kgr&aadi of Iffveatfoji

p)S2| Adhesive compositions are sed to bond glass (windows) into buildings and vehicles, see Ri¾k _s .US. 4,780 J20;. Bhat U.S. X M _l Hsieh et af U.S. 01S _S 47S and Zhou, IJ,S:. Meat i$;70„>,S3¾ all incorporated, herem by re&renee, ftt automobile factories windows are in ledw g robots and computer controlled processing which facilitates the use of a variety of high perf mtee adhesives, for i sfatice noncoiada tfive adhesives a high modulus; adhesives. The speed of ciire is not- a sigmfteasn issue because new vehicles are not driven a s gmfieasit distance for several days afte window installation. When a vehicle needs a window replaced,, it is often pe forate m a remote location by an instafe working- t the vehicle to be repaired. & his environment, speed of cure is importsat as the vehicle owner desires to drive the vehicle as soon as possible after installation, of the window. Adhesive* M hi replacing windows for vehicles, which facilitate last drive away times are know see: Bhat, U.S. 5,976,3 5 and Zhou. US. 6,709,539. The introduction of. various high performance adhesive compositions used for installing- windows in automobile factories presents a problem for replacement window installers. First, adhesives that rneet ail the varied performance requirements are not sy&iiahle in the market place. Second, it is difficult to Jbrnmlate many high, performance adhesive compositions to a!low r¾piti drive away times that do not sag or string. Sag i thedoss of the; shape of the adhesive bead, often as die result of gravitational forces. If severe enough, this, deformation can interfere In the proper installation and sealing of die- -window oft the vehicle, Siri.ag.in of an adhesive is- the formation of a long, string, of adhesive at the cad of the head alter dispensing which ca oprapfeate: application sod c ase imperfections i the installed adhesive bead. Replacement window iftstajiers often carry a/v&riety of adhesives to matc the adhesive o the properties of the original adhesive used , (0031 Isocyanate functional adhesives are utilized for bonding glass into structures and contain plastickers to adjust the rheoiogy and dispensability of these adhesives. Typically, piastkizers used in isoeyaiiafe ftaicfional adhesives were adopted initially from piastiekers developed -for use in poly vmyi chloride nkstisol eoffipQsSioirs beeau.se of their cost andavaiiibliity.

-i- 0¾e eom rr c¾m oiplastie srs used k iswy ≠& _. u cti nal adhesive? are alkyi phatfeat s. Such: e i«pOB»o¾ to date, ha^ ^' been available and: eosi ^' --efleei&e; Recently; however, BH eonoe s. have beers raised about these materials negatively impasting the cost aa availability, ^' There s a seed to find new lasikizers .for ixocyanate fractional adhesives, M\ What is needed is ^: a compos lioivwh eh is aseful as an. adhesive for bonding- glass into a sttuc-tam which may be■ formulated to exhibit a variety of high performance- properties (such as high modu!ysand noncondaetive- nature), exhibits fast sat drive away t mes hea applied. m)der a variet of conditions, last strength develo ment, can, fee applied wit ou the ne d for heating the adhesive, can be ap l ed Mder. a wide range f environmental conditions, does not require expensive ingredients, can be applied to glass ithout the need for a primer and does not. sag or string when applied. Compositions containing, plastje ers adapted for use with Kiosyanate functional adhesives having lo viscosities, desirable pokrity. high boiling j¾oi»t¾ low volatility, derived, from renewable - esources aire ne ded.

Si||¾n¾ of Invention

|0 | We have discovered plastieijsers derived front renewable sources that have or one or more of the following: a polarity fe form homogeneous, blends with an isocyanate adhesi ve; Sow water content pie-venting premature owing of such adhes es;: low viscosities to facilitate adhesive formulation flexibility including, for example, higher filler Concentrations and _. lower dispensing pressures; and high boiling points to prevent release of volatile organ? es to the environment

\ in one embodiment the Invention Is a: eoiil sltlon comprising: a) one or store- isaey«aaie _. functional components; b) a blend of one or more C _M alkyi esters of C aikenoates, wherein the total carbon atoms of the. alkenoates Is from 11 to 22, ami one or more C _} . _s alkyi esters. f C _¾ alkatioat.es, wherein the total carbon atoms of the aikanostes is from 11 to 22; and c) o s or rnore catalysts for the reaction of isoeyaiiaie moieties- with hydroxy! groups. Preferably the ^■ alkyi. esters of a!kenoates exhibit a melting point of about - 10 °C or less and one or more , alkyi esters of alkanoates exhibit a. mel ng point of about 30 *£ ^■ or greater, .-Preferably the blend, exhibits a dielectric constant of §5. or greater, a boiling point :of 200 ¾I- o greater, a viscosity of about- 40 eenlpoise or less at 25 ¾ and a vapor ressure of ahoa .!. MPa or less at..25 ^< ¾. Preferably the blend of one or more alkyi esters of alkenoat s and oae. or more alkyi esters of alkanoates- are derived fern one or more na oml oils, exemplar natural oils include soy, shallower, saffio er, rapeseed and cottonseed, oils. Preferably one or more carbon blacks a e present In the composition. fW7| ¾ another embodiment the inverrtiorr is a method of bonding two or more substrates tog^her ca prlsiag c irfseiing wo or more substrates to her with a composition of mention disposed along at least a portion of the are wherein the sabstrates are in contact, ίθδ8| Is ye another embodiment the invention is a met od of replacing a window of a ehicle comprising: i) removing the indow from the vehicle; li) applying a com sition according- to the invenHoa to a ^plac ment window or ip the flange of the vehicle adapted to hold the ind w Into the vehicle; jit) contacting the flange of the vehicle and the replacement window wit he; coftipceitian: disdosed between the re laceme t windo mA the flange: of the vehicle;, and iv) a!ipwmg the .ad esive to cure,

f The composition ¾ useful as m adhesive to bond suhshMes together. A variet of subsha es, similar or dissimilar, way &e b nded together wsin the eons position, for instarree, plastics, glass, ood ceramics, si¾etaL coated snbsttaics, such as plastics with an abrasion esis nt coal ng disposed thereon, and the like. The compositions are especially useful . for ^■ bonding glass or aplastic with aft abrasloa rosiistaai eosi g disposed thereon to other snhstra&s such as vehicles and buildings,. The .compositions are also yseihf in bohdmg paris .of modular eompMeaiy together, snch as vehicle Modular com o ents. The glass or plastic with an abrasion re&istaut coating disposed thsreos cab. be tended id coated and unseated, portions of vehicles.

[00101 The coaipodiions typically d monstrate, after being cared, for two weeks, a modulus of about 2,0 MPa or greater, preferably about 2.5 MPa. or greater and typically, about 5.0 MPs or less aceofdinf to ASTM . D4065 measured at 25 ^:3 C. Th compositions of the iave ierr .typically exhibit a.sterage.modttlus,. of about 1 x 10 ^¾ MPa or greater, prefeably akmt 11 x tit i½ or greater and aiost ^' iprefembly abopr 1.8 ^' x 10 ^β MPa or greater after being fully cured, for instance or 7 days at 25 °C 50 pereenirelativs kmudiry .

\ ίί] The eompositioij¾. pa pabil¾ isay be i dic ed by measurin the press flo viscosity according to the test described herein aod preferably, exhibit a press flow viscosity of ahotit 25 to about 19 ⁽ 1 s conds, most preferably abou 25 t about 50 seconds, Tbe eompos ons allow preparation of adhesives with: a ledncsd: fllierlevc! and an acceptable: modulus in the tmenrsd. siafe.(G~Modidus}, ih&tk tlie compositions maintain the .raodiihia at reduced filler levels.

Detailed De¾enptioa of _; ¾yept on (SOU) ^' Goeor more as. used nere¾ metift thai at least , or more than one, of tie recited components may be used as disclosed. Nominal as used wi respect to functional^ ifceans th theoretical i½ctio.na1My ₍ which can. be calculated from the stoiehiometry of the ingredients used. Generally, the actual fenc-tionalhy is■different due to imperfections in -raw materials. Incomplete conversion of the reaetant and. formation of. by-products. "Durability" m herein means- that the. composition once eared rema ns -sufficiently ^' stro g to perform its desiped -ftmetion,- in th embodiment wherein the e-u ^' red composition is an adhesive the adhesive holds substrates together, for the life or most of the life of the structure containing ^' ths cured composition. As an isdicator of his durability the curable c mp sition ^' {6.g, adhesive) preferably exhibits excellent results during accelerated aging _, testing as described herein, Preferably this means that after -a. set of substrates bonded with the adhesive of the invention is exposed to heat agm¾ the failure m de in -Quick Knife adhesion or Lap Shear testing is cohesive, meaning the adhesive breaks before the bond of the adhesive to the substrate breaks, "fsoepmrte eontent" ^' .m%s the weight percentage of isoeyanate moieties bssed on, the total weight of & pmpolymer. The tens soeyanste--reaeiive eompound" as ssed. herein- incl es- an organic compound having- riominaliy at least two isoeyasate-reae lve moieties. For me purposes of this invention isocyanate-reaciive moieties include active- hydrogen containiag moieties and preferably refer to moieties containing a hydrogen atom which, because, of its position in. the molecule, displays significant activit according to the Zetwitfeoff test described by Wohier m the Journal of the AmsriearvChemieai Society, Vol . 49, p. 318.1 (027). Iseeyanate reactive moieties include -COOH, -OH, -HH _¾ ~CGN¾ -SH, and -CORH-, Preferable isocyanate reactive moiety containing, comp unds include polyols, poiy- amines, po!ymercaptans . and poiyaejds, more. referably polyols, and most preferably a polyether polyols.

10 131 The compositions invention can- be any reactive system eontaidng isocyanate ^'

..functional components, which are curable. ^Reactive" means herein that the curable composition (eig-. adhesi e) contains comppnenis which react to form a polymeric -matrix that is set-irreversibly once etsred. The eunihle s stems can be either 01» or two-part systems. Preferably the curable systems are useful as aiShesives. f#u ) Isocyanate based (pol u hane or pol we forming) curable systems comprise as isocyanate functional component. An isocyanate functional com nen contains _: o¾e or mo e ^' compounds, having on average more tkm one isocyanate grou per molecule, The isocyanate fenotionai compound ca be any e-ompound h¾h. contains- n average more than one isocyanate itsoiety. The isocyanate functional compound can be in. th form of an. :isdeyanaie ^: functional prep0iya¾ef or la the form: of a monomer or oligomer having on average greater than i Isocyanate grou , arti! preferably 2 or more imey&riate groups. The i ocyasaie prepolymer car* be any prepoiyraer re ared by reaction of an isocyanate ^' functional, compound, with one or more Compounds having- on average more than one isocyanate reactive functional groaps, such as hydroxy!., anuae, thiol carboxyl and the like, unde -.eosditi ms such that the prepo!ymer prep red have ors average .mo e than one isocyanate moiety (group) per luolecitle. Preferably the -compounds having isoe arsiSe reastive ou s have on average about 2 to about 4 isdeyanais reactive groups. The isocyanate - functional component is: present is the curable, composit on in a. sufficient amount to fqrnt a cured component when ^' exposed tp _: o«rfag c ndi ns. In two-part adhesive compositions,, the isocyanate functional components when combined with isocyanate reactive compounds re capable of bonding substrates together in -a manner thai: the sabstrates remain bound together when exposed to temperatures of about -30¾ to about . H FC for long periods of time, such ^' as 10 ^' years; .and: ^ :t ^: ra era¾n¾s of about 1:8 *0 for bon periods of up to 3(1 minutes,: f8SI§! In a One-part system, the isocyanate functional eomjpoaerrf farther eoinprises a catalyst, and other components as described hereinafter:. The one component adhesive systems typically cure by moisture curing. Once formulated the one-part adhesive systems are generally packaged in air and moisture proof containers to prevent curing before, application. f¾M&| The curable: system -May be a two-part polyisOeyanate containing curable system..

The two parts are reactive with one another and when contacted undergo a caring reaction. One part of the composition comprises, or contains, an isocyanate functional component, typically referred to. as the resin-side or A side. The othe component of the composition is an isocyanate reactive component which comprises,, or contains,, one or more c m un s, oligomers or prepolymers having on average, more than am group reacti ve with isocyanate ^' moieties as described herein, connnonly known as th curative or B side. Compounds having on average one or more isocyanate reactive groups CM be ¾:p lymefs.o:r can be/ sjnall. chain compounds: such m difune- tipnal chain extenders or paiy&nciiona! crossiinfcing agents known in the art. A. catalyst as ^• described herein may be utilised in the curative side. The reaction product is a cured product which is capable of performing the. desired -function, such as bonding certain substrates together.

|0Θ1.?] Tfie socyanate ftnetlona! components, such -as isocyanate functional prepolymers, are present in sofilcient quantity to provide adhesive -character to. the composition. Such isocyasale functional Components ^' have an ^' verage isocyanate functionality sufficient"!© -allow the preparation ofa .ero inked:pdlyiirei aiie upos cure and not so hig that t e cu ble: e-oiPpositiOns are -unstable. St ¾i! in. this, context mean ^' s ^' iiiat the Isoeya te ft Otiomd COmpon ts or adhesi e prepared: fom ^'' the isoeyanate functional components have a s elf life of at ^; least 6 molis at - mbient, temperatures, in that it does not demonstrate an increase in Viscosity during such period which prevents its application or use. Preferably;, it does not undergo an ncrease in viscosity of more, than about 50 percent during the slated period. The isoeyanate functional components preferably have a ires isoeyartafc content which facilitates acceptable _. strength in . a hesi e prepared therefrom after 60 .minutes, and stability of the enable conipositioa. The isocyanate functional components preferably have a _. free isoeyanate content which, facilitates acceptable strength In the compositions prepared therefrom, preferably after 30 minutes, more preferably after 15 m nutes. In ris co&ponest. ad esives, the ftee ^: tseeysnate content is about 0.8 percent by weight or greater ba ed oft the weight of the prepolyroer and mons preferably about 0,9 percent by weight or greater, and preferabl about 2.2 percent b weight or less, more preferably about 2,0 or less, even more .preferably ^' about 1.4 percent by weight or and even, more ..preferably about 1,1 percent by weigh or less and most preferably about 1.0 percent by weight or less. In two par compositions the isoeyanate content in the isdeyanaie ibseiioaai components is preferably about 1 percent by weight or greater based on th : weight of the isoeyanate ftaftkmd eonipnnents, mots preferably about 2 percent by weight or gr ater, eves more . preferably about percenter greater, even more eferably about S percent by weight or greater and most preferably about 10 percent by weight or greater. The isoeyanate content, in the isoeyanate functional components of two part compositions is preferably about 35 percent by weight o less based on. the weight of the iSQcyas&te functional components, more: preferabiy abou 25 percent by weight or less, even more preferably about 20 percent by weight and most preferably about 15 percent by weight or less.

|9018 ^' | Preferable polyisoeyanates tor use- in preparing the isoeyanate nmetlonal

^•• com onent .include those disclosed in U.S. Patent 5,922,809 at eolitnm 3, line 32 to column 4, line M incorporated -herein by reference. Preferably; tlife polyisoeyana!e is an aromatic orcyclosliphatic poiyisoeyanate sueh as diphenyl:meihane-- ⁱ i4 ^! -di:isoeyariaie, isophorone diisoeyanate, tet asnethyl- xykue dbsocyanaie, and is most preferably diphenyimethmie^ _:! 4 ^s -d.iisoeyaiiafe. The polyols reacted with the preferably comprise one or more polyols having from about 2 to about 4 %dro¾yt groups, and. are preferably a. raptu e of diois and triols, Polyols useful in this invention, are. diois and triofe corresponding to the polyols described In US, Fateat S,92¾809 at column 4, ike 60 to _: column S, Hue 5 Incorporated herein by reference. Preferably, the polyols nlfo!s a trials) are polyether polyo!s arid, More prefera v polyoxyal tei¾ oside poiyols, The ^: most preferred triok are ethylene oxide-capped poiyols .prepared y eac ng glycerin with ropylene oxide, felfowed by reacting the prodw with eihyleijcoxlde. fWI&j ί» one preferred embodiment the isocyariate funciional prepeiymer coataias one ot more organic based poly erpaftic!es dispersed therein or grafted to the backbone thereof. Preferably, the organic based polymer particle is included m the prepolymer by el sson of a triol having dispersed therein or -grafted to the bbaekbose particles of an orgask based polymer. The preferable riois are disclosed in Zhou, 0,S. Patent 6,70%539 at ebtahin 4, .line 13 to c lonia l line 18, incorporated .herein, by reference. Preferably, the triol is a olyethertriol and aore preferably a. polyox alkyleee based trio!. Preferably, such polyoxya!kyiene Oxide triol comprises- a pdlyoxy- propylens chain with a po ox>¾ fc«e end cap. Preferably, the- orga ic based polymer particles comprise a thermoplastic, polymer, ruhbei-m-odi ied thermoplastic polymer or a poiy rea dispersed m triol Preferable thermoplastic polymers are those based o« ifto»oV½lide e aromatic motsomers arid c pol ers of on irfyliderie ammatk- m nomers with conjugated dierses, aor ia^. aidfc¾cfy|¾tes, unsaturated aitriles or « x¾res thereof. The eopolymers ears bo block or andom copolymers. More preferabl the particles comprise copolymers of unsaturated nitrites, coajugaied dienes and a. onovinylidene aromatic moaomsr, -a? copolymer of an u saturated nitrik nd a ffioitovmyhdsrse aromatic monomer or a olv es. eves more preferably a polyure or polystyfeae-acrylonitnle copolymer with the polystyrene-aerylonitrtle copolymers being- raost efe red. The organic polymer particles preferably have- a particle size which is- large eaoagh to improve the- impact properties and e!&stomerie properties _. -of the finally cured adhesive, but not so large so as to: reduce the ultimate strength of the adhesive fter, cure,. Preferably, the particle- is about 10 microns or ipmter add more preferably the particle size is about 20 microns or greater. Preferably, the partkk size is about 50 microns or less atfd more preferabl the particle size is -about 40 microns or less. The triol contains a sufficient amoani of orgamc polymer particles such that the adhesive: upon cure has sufficient ardaess-i rthe desired use and not -s much such that the cored adhesive has too much elasticity as defined by-^ongatioa. Preferably,, the poryo!s-coatain about 2 percent by weight or greater of organic polymer particles copolymer based, on thep lyols and parikks, preferably a u 30 percent by weight or greater and mor preferably about 35 percent by weight or greater. Preferably, the poiyols -c ntain- about 60 jperceftt by weight or less: of organic polymer particles based on the poiyols and particles, preferabl about SO e cent by weight or less and more -preferably about 45. percent -by -weight or less. The poiyols- containing organic pofymej? particles in a trioi may preset is the ¾oI mer in an amount of about 10 percen by weight sr ^' greater of the prepoiyrher and more preferably about 12 percent by ^' w¾fet ^' or greater, and about IS percent by weight or less of the prepo!y ef.

{6020} ^' Tlie polyo!s are presen in an mount sufficient to reset w th most of the jsoeyansie groups leaving enough isocyatiate groups to correspond ^' with (fee desired free isoeyanate eontent of the isoeyafiate ;&nenon&! component, Prefersbly, the po!yois are present in w amount of about 30 percent by weight or greater based ^' on the prepolymer, more preferably -about.40 ercent by weight or greater and most preferably about 55 percent by ei h or greater. F^eferahly, the polyols are present sn an. amount of about 75 percent by weight or {ess based on the prepo!ymer, more preferably about 65 percent by weight or less and most preferably about 60 percent by eight or less.

(0823 J The isoeyanate. functional com ne t may further eorspnss, a blend; of one or more C _t , ₂ aikyi esters of C ^ lkenoates and one or mo e C _M alkyfesters of C _iS . _2e aikanoates; one or m e cotnmoa pl s ki s or mktnrss hereo . The p!astici¾ers useful in the isoc n ^' ate hmctlouai component are commo plasticizers useful m p iywet ae adhesive applications and wet! knows, to those skilled in the a il The plastkkers are present in an amount sufficient to disperse the isocyanate funet nai componen in t he &a! adhesive composition, The plssii zers can; be added to the adhesi ve either during preparation of an isoeyanate functional component or during compounding of the adhesive composition. Preferably, the plasticizets ate present in about 1 percent by weight or greater of the isoeyanate functional component formulation (fot example prepofynier plus piastieizer), more preferably about 20 percent by weight or greater and most preferably .-about 30 ^■ percent b weight or greater, P efer bly^ the plas&isier is present in about 45 percent by weight or less of tho Isoc anate functional component formulation and mo e preferably about 3 percent by weight or less,

i22 The isocysuale fonctiona eon-iponents prepoiymera ma be prepared by any suitable htefStod, such as by reacting palyols with an excess ove stoiehipraetr of one or more pe ylsocyanafes under reaction: conditions sufficient to form a preppiynasr having isocyasMte fimciiohaiity and f ee isoeyanate content w iieh¾esis the criteria discussed above Preferable processes or the preparation of the isoeyanate functional components, are disclosed, in U.S. Patent $,922.809 at col man , lines 4 to 51 ineorpomted herein by reference, The isoeyanate functional, components are present in the: adhesive composition In an amount sufficient such that when the resulting adhesive cures substrates are bound together. Preferably, the. isoeyanate functional components are: pr sent in amount of gfeaui 20 parts ^' by ¾¾ight of the adhesive e i» esi¾ n or greater, more preferably about 30 parts by weight or greater &ϋ<ϊ. most pretoMy abom S parts by weight or greater. Preferably,; the !soesimate functional c m onents a e presets! m m amoun of about 60 parts by weight of the adhesive composition or less, more preferably about 50 parts by weight or less nd even, more preferably about 4 parts fey weight or less.

[8023] The eomposlton of the Invention, com rises a. blend of one or mor C ^' - alkyi esiers of€ j^ lken ates, wherek the total carbon atoms of the alkeiroates is from 11 to 22, and ooe or more C _if8 alky! esters of C a&aooates he ein the total esrbosi atoms of the aika«oates is from 11 to 22. Aay a bl nd of on or mom alky! esters of aiksrioates asd one of more alkyi esters of aikartoates; that euhaiiee the rheotegy and applicability of he composltioas may be ilixec! tie compositions. Preferably the blend e>dubii a polarity sufficient to farm hot ogeueoas blends with the components of the Isoeysnate fUaettonal adhesive, Prefathly, _. die blend has a suffidet l low water ^■■ content s¾eis thai the adhesive does not euro dbrihg storage, hat is the stored Ibrmu ons: are stable as discussed he e n. Prefeirbly the water £ t¾¾i is about -Ml per ent by weight or less and. More preferabl about QM weight peiceat or less..

W&4\ Preferabl the blend exhibits a strfl cie i. lo viscosity such that the formulations of the Invention cm e τ ά and ppl ed, preferably at temperatures from IS to 35¾ ₅ par&uiarfy with standard application equlptngrit used in original equipment manufacture and in glass replacement processes, Preferably the viscosity of the blend is such that the Isocyanate iUiict o l adhesive ex ositio is: applicable usixig stauda^d equipment. Preferabb/ lic viseosity of th blend is ab u 100 eearipoise or less at 25 and most preferably shout 60 eentipoise or less at 25 Preferably the viscosity of the blend is. about 40 eerhipoise at 25 ¾ and most preferably about 2 cemipoisc at 2 *C, f 80251 The blend desirably ex ibit a sufficiently high boilin point such that the com- posiePts of the biead do not voiafliiae hxto th ^v' e.n. toimeni during applieaiiotr aad use. ^' The blend exhibits a boiling point such that the eveht ioii of vols ile rianies is very low below 0.5 percent by weight or immeas rable., measured using EPA Methocl 2 , mi preferably is afaonl 160 °C or greater, more preferably aboot 200 °G. or. reater: md most preferably about 220 or greater, Preferably fee vapor pressure of the blend .is ahou 0.061. kPa or less at 25 *C md most preferably about: 0.01 RPa or less at 25 °C. Desirably, the blend exhibits a dielectric eoostaut to chiev the desired polarity* preferably atetti 6.5 or greater aod most preferably bout 7.0 or greater. 02& Th one or more G _t - alkyl esters ¹ of C _ws alkcooates preferably eorrfcspo»d to the fornuda R .€(0)OR ^s wherein R ^! is se arately ¾ each occurrence a C _S:(½¾ s!ksayi groB i R ² i separately in eaeb occurrence a€ ^ alky! group wherein the total, carbon atoms of ^! sad R ^J' is from Ή to 22 Mid h preferably from 16 to 20. Alkenyl group as used in this contes is a straight or branched carbon chain containing one or more double bonds. Preferably the carbon chains contain fr m one to three double bonds and preferably one or two double b nd * Most preferably the C t- _: alkyl esters of C alkeaoates are comprised- of ^' molecules haying carbon chains with one doable bond; (mone-ene) or carbon chasm with i^a doable, bonds (dienes). R ⁵ is ^■ . ^' separately in each ccu rence a C _½ ,¾- iUkenyl group. .Preferably Hi ⁵ is¾cparatoly in each occurrence C : alkyl _* more ^' preferably niet!ryl or ethyl and most preferably methyl. Preferably the alkyl esters of sik noates comprise one or more C _M aikyi esters of C al&eaoates, ma e preferabl one or ore C _M alkyl esters, of C alkanoates and ost preferably C .alkyl esters of€ _J&¾} alkeooates. The alkyi esters -alkeaoates may comprise both mon-enes and dhenes. The alkyl esters of albenoates preferably exhibit low melting- points and viscosities, Preferably the melting points arc about - IB X w below and more preferably about -20 X or below, Preferably the viscosities ar about 1 _. 00 eerftipoise or less at 25 X and m ^' osi preferably sbont SO eenti oise or less at 25 X. Preferably the C alkyl esters of C alkenoates. exhibit flash points sneh thai ihe blend does. not release volatile orgaaie comp unds: In use. Preferably the flash point ^' i about 260 X or less nd most: preferably about 160 X or less. Exemplary C « alkyl esters of C alkesoates include methyl cis 9 >ciadeeen¾a& (also named methyl oleate and. methyl ester ^' of. oleic acid) and methyl oetadeeadieaoate (also named et l hnoiekidie ester), methyl ester of Knolenie acid, methyl ester oi ^' ga eleic acid, methyl ester of eivetie acid, and methyl ester of palmhoieic acid.

£062:7] The one or more alkyl esters of alkunoafes may be any such compounds that provide the desired, properties of the blend described hereinbefore. Such compounds preferably raise the flash point of the blend, to rednee the volatile, orgamcs from. volatilizing off from the lsoeyasate .fhnet.ienal adhesives dnrmg applieattor!, care ^' and use., The presence of s«eh compounds maintains the -dimension and shape of the bead of isoeyante Junctional adhesi ves applied to the substrate nd pre vents them from flowing when not subjected to shear. Preferably the alkyl esters of aikanoates are solid at 25 X. Preferably the alkyl esters of a ifomestes exhibit a boiling point such that when present in the bie«<i the blend demonstrated reduced release of volatile organic*. Preferably the boiling point is about .1 10 or greater, more preferably about 150 X or greater, and more: preferably about 200 X. or greater. £0028] I¾e one or mo e ¾lkyl esters of &lk¾npate« preferably correspond id the formula.

R¾ G)O ^J whemis ^;i and R ² ar¾ as i∞be< here nbefore. More preferably R ^3' is a€ _½ ., _¾ a&y1 group, Preferably the alkyl esters of alkaao&te comprise one or more C _M. alkyl esters of C- _w . dkaaoates, more preferabl one or more C _M -alkyl. esters of C _H § dkanoates and most preferabl € ₃ alkyl esters of C alkanoates. Exemplary alkyl esters of alkan ste Include methyl, hexadeeanoate (also named methyl palmitafe and palm oil methyl ester), methyl octadecaaoate (also n&toed methyl stearate and. sterie -acid methyl ester), ethyl oetadeeasoate (ethyl svearate and sierie a id ethyl ester), m th l ester of margarie add, and methyl ester of archidie acid. 0O29] The blend comprises- sufficient amount of eac of one o more alkyl esters o aikshoates and. one or ^' more alkyl esters of aik&noates to achieve the recited properties listed hereinbefore. Preferably the blend comprises about .70 percent by weight or greater of one or more al.fcy! esters, of alkenoates based on the weight of the blend and more preferably about SO percent b weight orgreaier based on the weight of the blend. Preferably the blend comprises about 0 percent by weight or less of on or more alkyl esters of aikenoates based oh the weight of the blend and mom preferably aho¾t S3 percent fey weight or less based on the weig t of fee bieod. Preferably th blend comprises about 5 pereest by weight; or greater of oae or more alkyl esters of aJkarieatss based on the weight of the blend and m re preferably about 1.0 percent by weight or g eater based on the weight, Preferably the bieod comprises about.20 percent by weight or less of one or more alkyl esters of aikarseates based on the weight of the blend and more preferably aboat 15 percent by weight Of -less based on the weight of the blend. The blend is utilized In sufficient arnout to impro ve the processability and sag of the isoeygnate ¾.nctionai adheslves. Preferably, the blend is present ¾ t¾© compositions of the invention In an amount of about about S .percent ^' y weight or greater and most preferably about 10 percen by- weight or greater,. The blend is preferably present . an amount of about 35 percent by weight or less and most preferably about 25 p f¾ent,by weight or less. The blend may he present in one- or both pasts of a two part composition, and preferably some Is present in the A part.

|0OMf The -blend of the one or --more alkyl esters of alkenoates and the one or more alkyl esters of .a!kanoates _. mm be prepared by mixing the comp nent or may be derived from natural, oil compositions. In. some embodiments they may he derived from natural oils. They may be derived from any source of natural oils thai allow the one ormore C ^ alkyl estersof C alkenoates and one or more C alkyl esters of€ alkaBoat.es to perform the recited functions. Exemplary natural ^' oils include soy, sunflower, safflower, rapeseed (e-anok), and mixtures thereof. More

- I I - preferred natural oils include s y* sunflower, .safilow, rep es ed, oil (ear¾>la and mixtures, thereof with soy and ..e noia p0s i^l.n .« o.si ^: p eife .r^> The natural oils eoriialn ^' triglycerides. The triglycerides are converted to esters Usin ail esterification processes, that is reactin the triglycerides with alcohols, such as .met anol Suitable processes include those- well koown in the art such s those ¾sed in biofttel- production. Preferably the resul in products contain 95 mole percent o greater of ester groups and most preferably about 99 mole percent A portion Of the resulting acyi groups may be aeids. ©δ?ί} The compositions may comprise blend of ^" the One or sno e alky] esters of a!kervoates nd the one or more aifed esters of a!femoates and cormrion plastic iscrs. Such materials should .be tree of water, inert to Isoeya te groups and compatible, withisoeyarsaie fiinctippal components. Exem l ry- comm n plasticissers in ^' clqd ne or snor of affcyJ. esters of stdfo s- acid, . a&yl aikyfeihefs diesters, polyester resins, fonnals, poiyglycol diesters, polymeric polyesters, t ica box lic esters, dialkyleihef iesters, - talkykther aromati esters, aromatic phosphate esters, ^• and aromatic lfott&mides, aromatic, diesters,: aromatic triesters, ^■ aliphatic (Hesters,, epoxidiaed esters, ep xide oils, chlorinated hydfoeafbons, aromatic oils, alfcylether olester , naphth nie oils, slkyl raonoe-sters, glyeeride oils, parr&fffoie ill and silicone oils. Common- plasl zers may be used in the adhesi ve composition in. a» amount of about 5; parts by weight or greater .based on the weight of the adhesive composition, ^, more preferably about. 10 parts by weight or greater, and most preferably about I S parts by weight or greater. The common plastieizers may be used in an amount of -about 40 parts b weight or less based on the total amount of the adhesive oomrx^ition, more preferably about 30 parts by weight or less and most preferabiy about 25 parts by weight or less. ffM)32] The composition: may comprise one or more isoeyanate fanet ^' tohal prepoiymers containing one or more polyester based polyols -whic are solid -at ambient temperature, about ^' 23 -C. The polyester based polyols have, melting points: such that the .pr^porymer provides sufficient; green ^' strength fo prevent the substrates from moving in relation to one another dse to gravitational forces at ambient teraperatares, In terms of Installing a indo m a vehicle or Hdiog, the polyester based prepolymer prevents the window from sliding after instal ation, P ferably, the polyester polyols have meitiag points: of about 4t °C:or greater, even more referabl : about 45 ^a C or greater and most preferably about 50°C or greater. l¾¾.fer¾bly, the polyester polyols exhibit melting points of sh rn S5*C or less, even mor preferabiy about 70°C or less and most preferably about 60°C or less. The polyester based isocyanate prepolymer can be prepared using one or mor polyester polydls. The amount of: olyester polyol m .the prepolyraer is a.sttfReieat .a omrt : fe provide the needed greea slrength to the composition of the invetttt p. aiPd to ender it solid ambient ie«ip*ratnres. Preferably, he polyester polyol is present in the polyester polyol based isoeyanats prepolymer in an amount of about 70 ercent by weight or greater based on the weight of the" prepolyrner and m re preferably about ^' 80 percent by weight or greater. Preferably, the polyester polyol. is present s the polyester polyol based isoe ahare prepolyaer hi an amount of about" 95 percent by weight or less based cm the weight of the prepolyraer -and more preferably about 90 percent by weight or less. Preferably, the polyester polyol based isocyanate. prepo!y er Is present in the adhesive composition in. ^' sufficient ..amount to give the seeded green strength and the desired theology of the condit on. Preferably, the polyester polyol based i ocyanate pfepolvter Is esent m the adhesive eomposhioa is an amoyat of b ut 0 parts by weight sr greater based, on the weight of ijbe adhesive composition, more preferabiy about 1 parts by weight or greater and most preferably about 2 parts by weight or greater. Pretobty _* th polyester polyol based isoeyasste prepolymer is present in the adhesive comp it on in an arnoan of about 1.0 parts b weigh or Jess, even more preferabiy about 5 parts by weight or less and . most preferaMy ahesstt 2.5 parts by weight or less. The polyester polyol can fee aay polyester composition that meets the property requi e e ts defined, which is crystalline at ambient temperatures and melts in its* desired temperature raoge Preferred polyester polyo.ls are available from€rsanova under the trad naise Bynaeo! arid the designations 7360 a 7330, itb7360 raore preferred..

[0033] The composition ma -further comprise a poly.t½ction¾l isocyanate tor the purpose of improving the modulus of the composition m the cured form, oly&actional as used the context of the .ispcyanates. refers to isocyariaies having a _: functionality of 3 or greater and Biore preferably abont 3,2 or greater. Preferably, the polyftmetionai isoeyanats has, a nominal fimciiofialtty of about 5 or less, even more preferably about 4.5 or less and: most preferably about 4,2 or less. The polyfunctions! isoeyanate can be -any isocymude . ^' which is reactive with the isocyanate polyi ^' soeyanste prepolymers ased i ihe eompositian and which - improves the modulus of the cured composition. The poly isocyanates ears, e m oiheric; tritnerc isoeyanurates or biurets of .ffiohoiiierie isoeyasates.; oligomer® or polytdefie, the reaction prodnet of several imits ; of one or more mono ersc isocyanates. Exainples of preferred olyfunetional. isocyasiates ^'" include tnmers- of hexamethyiehe dhsoeyanate, such as those available from Bayer under the trademark and designation Besmtodur* N330Q, a¾d polynienc isoeyanates such as polymeri MDI (methyleae diphsayi dlisoeyanaies) such as those marketed by The Dow Chemical Company: idtt the traum * of PAPF ωα)« ¾· PAPI ^ 20 polymeric isocyanate. The- polyfunctiona( sw aates are present in sufficient amount to impact the raodnh of the cured compositions of the Invention. The psjyfhtiotional isocyahate is preferably resent m m amount of about ⁽ ,5 arts by wei t Or greater based on the weight of the adhes e composition, ow t&hm &hmt L0 pans by weight or rea er and most preferably about 1.4 parts by weight or greater. The polyfttncti&oai isoeyanate is. preferably present in -an amount of about 8 parts by weigh or less, based oh the weight of the adhesive composition, more preferably about S pasts by weight or less and .most ^' preferably about 2 parts by weight or less,

|fMl34J The composition. «¾ay eora rise ope or more reinforcing fillers. Such 11 hers are well known to those skilled i the art and. include- carbon black, titanium dioxide, calcium carbonate, surface treated silicas,, titanium oxide, furoe -silica, talc, and the like, deferred reinforcing fillers comprise carbon black. More than one reinforcing filler may be used, preferably one. is carbofi. black. Th remforcisg fillers are w ed hi sufficient :.smounl to iti ea the stre¾igth of the adhesive, to provide ipotr c prbpenies te the .adhesive* arid t give the -composition the: desired viscosity and sag resi tance. Carbon black is eontmouiy lised So provide the. desired black color. The carbon black used in- this invention may be standard carbon black which is not specially treated (surf ice. treated or oxidized) to render ifcnoacondtsctive. Alternatively one or more noneonduetrve carbon, blacks ay: he used exclusively or in conjunction with the standar carbon black. The amount of carbon black in the composition, is that amount which provides the desired color, viscosity, sag resistance and where noncond ctivily i important in m amount such that the composition is noncondueiive to the level defined herein. The reinforcing fillers are preferably used in. the araount of about 10 parts by weight or greater based _. on the weight of the composition, more preferably about 12 parts by weight o greater and most preferah.lv about 14 parts by weight or greater:. Where- aon~eoudeetiv¾ properties are desired, standard carbon black is preferably present in an amount of about 20 parts by weigh or less based on the weight of the composition, more preferably about I S parts by weight or less and most preferably about 16 parts b weight o less,. The total reinforcing filler present, including: conductive or standard and non-conductive carbon black, is preferably about 35 parts by weight or les$ based on the weight of the composition, more preferably about 30 parts by weigh or less and most preferably about 20 parts ^' by- weight or less, Standard carbon blacks are well known in the art and inclade RAVEN ¹ * 790, /VER™ 4S0, RW « 580, RAVENS 43% RAVEN™ 420 .and RAVEN™ 410 carbon Blacks available from Colombian and CS ™ carbon blacks available frotrs Cabot, and ΡΜΝ ^' ΪΈΧ™30 carbon black

-1 _. 4- available from Begussa, ELFTEX S ^" !Oi\ MONARCH 470, MONARCH 570 and MOK Cil 580 carbon blacks. Nonconductive carbon blacks are well known m the art sad include R Vlif™ 104.©. and RAVE ™ I06€ carboa black from Colombian,

1 935) The eomposjton contains catalyst which catal es the reaction of isocyatiate moieties with water or m activ hydrogen, cos s king compound, whic are well knowB-la the art, exemplary . catalysts are Ofga!iotia compounds,, me al a kaaoates, and tertiary amines, and mixtures thereof, A mixture of a tertiary mnm, such as dimor ltoUao diethyl ether, and a metal aikaaette, sac , bismuth oeioaie is preferred. Organe-ti compound ^' s ineude alky! tip xides, stannous alfcanoates, dialkyi tin carboxylases and tin raereaptides. include stannous oetoate. Alky! tin oxides include dialkyi tsa Oxides, such as dibutyl tm oxide and ^' its derivatives. The organotia compounds preferably include, a. dialkyltin d catboxy!ate or diaikylliu dimereaptide-. The preferred dialkyi diearboxylafes .include J~dim© ft dilaurate. l.J--d kityltm diaeeiaie and ] _s !~ dimethyl d nmleate. Preferred metal aikanostes ^' include bismuth- alkanoates, such as bismuth oet ate or bismuth needeeanoate aad mtofthim alkanoaies. The organo rift compound or .metal aikaso&te catalyst is present in an amount of about §0 parts per million or greater based an. the weight of the adhesive, more preferably .20 parts by million or greater. The organo iifi c ound or metal aikanoate catalyst is p esent in an amount of . a out 1.0 percent or less based on. the weight of the adhesive, more ^■ preferably 0,5 percent by weight or Je&s and most -preferably 0.1. percent by weight or less, Exemplary tertiary amine catalysts include dlmofpheih½dlaikyl ether, a d¾{diaikytoorphoiffio)alky3) ether. bis 2-dimeihyisrnino etbyl>ethety trfcthyiene diamine, pep assethyldicthylsae triamlne, K ₅ N-dimeihyl cye hexyi am ne. N-dimethyl piperazias 4- methaxyethyl norpbolme, N-methyS morpholine, N-eftyi morpholine and mixtures thereof. A preferred dhuorpholmo dialkyi ether is dintorpholmodieahyi ether. A preferred ^■ di((diaikyimorphotmo)alkyl} ether is idi-{2-(3 ₅ 5~dimemylmofph0iin&} ethyl) ether). Tertiary -mums are preferably employed m an smous t based on- the weight of the adhesi of about 0.01 percent by weight or greater, more preierably about 0,03 percent by weight or greater, . even more preferabl about.8,1 percent by weight or greater and most preferably about 0; 2 erc n by weight or greater and about 2.0 percent by weight or less, more, preferably about ,75 percent by weight or less, even more, preferably about 1.0 percent by weight or less and most preferabl about 0.4 percent by weight, or less.

\ ⁽ Μ\ The adhesive ma be formulate with fillers and additives known in the prior art for use in adhesive compositions. By the addition of such -materials, physical properties sueh as

^' - I S- _. viscosity Sow rates and the like can be modified. However, to prevent premature hydrolysis oft¾e moisture sensitive grou s of !belsocyanaic: hmetioM! compounds, filler should be thoroughly dried before, admix&r therewith .Ixetttplar? fsllers include clays. Preferred clays useful in the invention include kso!iii, . surface treated kaolin, caicked kaolin, duniinum silicates, and surface treated anhydrous.: aluminum silicates. ^" The clays ean he used vs. an form _* - which .ioiiitales formulation of a purapable adhesive. Preferably, the clay is in the -ferm of pulverized powder, spray-dried beads, or firml ground particles. Clays may be «sed in m amount of about 10 percent fey weight of the adhesi e composition or greater, mere preferably about .1.2 part, by weight or greater and even more preferably about 18 percent by weigh! or greater. Preferably, the days -are used in an moun of about 30 percent by weight: or less of the adhesive composition, more preferabl -about 28 percent by weight or less and most preferably abou _. 24 percent by weight or less. Other components e mrnon!y used in adhesive compositions may be. nsed is t¾e, composition of this ventioa. S . ih material are well known to those skilled is the ar and may ! eWe- ultraviolet s abilisers and anifeslda s and the like. A used herein all isa&s by ^' weight relative to the components of the adhesive composition, are based on IW total parts hy weight of fee adhesive composition..

1 _. 0037]- The composition may further comprise stabilizers,, which fbnctiou t protect the adhesive exp siti n from m isture, thereby inhi it ng advancement and. preventing premature erossimking.of the isocyanates in the adhesive fonnalalion. Stabilizers known to the skilled artisan for moisture caring adheslves may be used preferably herein. Included amon such stabilizers are diethylmaion e, alkylpheiiq!. alkylates, paratoiuene sulfonic isocyanates, benzoyl chloride and Orthoalkyl formates. Such stabilisers are preferably used in an amount of about 0,1 parts by weight or greater based on the total weight of the adhesive composition, preferably about 0.5 parts by weight or greater and m e preferably about 0.8 parts by weigh m greater. Such stab¾iz rs axe used In an amount of about 5. parts by weight o less based on the weight of the adhesive composition, more preferably ^■ about 2,0 parts by weight or less -and- most preferably about 1.4 parts by weight or less,

|0038| The com osition may further comprise an adhesion promoter or adhesion promoting component, such as those disclosed in Mahdi U.S. Patent - Publication 2002/O1 55O paragraphs 0055 t 0065 and Bsieh, OS, 6,013,475 c lum 5, line. 2? to column: 6: ₅ line 41 incorporated herein by reference. Preferably the adhesion promoter contains a silane present in some fonn. Preferable methods of including sikme ftnctioftality In the compositions are disclosed. in Wu -et aL U.S. Patent S,512,033 si eohmm 5 _y liae 3S to co umh 7, line 27; VS, Patents 5,6 3,0 J 4,374,237- 4,345.033 and ^iSSJ 12, relevant p km incorporated -herein by reier¾ace. The silsne may be blended . with the prepoiymer. & s me embodiments the has oae or mo e active hydrogen atom which are reactive with an isocyanafe. Preferabl such silane is a mereapto-siiane or an ammo-siiane and more preterahiy is a mereapto^naikoxy-silane or an araiiio-trialkoxy silane. In some embod ment, the st!anes having, active hydrogen atonis reactive with isoeyanatejaoieties, caa be ftaeted with t e rmin l isoeyauate moieties of the prepoiymsr. Such reaction, products are disclosed ¾tU,S. Fat. No, 4,374,237 arsd. 4,345,653 relevas parts incorporated hereto hy reference to: other embodiment, s anes. having reactive hydrogen, m ieties rsactive with isocyaaate snoieties can be reacted into the backbone of the prepoiymer by reacting such si m i the starting rtiaterkls during the pi¾paraii i\ of the.prepolymer _* The process for the preparation of repolymers ^' containing silane in the backbone- is disclosed in IIJ. Pat. No, 4,625,012, .rele a portions moo po el herein by reference. Such silane, having acti ve jwdrogets inoie ies, can be reacted with poiyisdevariaie to Ssur an adduo whfch i:s ¾ikde i with the ^po! mer reacted ^' with a: oiyiirethane prep lyraer or reacted with a poiyisocyanaie aa a c mpound having: on average niore than one moiety reactive, with an Isooyanafe moiety, Preferably the addnet ia a reaction product of a secondary amino- or roercapto-aikoxy silaae and a polyiso.cyan.ate, the adduci having ail average of at least one silane group and at bast one isocyanate group per moleeoie ereffia ter ^' "addac ). Exem lary organofimctioaal siianes use&l as adhesion promoters or to . re are addoets include amino- or meteapto-alfcoxy silanes. isoeyanato alkoxy silanes. meihaerytey dimes, epoxy alkoxy silanes, a kenyi alkoxy silasies and the like. Examples of such compounds hicludei: ¾i„N- bis|;{3-tiiethox siiyl) propylamine;. N,N~his [(3 ripm ¾¾i| ]) propylamine; N 3 ri edroxy- sily!) propyi-3-fN-(3-lriniethosysilyl)-propyi ammo]propionam.ide <3 riethoxysi1yl) propyl-a- f "34rie¾osysiiy|>-prapyI ^« amii}ojprppio!! amide; -(3-trimethoxysilyl) ropyI"3* N-3-' P ethoxysilyi^propylamlnojpropionaaiidc; 3-trimetli- ox siiyS ropyl 3-[] i-{3~mmeth-o ysiiyi}- prapyIami«o]-2-metl¾yl propionate: 3-trieihoxysiiyl propyl 3»[f4-(3-tiiethpsysIlyI) -pr pylam e:]- andno]4«¾ieihyl -mereaptppropyl- methoxysiiane (available as MW from. Union- Carbide.) or N _? '"bis(i3~ tomsihaxysiiyl)propyl)amme. The amount of adhesion promote present is thai mount which enhances the adhesion of the adhesive io rise substrate surface. The amount of adhesion promoter present is preferably about 0.1 percent by weight or greater based on the weight of the adhesive and most preferably abofc ^' t Oi pereeRt by Wei ht or greater. The amount of adhesion promoter used is

- I T- preferably about 1-0 per ent by weight Or less ami Most preferably about 2,0 percent by eight or less The adb^sioa promotef ears be located s ^' eit r or both parte of a two part adhes ve Or In a on part adhesive. t)3 j The composition may further comprise, a hydrophilie material thai; functions t draw atmospheric ^' moisture is o the composition. This material eahaneea the cure speed of the fbmiokCiOo by drawing atmospheric .moisture to the composition.. Preferably, the hydrophilie material is a liquid-. Among preferred .hydroscopic materials are pyrolidinoses soeh as .1 nie%l~2- pyrolidkone, available from umler the trademark M-PyroL The Irydrophiile material is preferabl present ia .an amount of about 0.1 parts by weight or greater sad more preferabl about 0.3· parts by weight or greater and preferably about 3.0 parts by weight or less and most preferably about 0,6 parts by weight or less. Optionally the adhesive com ositio may fnrtber comprise a thixotrope. Such thkotropes are well known to those skilled ia the art m$ Include alumina, Bhiestehe, talc, zinc oxides, snlfer oxides, calciinrs carbonate, perlite, slate i!our, salt (NaC¾ eye dextrm mi the- like. The thixiArope may be added: to the .adhesive of coiri miti s in a . ^' sufficient amount give the desired theological p operties, reierably, the thk-otmpe is present in an amount of aboat 0 parts by weight or greater baaed on the weight of the adhesive -composition, preferably about 1 part by weight or gr ater > Preferably, the opt onal thixotrope is present in an amount of about 1.0 parts by weight w less based on the weight of the adhesive, composition and more referabl aboih 2 parts by weight or less, j fMftf The two part eomposk ions may contain a curing agent located in the B side. Such curing agent comprises one of more compounds that contain greater than one isoeyanaie reactive : group. The curing agent preferably contain hydroxy! groups. The curing agents ^' can be one or more low molecular weight, compounds or poS ols, Polyol as described hereinbefore-; can be utilised as curing agents. One class of polyols ^' -¾ρ be prepolymers as described hereinbefore prepared utilizin excess equivalents of isoeyanate reactive _: groups such that the resulting prepoiymers contain isoeyanaie inactive groups, preferably hydroxyi. The one or more-- low rnoleeniar weight compounds have two Or more isoeyana e reactive groups: and a _. hydrocarbon backbone whereia the backbone $nay further comprise one or more hete atous. JSueh low molecular weight compounds may b compounds; know) in the art -as chain extenders _. , such compounds are dif net nal, or eross!inkers. which have,, on average, greater than, two -active hydrogen ou s per compound. The he eroaioras in. the backbone can he oxygen, sulfur, nitrogen or a mixture ^' thereof; wherein oxygen, nitrogen or a mixture thereof is- moire preferred and oxygen 8- ^• ffiosl.pfeferred. Preferably, the molecular weight of the low molecular weight com un is a$ou$ 120 or less nd more preferably about 100 or less. Preferably, the low ino!ecular weight compoun comprises one or more, mnlttimetional alcohols, or one or more addueis of roalti etioa&l alcohol and an a!ky!erte oxide or a mixture thereof. Amon preferred multiiaactlonal alcohols are ethan diot, propane diol, butane diol hexsne diol, heptan diol oc ane dio!, gl eerine _? irimethylo ^' i propane, pestaeiyibritoi, neopentyl .glycol, and the like. Bleads of ' various l molecular weight compounds may; be psexl The lo molecular _: ei ht compound is used n s. suffieieat amount to obtain the desired G-Modulus (B-Modufus). Irs two-part eompositions _? the lo molecular compound may be located is tike resin side, the surative side or both. Preferably, tire low molecular weight compound is located in the curative side. _: freferahfy _s the low mo aiter weight c mmand present In the composition in mi amoun of about 2 percent by weight or greater, mm referabl about 2 J percent weight or grea er and most preferabl about 3.9 percent by weight, or greater, ihe&ihl ,. the lo molecular weight comp nd is present in the ^■ com osition, m amount of Shout IS ercoBt hy weight or less, ore preferabl about 8 perc nt by weight or and most; preferably about 6 percent b weight o less;

0141] The composition or a pad of tire fomitfeiion may be formulated by blending th eoBiponerrts together using means well know**- in the art. Qenera , the co o ents are blended in a suitable mixer. Such Mending is preferably conducted in an inert atmosphere Its the absence of oxygen and atmospheric moisture to prevent premature reaction, hi embo imen s where a polyester based is$sysnate functional prepor mer is used, the adhesive compositions are blended -at a., temperature above the melting, point of the pol este based _, oc asate .ftnetioaal prepslymer and ^■ below a temperature at which significant side reactions occur. In this embodiment the .temperatures oi ^' ifcsed ar¾ from about 40*G to less, than about %PC, more pteftabiy ab ut S0°C to about ?i) ^a C. it may be advantageous to add any pjasticiseis and/ or a Mend of one or more alky! esters of alkenoates and. one or more alkyl esters of alkaaoa es to the .reaction mixture t preparing the isoeys te. containing prepoiymer so thai such mixture my be easily mixed and haftdtedL Alternatively, the plastkissers ^■ atid/ot a Mend, of M or more alkyl esters of aikenoate and one or more alkyl esters of alkanoates can he: added arin Mending of all the components. Once the adhesive composition is ^' formulated, it Is packaged m suitable, eontamer such that it is protected from idnitospherie moistu e and oxygen. Contact with atmospherie moisture and oxygen could result in premature eross!mking of the feocyanafe ihnetloaal prepoiymer, PtMffi ^' j !¼. composition is used: its bond variet of sabstraies together as described hereinbe&re. The composition c&a be used to bond , orous and Mn o substrates together. The adhesive composiiioa is applied to a. substrate arid the adhesive on the first substrate ^' is fereafter contacted with a second sabstmte. In prefen eirib dimeo the surfaces to ich the adhesive i$ p lied are cleaned and primed prior to application, se for example, U.S. Patents 4,525,51 1; 3,707,52} and 3 _* 779,794; relevant parts of all aire incorporated herein, by reference. ener&Uy the adhesives of the invention are applied at ambient temperature, in he presence, of atmospheric moisture. Exposure to atmospheric moisture is sufficient to result -in. curing efone part adhesivse, Car tag can be accelerated, by the -addition of additional water or by applying heat to the curing adhesive by means of c nvection heat, microwave,, in&ared or ultrasonic heating -and the like. Preferably, the adhesive of the invention is formulated to pr vide a working time of about 6 minutes or greater snore preferably about 10 .mmnies or greater. Preferably, the wo king time is about iS ffiinii es or !ess and more preferably about 12 minutes or less,

|iH 43] The composition shay be used to bond glass or plastic coated, with an abrasion resistant, coatings to other substrates ^: s¾eb as metal or plastics,. M a preferred embed ίηκηί, the first substrate is a glass, or plastic coated with an abrasion resistan coating, window and. the ^' second substrate is a window trams. In another preferred embodiment the first substrate Is a glass, or plastic coated with an abrasion resistant coating, '¾dow .and the second substrate, is a window frame of an automobile. Preferably, the glass window is cleaned and has a glass: _: prhner applied to the area _: to which the adhesive is to be bonded. The plastic coated with an abrasion resistant coating eat) be 'any plastic which is clear, such as polycarbonate,, acrylics, hydregenated ^' polystyrene or h drogeaated styreae conjugated diene block copolym s having greater than SO percent styrene content. The coating can comprise any coating which is abrasion resistant such as a polysiioxane coat¾g, Preferably, the coating: has an. ultraviolet pigmented light blocking additive. Preferably, the glass or plastic window has m opaque coating disposed in the ^' region to he contacted with the adhesive to block UV light fern reaching the adhesive, fOS44J n a preferred e b dunent the composit½5 of the invention. ¹ is ased t re lace windows in structures or vehicles and most preferably in vehicles. The first step Is removal of the previous window. This can be achieved by cutting the. bead of the adhesive holding the old -window In place and then removing the old window. Thereafter the new window is cleaned and primed. The old adhesive that is located on the window flange can. be removed, although it is not. necessary at¾d in most cases it is leif hi place, he window flange is preferably primed with a paint primer. The adhesive h applied: m a bead to: fe periphery af ^' the wisido located Such thai It will eohtaet the window flange whe _: laced is. fee vehicle. The window wife the ad es located thereon is then placed fet the ^' ..flange wife the adhesive loca ed between the window and the fian . The adhesive head is a eontinnoas bead that fmw m to sea! tb* jtatetioa between the window Md the window flange. A e^tinMs ted of adhesive is a bead feat is located saeh thai . e bead connects at eac esd to. form a conunttotrs sea! between the window and fee flange _: when contacted. Thereafter the ad esive is allowed fe cote, is tise, fee components of two-part compositions are blended as would normally be done when workin with- sneh materials. For a two-part compositions to be most easily used in epmrnercia! and industrial e i nments, fes volume ratio at which the two parts am eon felned should be a convenient whole ..number.. This facilitates application oi the curable composition, with convention l, commercially avaiiabfe dispensers including s ie and dynamic mixing. Seek dispensers with static mix n are shows In US. Patent Humbe J38 _y ¾ ^: and 3,6 2,147 ^' {kooi amted ke a. by ref rence} and are avaiiahk fern C¼prbiec, Inc. (Salem,; New Jersey) under me trade ame IXPAC or St LiER QtJADR ^' O of Sulzer Ltd., Switzerland. Typically, hese dlspe«sett _; .o.s© a: pair of tubular reoeptaoles arraaged side- by-side wife each tu e being intended in- receive one of the two parts of fee p fymenzable composition. Tw plungers, oae for each tube, are simultaneously advanced (e,g,, m ualiy or b a. hand-aeteatacbrjitchetin mechanism) to evacuate fee contents of the tubes iafo a eom»on, hollow, elongated^ mixing chamber that ma also contain a static mixer to feeiiitate blending of the two parts. The blended poiyfner ble coinjroiita) is extruded from the mxing chamber onto a substrate, When using electrically-driven equipment, dynamic mixmg may be/used. Ones the lutes have been . emptied, the cars fee replaced with fresh tubes and the application process continued. The volraneirie ratio at which the two parts of the poiynmrizsbfc composition axe _, eqmbped is cantrolled by the diameter of the tubes. (Each, plunger is sized to be received within a abe of fixed diameter, and the plungers are advanced into the tubes at the same speed.,) A; sin le: dispenser is often Intended fo use With a variety of dlffeftt twp- ari polymcriKahle compositions and the pinngers are sixed to deliver the two sarts of the polyfeerizabi eomposition at a convenient mix ratio. Alternatively ths two part composition may be disposed in a single tube with the curative part located in a bag within the .resin, hi this em odin nta single tnbe is used and when the two parts are extruded from fee tube they are passed through a nozzle containing mixing elements so as t tmx the com nerrts. sufficiently such tha he ecniposifion ca t undergo cure once mixed.. Some common k ratios are. 1 : 1 , 2:1, 4: 1 and 10:1 and can also he odd ratios. Preferably, fee two parts am Mertde at a. mix ratio of about 1:1.

1" | 45| Ptsfembfjy the mfc&ed two- as : ompo tio of the vmtim a mi bte viscosity to allow af¾*¾tSi¾ft without drippkg. inferably, the ^sisos& of the two individual components should be of the -same order of inagrrifeide. For lower viscosities* the e iHpojjmis may require gelling agent known in. the art to preven sag of t scared adhesive system. Two-part ad es e compositions start: to cure u on mixing the two parts. Curing can be accelerated- by applying heat to the curing, adhesive by means of infrared heat, induction heat, convection he t, microwave hearing, application of ultrasonic vibration and the like, M46j M toother embodimen the compositions of the invention- cat) be used to bond modttkf components to a car body or to each other. Exam les of modular com onents Include vehicle modules, · mc as door, window or body. Molecular weights as described herein are number average molecular weights, which may e dete-n ned by Gel Permeation Chromatography (also referred to as PC). For polytifethane prepolyniers, it is also possible to calculate approximate samber average molecular weight from the equivalent ratio of the isocyanate cemponrids. and of the :|j ly0l c-osnpoua<i$ ^: with which they are reacted m -known to the e sons skilled in- the art, Viscosi ies as described herein re determined ^' aeeofding. ^" to ¾e -procedure -disclosed, in i ,. IJ.S, Patent 5,9 2, 809 at eola n 12, lines 38 to 49, .incdjrporaisd. herein by reference. I» reference to pol urethaae i¾pdl iaers, average isocyaaate fuikiio«al.iiy Is determined according to the procedure disclosed in Bhat, O. . Patent 5,922,809 at column 12 lines 65 to coMmra .13, line- 26 ^' , ine rporaivd herein fey referenc ;

\M4 \ The following examples are provided to illustrate the in ention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless- otherwise indicate*!

1.3 81 Prepay¾li¾a-¾if: PrajKsiym s - f pol mers are fe aed according to a. roced re siffiiiar t †h« following pmeodyr : m $. the composii os !isied in Table I, & iyetlter Is prepared by; thoroughly 'mixing 27.11 grams of a poiyoxypropyleae dio! (VORANOL™ 220-056 p Jyol hving aa average molecular weight of 3000), 26.77 grams of polyoxypropy sie ino! (VO NOt™ 232-23:6 paiyisi having ayerags moiecplaf weight of 4500 V RANOL ^!'M is a _. tade ark of e Dow Chemical Compaq) or TP 4542 trk>! torn- BASF, and 30,224 gram&ofaikyipifchaMe plastisizer ( r ofe p!astieisjr as showa¾©r¾m).¼a2- Kter resia kettle e up d it!i a mechanical;, agtato, & ultrogetr inter, adapter ami a thermometer. Un er mtrogen purge, the mixture is heated to 5 " C.9.$% ms of molten diphenylene mehane 4,4' dlfeoeysriaie are added its s mbitm and tax hly mked, T ea 0,004: gj^s of tin di(octoaie) are iatrodaoed and the raktee is ^' mixed for one hour.0.42 grams of diethyl rtiate e are added to M mature- which was then, mixed for 15 mirmtes. Thereafter, 0,812 grams of bi¾-(3- tr!mei ^: hoxysilylpropyiamme isadded arid ^■ the .mixture, is mixed ibr two horns. Then 5.62 grams of DE MG iJE ^T¾ N-33Q0 (an aliphatic poiyisoc aaie r® based ti ^: exame feue diisoey&nafc, supplied by Bayer USA Mc m. addsd aaSihe irr&teis is m&ed for IS minutes.

Table I

Compounding of .Adhesives - All of the adhesives are made ac»di»g ·«ø: the foftpwiag' compounding prcsedyrt asiag th raw nmferiai percesiages lised HI table 2. The. only: ehaage between the _. different formulations is the compounding, temperatee. The esie are c m ounded at .ro m temperature. The a ropiate mounts of polyeite ^' pi¾ppyin«r _; arfe charged to the vessel and degassed miter v m. 1 jriyes..The _: carbon black aid clay fillers am added mi mixed for five minutes a slow speed toder vasuum until the fillers are sufleknily wetted by he prepdlytners. The jraixii speed s incre sed and: the fillers dispersed: for 20 mi ics. Finally, the diiBorp olino diethyl ether,, phosphite nd adhesion promoter md the are added to the mixing vessel and the mixtue- h ^" mixed, wider v&cmiifrfbr aa-addltioaal Ϊ0 minutes. SOf Tahfc 2 deseribes the for ulations tested, and. the m compiled in Table 3 Table 2,

Testing Procedures - Press Flow Viscosity: The press flow -viscosity is determine as the tim (seconds) required to extrude 2,0 grams, of adhesive through a capillary. The width of the capillar is .fixed at 0.203 m (5.1 mm) and die applied pressure fs SO psi (5,5 x W Pa). Doless otherwise noted, ah press flow viscosity values were detenn ed at 23+/ *ϋ.

Stringing Test, The swinging testis-conducted

o ered caulfc g gun. After dispensitg approxlffia^ly sis inches of an $ mm by 12 mm isosceles triangle: shaped ead the dispensing tip is immedi te pulled away firorh ^' the adhesive bead . motion- -parallel to and in the same plane as the adhesive head. The sttmgbg is: eas re fey t e length of ill® tail, mi¾ thai is left stpon separation. Table 3

(9051] Examples to 10 are pre are using ih«. above described processes- wherein prepolymer contains different plastiefeirtg compounds,. The ad esive om osit ons are described in Table 4.

Table 4

[;0052| He prepoiymer with the variotss jp!astichser eompositoas are prepared as described

The properties of adhes ^' ives of examples 7 to: ] (5 re eontaiaed ia Table.5. 1005*] ^' Table!

esuts are avera es o or n v ua ms.

[0ftS5j This data illustrates ibe 1:1 weight substfcutfca* af diiso¾o l phthalate with soy methyl ester or carjo!a methyl esters, specifically SoyOoid 1 00, Columbus 97Θ (soy 2) , m& Co snbus (Carjok) 973 perform similarly w h otabie exceptions. Iniikl adhesive-viscosities are sigsll¾a«% lower with the- vegetable Oils, based w their much lower inherent viscosities hat the G mod lus is nearly identical grid emains- -high- alter aging. This adv iitageois in ^' adfeive forradatfens ^' that require low dispense pressures but high gap filling, sag resistance and; green- strength. The molecular weight distribution for all of the sam les- is -comparable before arid after aging; indicating so thermal degradation r side reactions are taking place. The initial -and heat aged isoeysnte -content are d measures of the completion of reaction and indicate m unex ected reactions Occurred.