Wedge Impact Peel Sample Nos. 0.165. Using the same procedure as described in connec (N mm) (a) I II III IV tion with the formation of Adduct 1a except that a blend of RT X. 49.73 39.44 45.80 39.08 functionalised polyether backbones—a 70:30 mix ratio of CS 2.36 3.53 O.15 1.33 TERATHANE 2000/PPG 2000 was used to form Adduct Failure Mode* cf af af af 1f. -40°C. X. SO.80 2.46 47.84 4.28 0166 Table 1 represents a set formulations (Sample Nos. CS 2.43 1.89 O.71 O.81 I-IV) prepared with Adducts 1a-1d. Failure Mode* cf af 75% cf af * af= adhesive failure, cf= cohesive failure TABLE 1. X is the mean result, O is standard deviation. Component Sample Nos. Amt (wt %) (0169 Table 3 shows that each version of Adduct 1 dem Type Identity I II III IV onstrates excellent wedge impact peel values at room tem Epoxy EPON 828 8.4 8.4 8.4 8.4 perature and -40°C. Table 3 also demonstrates that Adducts ADEKAEP 49-1ON 7.0 7.0 7.0 7.0 1b and 1d (in Sample Nos. II and IV, respectively) have poor Toughener Adduct 1a 17.7 impact peel at -40°C. In contrast, Adducts 1a and 1c (in Adduct 1b 17.7 Sample Nos. I and III, respectively) provide low temperature Adduct 1c 17.7 toughness. Adduct 1d 17.7 ZEON F351 9.9 9.9 9.9 9.9 TABLE 4 KANEKAMX 153 44.4 44.4 44.4 44.4 Filler CABOSILTS 720 3.1 3.1 3.1 3.1 Component Sample Nos. Amt. (wt % MONARCH 28O O.3 O.3 O.3 O.3 Type dentity V VI VII VIII IX X CAO 3.1 3.1 3.1 3.1 Curative DYEHARD UR 700 1.O 1.O 1.O 1.O Epoxy EPON 828 8.O. 12.0 8.O. 11.6 116 116 CARDOLITE 1.6 1.6 1.6 DYEHARD 10OS S.1 S.1 S.1 S.1 2513 EP49-1ON 6.O 6.O 6.O 2.O 2.0 2.0 EP 49-1ON = chelate modified epoxy resin adhesion promoter, commercially Toughener Prepo 2000LV 1S.O — 15.0 available from Adeka Adduct 1 a — 15.0 — 15.0 Adduct 1e — 15.0 — 15.0 ZEON F351 = core shell particles DY965 CH 7.0 7.0 7.0 QR 94.66 4.4 4.4 4.4 0167 Table 1 shows four formulations each using a dif ZEON F351 7.2 7.2 7.2 6.0 6.O 6.O ferent version of Adduct 1. The different versions of Adduct KANEKAMX 42.O 42.O 42.O 42.O 42.O 42.0 53 1—Adducts 1a-1d have different molecular weight back Adhesion ZP5070 HV 2.0 2.0 2.0 2.O 2.0 2.0 bones (650 or 2000) and with/without chain extender. Promoter SILQUEST O.2 O.2 O.2 O.2 O.2 O.2 A-187 TCP 2.0 2.0 2.0 2.2 2.2 2.2 TABLE 2 NIPOL 1411 1.O 1.O 1.O NYAD 400 1.4 1.4 1.4 T-Peel Strength Sample Nos. CaO 3.0 3.0 3.0 2.O 2.0 2.0 SYLOTHIX 53 O.S O.S O.S (N mm) I II III IV CABOSILTS 3.0 3.0 3.0 1.5 1.5 1.5 720 Oiled HDG X. 9.07 11:44 8. SO 9.52 Curative DYHARD 1.O 1.O 1.O 1.O 1.O 1.O Steel CS O.12 O.85 O.13 1.21 250 m gap, Failure Mode* af af af af UR700 100 mm/min DYEHARD 10OS 4.6 4.6 4.6 4.7 4.7 4.7 Oiled EG X. 7.38 7.29 6.09 6.52 Steel CS 0.79 1.57 O.31 O.O2 DY965CH = PU adduct, commercially available from Huntsman (now Hex cion) 250 m gap, Failure Mode* af Af af af ZP507OHV = adhesion promoter 100 mm/min SILQUEST A187 = alkoxysilane epoxy adhesion promoter Oiled CR X. 11...SO 15.07 13.51 16.33 TCP = tricresyl phosphate Steel CS 1.30 18O O.66 1.07 NIPOL 1411 = acrylonitrile-butadiene rubber for adhesion 250 m gap, Failure Mode* af af af af SYLOTHDX 53 = thixotrope thickener 200 mm/min * af= adhesive failure, cf= cohesive failure 0170 Table 4 provides structural adhesive formulations of X is the mean result, O is standard deviation. two adducts using Adducts 1a and le—with similar molecular weight backbones (about 2000) but based on dif 0168 Table 2 shows that each version of Adduct 1 gives ferent polyether backbones i.e., PPG 2000 and polyTHF good T-peel strength/adhesion on various types of oiled steel. 2OOO. US 2009/024.0003 A1 Sep. 24, 2009

0.174. The evaluation in Table 8 was conducted on oiled TABLE 5 hot dipped galvanized steel peel test coupons of a 0.8 mm thickness in accordance with ISO 11343, using a bondline Wedge Impact Peel Sample Nos. thickness of 0.25 mm for T peel strength at 180° C. (N mm) (a) V VI. VII VIII IX X TABLE 8 RT X. 40.O 44.5 45.3 37.O 42.6 45.2 CS O.3 1.S 3.3 1.9 4.1 1.9 Sample Nos. –40° C. X 27.O 42.9 39.2 3OS 46.3 39.1 CS O.S 1.8 1.5 0.4 3.2 1.8 T-Peel Strength (a) 180° C. XI XII HDG 100 mm/min oiled 10.9 8.6 0171 Table 5 compares Adducts 1a and le in structural % Cohesive Failure 10 5 EGS 100 mm/min oiled 9.1 5.7 adhesive formulations. The performance results of the evalu % Cohesive Failure O O ation of the formulations indicate that replacing polyTHF CRS 200 mm/min oiled 13.7 13.5 2000 in the adduct backbone with PPG 2000 shows some loss % Cohesive Failure O O of toughness. But, overall the results for both adducts are excellent compared to control Sample Nos. V and VIII, which contain Prepo2000LV and neither adduct. (0175. In Table 12, Sample Nos. XVI, XVII, XVIII and XIX have been prepared with increasing levels of barbituric TABLE 6 acid for comparison against Sample No. XVI, which contain no barbituric acid. Sample Nos. Component Amt (wt % TABLE 12 Type Identity XI XII Component Sample Nos./Amt. (parts Epoxy EPON 828 15.6 15.6 Type Identity XVI XVII XVIII XIX EP 49-1ON 2.0 2.0 Toughener Adduct 1f 1S.O 1S.O EPON 828 15.6 15.6 15.6 15.6 ZEON F351 6.O ADEKAEP 49-1ON 2.O 2.0 2.0 2.0 DY965 CH 7.0 7.0 Stabiliser Barbituric acid 2.0 4.0 6.O Filer NIPOL1411 1.0 1.0 Toughener Adduct la 1S.O 1S.O 1S.O 1S.O CABOSILTS 720 1.5 1.5 DY965 CH 7.0 7.0 7.0 7.0 CALCIUMOXIDE 2.0 2.0 ZEON F351 6.0 6.O 6.O 6.O SYLOTHIX 53 O.S O.S KANEKAMX 153 42.O 42.O 42.O 42.O Adhesion SILOUESTA-187 O.2 O.2 Adhesion ZP5070 HV 2.O 2.0 2.0 2.0 Promoter ZP507OHV 2.0 2.0 Promoter TCP 2.2 2.2 2.2 2.2 TCP 2.2 2.2 SILOUESTA-187 O.2 O.2 O.2 O.2 Curative DICY 4.7 4.7 Filler NIPOL 1411 1.O 1.O 1.O 1.O DYEHARD UR700 1.O 1.O NYAD 400 1.4 1.4 1.4 1.4 CaO 2.O 2.0 2.0 2.0 *70% polyTHF + 30% PPG 2000 + TMP + HMDI+ 3,6-dioxa-1,8-octane CABOSILTS 720 1.5 1.5 1.5 1.5 dithiol SYLOTHIX 53 O.S O.S O.S O.S Curative DYHARD 100S 4.7 4.7 4.7 4.7 0172 Table 6 shows Sample Nos. XI and XII as structural DYEHARD UR 700 1.O 1.O 1.O 1.O adhesive formulations that use Adduct 1 f as an additional toughener. The results of the wedge impact evaluations of Sample Nos. XI and XII are set forth below in Tables 7 and 8. (0176). As seen in Table 13, the addition of barbituric acid 0173 The evaluation in Table 7 was conducted on grit was shown to stabilize the viscosity of the formulations. blasted mild steel impact peel test coupons of a 0.8 mm thickness in accordance with ISO 11343, using a bondline TABLE 13 thickness of 0.25mm for wedge impact performance at room temperature and -40°C., for dynamic resistance and impact Sample Nos. energy. Viscosity Stability (a) 50° C. XVI XVII XVIII XIX Initial Yield Point 2004 1847 1933 1643 TABLE 7 n (c) 20 seconds 1643 151.3 155.7 136.8 16 Hours Yield Point 12560 S841 4786 4376 Sample Nos. (a) 50° C. m. (a) 20 seconds 696.4 344.6 296.6 275.6 40 Hours Yield Point Torque Torque 6214 6362 Wedge Impact (a) XI XII (a) 50° C. m. (a) 20 seconds Overload Overload 376.6 375.2 64 Hours Yield Point Torque Torque 9646 883O RT (a) 50° C. m. (a) 20 seconds Overload Overload 559.9 526.4 160° C. for 22 minutes 40.7 - 1.1 43.21.3 180° C. for 30 minutes 43.3 O.7 47.4 O.7 190° C. for 1 hour 34:12.7 31.6 4.8 0177 Table 14 provides Sample No. XX containing -40°C. Adduct la that was prepared for determination of fracture toughness. Fracture toughness ("Glc') is measured using the 160° C. for 22 minutes 32.6 0.6 32.72.O 180° C. for 30 minutes 37.3 1.5 40.6 - O.3 tapered double cantilever beam methodology as laid out in 190° C. for 1 hour 27.6 2.1 33.33.0 STM-799, using an adhesive layer thickness of 1.0-5 mm, a pull rate of 0.1 mm/min, a test temperature of 21-23° C. on grit blasted steel substrates. US 2009/024.0003 A1 Sep. 24, 2009 20

TABLE 1.4 TABLE 15-continued Component Sample No. Amt (wt %) Specimen G1c Integral No. J/m2 Type Identity XX 5 7750 Epoxy EPON 828 13.17 Mean 7405 EP 49-1ON 1.78 CS 337.1.24 Toughener Kaneka MX 153 41.0 Adduct 1 a 1S.O ZEON F351 6.O What is claimed is: Adeka QR9466 7.0 1. An adduct comprising: Filler NIPOL 1411 1.O CABOSILTS 720 1.5 I CALCIUMOXIDE 2.0 H H SYLOTHIX 53 O.S X N-N X-Q-SH NYAD 400 140 R R WOLLASTOCOAT Adhesion SILOUESTA-187 O.15 Y Y Promoter ZP507OHV 2.0 TCP 2.2 wherein R is selected from the group consisting of backbones Curative Amicure CG 1200 4.3 of polyethers, perfluorinated polyethers, polyesters, perflu DYEHARD UR700 1.O orinated polyesters, polydimethylsiloxanes and hydroxy ter minated polybutadienes; 0.178 Sample No. XX was evaluated for fracture tough- R" andfrom Q the are groupindependent consisting from of one alkylene, another arylene,and are selected alkyle ness, results of which are summarized below in Table 15. neoxy and aryleneoxy; X is selected from the group consisting of O, NH. S. S=O, TABLE 1.5 and O—S—O; Y is selected from the group consisting of O and S; and Specimen Gc Integral n is 1-4. No. Jim 2. The adduct of claim 1, wherein the polyether backbones 1 7553 are selected from the group consisting of polypropylene gly 2 6930 col, poly THF, polyether diamines, and mercapto-functional 3 7606 ized polythioethers JEFFAMINE type backbones. 4 7187 3. The adduct of claim 1, selected from the group consist ing of

1 O O s1n-1'N-1N1)-1 N (OCH2CH2CH) (OCH2CH2CH2O) N1 O r S N-1 no-1S-1 O N-1Ns. O

O O HS N-1 no-1-1 O N-1\s us N-(H.C.-N ls (O(CH2)5CO) O(CH2)3 y —o y – Me Me O O -(CHOO-(CO(CH, O,ls N-(CH-N 1N1'N-1-1-1O SH O O y y HS N-1 no-1S-1'N-1NsO ul HN-(CH2)-NH lsO- (CH2CH2O)(CH2)3 Me–o Me– O O -l NH-(CH2)-NHls s1N1 O N-1 no-1N-1 SH

US 2009/024.0003 A1 Sep. 24, 2009 22

17 y y OH No in-N-N- n-chi-o- Me Me CH O l H -CHCH-NH N H Nin-r-in CH3 O 2 wherein n is 1-40 and X is 2-50.

18 y y No N-N- Ni-cis-os Me Me CH

H -CHCH-NH N H NS-S-N- CH3 O 2 wherein n is 1-40 and X is 2-50.

19 O O y y ls ls Si"No-h1 Si-(CH2)-O NH-(CH2)NH NH-(CH2CH-O).- Me Me CH3

O -CHCH-NH l N S N-1N1)-1'N-1O ns CH3 O 2 wherein n is 1-40 and X is 2-50.

Me Me O O

inO -city. ls Me Me HN-(CH2)-NH N-R-(CH2):NHCO-((CH-CH)-(CH,-H CN US 2009/024.0003 A1 Sep. 24, 2009

-continued O l H -CH=CH-CH), ICO-NH-R-NH N NS-S-N-> O wherein n is 1-40, m is 3-10, X is 0-10, Y is 0-10, Z is 0-2, R whereino is 1-4, X is selected from a direct bond (when o is is an alkyl or a cycloalkyl radical and p is 1-4. 2), alkyl (when o is 1), alkylene (when o is 2-4), carbonyl 4. A thermosetting resin formulation comprising: (a) the adduct of claim 1; and (when o is 2), thiol (when o is 1), thioether (when o is 2), (b) a thermosetting resin. sulfoxide (when o is 2), and sulfone (when o is 2), R is 5. The formulation of claim 4 wherein the thermosetting selected from hydrogen, alkyl, alkenyl and aryl, and R is resin is a member selected from the group consisting of epoxy, episulfide, benzoxazines and combinations thereof. selected from hydrogen, halogen, alkyl and alkenyl: 6. The formulation of claim 4 further comprising a solid organic acid. 7. The formulation of claim 6 wherein the solid organic acid is a member selected from the group consisting of quino nes, phenols, and enolisable materials. 8. The formulation of claim 6, wherein the solid organic BOZ-B acid is a member selected from the group consisting of be selected from 4-nitroguaiacol. 3,4,5-trimethoxy benzoic acid, hexachlorophene, 3,5-dinitrosalicylic acid, 4.5,7-trihy droxyflavanone, 2.2-dithiosalicylic acid, phloroglucinol, fumaric acid, 3,4-dihydroxy benzoic acid, 3,4,5-trihydroxy benzoic acid, trolox, pamoic acid, ascorbic acid, salicylic acid, citric acid, 3,4-dihydroxy cinnamic acid, 2,3-dicyano hydroquinone, barbituric acid, tetrahydroxy-p-benzo quinone, parabanic acid, phenylboronic acid, 5-phenyl Mel drum's acid and Meldrum's acid. 9. The formulation of claim 4, wherein the thermosetting resin is a member selected from the group consisting of wherein p is 2, Y is selected from biphenyl (when p is 2), BOZ-A diphenyl methane (when p is 2), diphenyl isopropane (when p R is 2), diphenyl sulfide (when p is 2), diphenylsulfoxide(when p is 2), diphenyl Sulfone (when p is 2), and diphenylketone (when p is 2), and R is selected from hydrogen, halogen, (. o X alkyl and alkenyl. 10. The formulation of claim 4, further comprising a \/ toughener.