Background of The Invention Commercially available polyurethane has been used to adhere FRP structural adhesives on personal watercraft substrates but only if the surface to be bonded is pretreated, such as by sanding or priming with a solvent before applying the adhesive to the substrate. As watercraft manufacturers become more aware of the labor intensity and the environmental probiems caused by such surface treatments, new adhesives are needed to bond these structures together without any surface treatment.

Detailed Description of The Invention Personal watercraft are made by hand laying glass mats or glass fibers on a mold or form. The glasses then bo'nded:together with a resin, usually unsaturated polyesters cured at room temperature by free radical chemistry initiated by peroxides. Typically, such parts are cured in the open air, although sometimes they are compressed briefly to control thickness uniformity. In either process, air in the surrounding atmosphere inhibits the

crosslinking reaction resulting in a partially uncured top surface. It is well known that such an inadequately cured surface is difficult to adhere without some surface treatment, such as a solvent wipe or sanding.

It was discovered that if the adhesive contains unsaturation functionality, hereafter referred to as an Uunsaturated polymer", it can be cured by free radical chemistry initiated by peroxide and used to bond watercraft parts without any surface treatment. However, the unsaturated polymer / peroxide cured adhesive is very brittle, since there is no strength reinforcement in the adhesive such as the glass fibers used to build the watercraft itself. It was discovered that such peroxide cured adhesives can be toughened or flexibilized by a cocuring polyurethane adhesive.

In addition to adhesion, this very flexible unsaturated polymer / polyurethane adhesive for watercraft showed excellent sag resistance, fast green strength development and a tack free surface. Retention of adhesion was also demonstrated by exposing the bonds in 100% relative humidity environment at 100"F (380C) for eight weeks. Testing of bond strength after such exposure typically showed greater than 230 psi.

Examples of unsaturated polymers forasuch adhesives include the same type of unsaturated polyesters used to construct watercraft as well as unsaturated polyurethanes. Typical unsaturated polyesters are the reaction product of a glycol and an unsaturated carboxylic acid or anhydride and dicyclopentadiene or styrene. The unsaturated polyurethane is typically

prepared by end capping a polymeric polyol with a polyisocyanate to prepare a prepolymer. Then, the isocyanate end groups are converted to unsaturation by reaction of the isocyanate with the hydroxyl group of an unsaturated alcohol, such as hydroxylethyl acrylate or hydroxyethyl methacrylate (HEMA). U.S. Patents 4,480,079, 5,126,396 and 5,250,608 describe the preparation of unsaturated polyurethane.

To reduce the viscosity of the unsaturated polyurethane product, one commonly adds more isocyanate to the prepolymer to prepare a low molecular weight adduct of HEMA-capped polyisocyanate simultaneousiy with the prepolymer preparation step. Also very effective in viscosity reduction is the addition of low molecular weight reactive diluents such as styrene, acrylates or methacrylates. These diluents also cocure with the unsaturated polymer when exposed to a free radical initiator such as a peroxide.

Alternatively, the prepolymer step of such unsaturated polyurethane may be bypassed by simply reacting HEMA, polyol and polyisocyanate in one step to form an unsaturated polyurethane.

A room temperature curingadhesiye for bonding personal watercraft without surface preparation is formed by combining the unsaturated polymer with a polyurethane. Exemplary polyurethane adhesives are described in U.S. Patents 4,923,756, 5,002,806 and 5,548,056. Examples of such combination include 1) having polyisocyanate and peroxide as Part A and

polyollpolyamine and unsaturated polymer as Part B or 2) having polyol and peroxide as Part A and polyisocyanate and unsaturated polymer as Part B.

Interpenetrating network structural adhesives are prepared by mixing Part A and Part B using a propeller type mechanical mixer or a mix machine such as Model 200 from EMC2, Sterling Heights, Michigan. To facilitate room temperature curing, a peroxide such as benzoyl peroxide to initiate free radical formation at room temperature and conventional catalysts such as tertiary amine, organotin, and organocobalt may be used.

Alternatively, since many commercial peroxides are available for the initiation of peroxide formation above room temperature, a peroxide other than benzoyl peroxide may be used for the adhesives of this invention, if the curing at elevated temperatures is desired. In such cases, the formulator has the option of combining all the ingredients into a single mixture, instead of Part A and Part B. When the adhesive is ready to be cured heat is applied to initiate free radical formation and thus crosslinking.

Among the fiberglass reinforced polyester substrates useful in the practice of this invention are those hand layup and cold press substrates provided by Arctic Cat, Inc, Thief River Falls, MN (formeriy known as Arctco) or Mercury Marine, Hartford, WI. ;~ The unsaturated polymer polyurethane adhesive of this invention is made by combining a polyisocyanate, a component reactive toward polyisocyanate, an unsaturated polymer and a free radical initiator. Among the polyisocyanates useful in this invention are:

diphenylmethane diisocyanate, toluene diisocyanate, 1,4-phenylene diisocyanate, 3,3'-dimethoxy4,4'-biphenyl diisocyanate, 3, 3'-dimethyl4,4'-diisocyanatobiphenyl, 3,3' dimethyl4,4'-diisocyanato diphenyl methane, or their polymerized versions or mixtures thereof. The most preferred isocyanate in the practice of this invention is poiymeric Rubinate 9310 available from IC1, Sterling Heights, Michigan or Isonate 143 L polyisocyanate from Dow Chemical, Midland, Michigan.

Alternatively, the polyisocyanate useful in this invention may also be derived from the reaction product of a polyisocyanate and a polyol of 1.8-6 functionality. The polyols useful for the preparation of such prepolymers may be 700 to 10,000 molecular weight polypropylene oxide ether diol, polyethylene oxide polypropylene oxide ether diol, polytetramethyiene ether glycol, polythioether diol, polyester diol, polyepsilon caprolactone diol, polycarbonate diol, polybutadiene diol or mixtures of these diols. The preferred polyol is a polypropylene oxide ether diol of 1000 or 2000 molecular weight available from Olin Chemicals, New Haven, Connecticut as Poly G 20- 112 or Poly G 20-56, repectively.

The component selected to cure the polyisocyanate in the unsaturated polymer polyurethane adhesive of this invention inciudes the polyols used to make the prepolymer and polyamines. Other polyols include polyester and polyether polyols which have a functionality of 1.8 to 6.0 and a hydroxyl number from 100 to 1200. A hydroxyl number range of 200 to 700 and a functionality range of 3 to 5 are preferred. Suitable active hydrogen containing materials include diols, triols and tetrols, having primary, secondary and/or tertiary alcohol groups. Among the preferred polyether

polyols are: Pluracol PeP 550 polyol, a propoxylated derivative of pentaerythritol having four secondary hydroxyl groups, a hydroxyl number of 450, and a molecular weight of 500 available from BASF Wyandotte Corporation, Parsippany, N.J.; Arcol F3220, an ethoxylated I propoxylated derivative of glycerin having thee secondary hydroxyl groups, a hydroxyl number of 52 and a molecular weight of about 3200 available from ARCO Chemical Company, Newtown Square, PA; Fomrez ET3500, a propoxylated derivative of glycerin having three secondary hydroxyl groups, a hydroxyl number of 48 and a molecular weight of about 3500, available from Witco Corporation, Organic Division, Houston, Texas; Pluracol P-355 polyol, an ethoxylated/propoxylated derivative of ethylene diamine having about 80% of its hydroxyl groups as primary and having a hydroxyl number of 450, also available from BASF Wyandotte Corporation; Ethanol R470X polyol, available from Texaco Chemical Co., Bellaire, Tex., a propoxylated derivative of diethanolamine with a functionality of about 4 and a hydroxy number of 500; Thanol SF-265 polyol, also available from Texaco Chemical Co., a propoxylated derivative of triethanolamine with a functionality of about 3 and a hydroxyl number of 600; Voranol 230-660 polyol, a polyether triol of 85.4 equivalent weight based on the propoxylation of glycerin, available from Dow Chemical Co., Midland, Mich.; and Dianol 2210 polyol, an ethoxylated derivative of bisphenol-A with a functionality of 2 and a hydroxyl number of 280, available from Akzo Chemie America, Chicago, Ill.

Among the numerous diamines useful for curing the unsaturated polymer polyurethane adhesive of this invention are the following aromatic diamines: toluene diamine 1 -methyl-3, 5-diethyl-2,4-diaminobenzene 1-methyl-3,5-diethyl-2,6 diaminobenzene (also known as DETDA or diethyl toluene diamine) di(methylthio) toluene diamine

1 ,3,5-triethyl-2,6-diaminobenzene toluene di amine derivatives containing halogen groups, cyano groups, alkoxy, alkylthio, alkenyl or carbonylic moieties m-phenylene diamine p-phenylene diamine 4,4'-methylenedianiline 4,4'-diaminodiphenyl sulfone 2,6-diamino-pyridine 4,4'-methylene bis(3-chloroaniline) 4,4'-methylene bis(3-chloro-2,6-diethylaniline) 4,4'-methylene bis (3-chloro-2,5-diethylaniline) 3,3'-di-isopropyl4,4'-diaminodiphenylmethane 3,5,3', 5'-tetraethyl-4,4'-diaminodiphenylmethane propylene-di-4-aminobenzoate isobutyl 4-chloro-3,5-diaminobenzoate bis (2-aminophenyl) disulfide bis (4-aminophenyl) disulfide di (alkylated amino) benzene secondary diamine bis (alkylated aminophenyl) methane secondary diamine 3,3'-carbomethoxy-4,4'-diamino diphenylmethane and mixtures thereof. The most preferred diamine for the adhesive of this invention is diethyl toluene diamine (Ethacure 100, from Albemarle Corporation, Orangeburg, SC), which also contributes to the sag resistance of the adhesive beacause of its high reactivity.

Another ingredient in the formulation of the adhesive of this invention is an optional catalyst to faciliate the crosslinking reaction of the adhesive between amines and isocyanates, and between polyols and isocyanates.

Suitable tertiary amine catalysts include N, N', N"- dimethylaminopropylhexahydrotriazine (Polycat 41) and 1,4- diazabicyclooctane, and suitable organo metallic catalysts such as those

derived from zinc, potassium, bismuth and tin including dibutylin dilaurate, dibutyltin diacetate, ferric acetyl acetonate, nickel acetylacetonate, dibutyltin dialkyl acid, stannous octoate, dibutyltin diiso-octyl mercapto acetate, dibutyl tin diisooctyl maleate, and mixtures of these catalysts. The preferred organo metallic catalyst is the dibutyltin diacetate known as DABCO T1 available from Air Products, Allentown, Pa. The preferred tertiary amine catalyst is dimethyl aniline.

Other optional ingredients in the formulation of the adhesive of this invention include thickening, coloring, odor control agents and drying agents.

The preferred optional thickening agents are: aluminum silicates, carbon black, talcs (magnesium silicates), calcium carbonate, calcium siiicates, barium sulfates, graphite, or mixtures of fillers. The preferred filler ingredient is Aerosil 200 or Aerosil R972 fumed silica from Degussa Inc., New York, N.Y.; and Cabosil TS 720 fumed silica from Cabot Corporation, Cab-O-Sii Division, Tuscola, IL.

Small amounts of other optional materials may also be added to the adhesive formulation. These include coloring agents, for example, Stantone HCCC. 6783 green coloring agent from Harwick Chemical Company, Akron, Ohio, which is a blend of C.I. Pigment Green #7 and C.I. Pigment Black 3W7 dispersed in a polyoxypropylene polyol at 17.8 parts of pigment to 82.2 parts polyol.

It maybe desirable also to use from 0.5 to 15.0 percent of a drying agent such as a Molecular Sieve powder of the 5 Angstrom size available from Union Carbide or anhydrous aluminum sulfate powder from Geo Specialty Chemicals, Inc, Little Rock, Arkansas.

The customer combines Part A and Part B in the desired ratio, usuaily 1 weight part Part A is blended with 1-10 weight parts Part B. Unsaturated polymer polyurethane structural adhesives are prepared by mixing Part A and Part B typically using a mix machine Model 200 from EM C2, Sterling Heights, Michigan. The adhesive is applied to the first substrate by conventional

means. The second substrate is then laminated over the first adhesive coated substrate. The adhesive is typically cured at room temperature, although other energy sources such as microwave, radio frequency or dielectric energy or electromagnetic energy maybe used to accelerate the cure of the adhesive.

Crosspeel adhesion samples were prepared using room temperature cured hand layup fiberglass reinforced polyester plaques, prepared from dicyclopentadiene, vinyl esters, or the reaction product of unsaturated dicarboxylic acid and glycol. Representative types of theses substrates are the Arctco FRP or Arctco Cold Press or Mercury Marine FRP constructions used to manufacture personal watercrafts. A fiberglass reinforced polyester plaque was cut into 1 inch by 3 inch strips. Adhesive was applied onto the center 1 inch by 1 inch area with no surface pretreatment. A few glass beads of 30 mils diameter was spinkled onto the adhesive to control the bondline thickness when the center of a second 1 inch by 3 inch fiberglass polyester plaque was mated onto the first strip with the adhesive. After curing the adhesive at room temperature, the crosspeel samples were pulled on a Monsanto Tensometer 10 tester fitted with a jig to hold the four unadhered ends of the crosspeel samples. The upper strip of the crosspeel was pulled until it is separated from the bottom strip. Adhesion strength values over 600 psi were observed with failure occurring by tearing apart the cured polyester resin from the fiberglass used to reinforce the substrate. This is referred to in the industry as fiber tear" or "FT" and is a very desirable result. The performance of an adhesive is rated on the amount of fiber tear based on the

percentage of the adhered one square inch. The data is recorded as pounds per square inch (psi) followed by a parenthesis which contains a first % of fiber tear and a second of cohesive failure. When the summation of the percentage values in the parenthesis does not equal to 100 the remainder is understood to be adhesive failure. Cohesive failure is designated to be a failure leaving adhesisve on both pieces of plaque forming the crosspeel adhesion sample. Adhesive failure is designated to be a failure with separation of the adhesive from the substrate without exposure of the giassfiber reinforcing the substrate.

Green strength development of an adhesive is evaluated by testing adhesion crosspeel samples after they are cured at different intervals of time at room temperature, typically at 20 and 30 minutes. An adhesion strength of about 50 psi is considered adequate for handling the weight of personal watercraft parts in the production assembly line. Fiber tear accompanying failure of the crosspeel sample is considered superior performance of the adhesive.

The nature and advantage of this invention can be more readily seen and appreciated by reference to the following representative examples, where all components are expressed in parts by weight (pbw). All patents mentioned herein are expressly incorporated by reference.

EXAMPLE 1

This example one describes the preparation of a polyisocyanate / peroxide Part A to be cured by a polyol / polyamine / unsaturated polymer Part B.

Formulation: Polvisocvanate 4495 Rubinate 9310 polydiphenylmethane diisocyanate 11.92pbw Moisture scavenger Molecular Sieves 5A powder 0.18 Cabosil TS720 treated fumed silica 0.88 Luperco ATC 50% Benzoyl Peroxide 5.29 18.27 Procedure Rubinate 9310 was charged into a 22-liter flask. With an efficient, high shearing stirrer and under a nitrogen blanket; Molecular sieves 5A powder was added, followed by Cabosil TS720. Then, Luperco ATC was added to the resulting very viscous mixture. Mixing of the peroxide was initiated by handmixing with a paddle. Final thorough mixing was achieved by low shearing with a mechanical mixer for 15 minutes. Degassing of the final

mixture was initiated by slowly opening the vacuum line. When full vacuum was achieved the product was degassed for 30 minutes before discharge.

The product was stored under a nitrogen blanket.

EXAMPLE 2 This example 2 describes the preparation of another polyisocyanate / peroxide Part A, a polyol is reacted with the polyisocyanate before the addition of peroxide.

Fonnulation: Polvisocyanate 4627 PolyG 20-112 ethylene oxide capped polypropyline ether glycol (MW 1000) 50.00pbw Moisture scavenger Molecular Sieves 5A powder 3.86 Rubinate 9310 polydiphenylmethane diisocyanate 158.40 Mistron RCS Talc 46.31 Aerosil R972 hydrophobic fumed silica 11.58 Luperco ATC 50% Benzoyl peroxide 115.78 385.93

Procedure Polypropylene ether glycol (PPG) (MW 1000), PolyG 20-112 was dehydrated in a vessel at 100-105"C and at a vacuum of less than 1 mm Hg, or until the moisture content was less than 0.05%. The dried PPG was cooled to 85"C before adding Molecular Sieves 5A and Rubinate 9310.

Degassing was resumed and the polyol and polyisocyanate reacted at 85- 95"C for an hour or until the isocyanate content reached the theretical value of 19.79%. The mixture was cooled to 50"C and the vacuum was broken. A nitrogen blanket was introduced before the addition of Mistron RCS and then Aerosil R972. When the addition of the filler was complete Luperco ATC was added. Mixing of the resulting viscous mixture was initiated by handmixing with a paddle. Final thorough mixing was achieved by low shearing with a mechanical mixer for 15 minutes. The final mixture was degassed. When full vacuum was achieved degassing was continued for 30 minutes before discharge. The product was stored under a nitrogen blanket.

EXAMPLE 3 This example 3 describes the preparation of an unsaturated polyurethane (UPU) to be blended with a polyol and/or a polyamine to form Part B.

Formulation:

Unsaturated Polyurethane (UPU) Methyl Methacrylate, MMA 48.0 pbw Hydroquinone, HQ 0.008 p-Benzoquinone, BQ 0.008 Hydroxyethyl Methacrylate, HEMA 9.6 Rubinol F428 ethylene oxide capped triol (Hydroxyl No 28) 29.3 Rubinate M polydiphenylmethane diisocyanate 11.5 Dibutyl tin dilaurate 0.68 MMA 0.86 99.96 Procedure MMA and HEMA were charged. Hydroquinone (HQ) and p- benzoquinone (BQ) were added and stirred until homogeneous. Rubinol F428, an ethylene oxide capped polyether triol with a hydroxyl number of 28 was charged. The moisture content was less than 600 ppm. Rubinate M was charged and stirring continued. Dibutyl tin dilaurate predissolved in MMA was charged. The reaction was stirred and continued for 90 minutes.

EXAMPLE 4 This example 4 describes the preparation of another unsaturated polymer similar to the unsaturated polyester (UPE) chemistry used to bind glass fibers for the manufacture of watercraft.

Unsaturated Polyester UPE

Diethylene glycol 467.2 pbw Dipropylene glycol 31.1 Maleic anhydride 99.3 Isophthalic acid 536.3 Styrene 538.0 Monotertiary butyl hydroquinone 0.193 Methanol 0.772 Procedure Diethylene glycol and dipropylene glycol were charged and heated to 140"C under an inert blanket. Maleic anhydride and isophthalic acid were added and heat to 210"C. The reaction continued until a viscosity at 28% styrene of 13-15 stokes. Styrene and monotertiary butyl hydroquinnone dissolved in methanol were added. The product was cooled to 1 700C and discharged.

EXAMPLE 5 This example 5 describes the preparation of a polyol / polyamine / unsaturated polymer Part B to cure a polyisocyanate such as Example 1 polyisocyanate 4495.

Curative 4600 PeP 550 Propoxylated pentaerythritol (Hydroxyl Number 450, MW 500) 2.67 pbw ET 3500 Propoxylated glycerin (OH# 48, MW 3500) 10.98 Ethacure 100 Diethyltoluene diamine 2.72 Example 3 unsaturated polyurethane 43.59 Methyl methacrylate (MMA)<BR> <BR> Q

Diallyl Phthalate (DAP) 6.70 Cabosil TS720 treated fumed silica 7.54 Moisture scavenger Molecular Sieves 5A powder 0.42 StanTone 6783 green dye 0.17 Dimethyl aniline (DMA) 0.59 Dabco T1 Dibutyl tin diacetate 0.059 83.819 Procedure PeP550, ET3500, Ethacure 100, Modar 839 and DAP were charged and stirred to mix thoroughly. Half the required Cabosil TS720 was added.When the mixture was still quite fluid Molecular Sieves 5A, StanTone 6783, DMA and Dabco T1 were added. Under a nitrogen blanket, finish adding the remaining Cabosil TS720. When the filler was thoroughly wetted and dispersed the mixture was degassed. When full vacuum was achieved degassing continued for 20 minutes before discharge. The product was stored under an air atmosphere.

EXAMPLE 6 This example 6 illustrates the adhesion performance of an unsaturated polyurethane plus polyurethane hybrid adhesive 4606 by mixing Polyisocyanate 4495 of Example 1 with Curative 4600 of Example 5. After curing at room temperataure on Arctic Cat, Inc., Thief River Falls, MN 56701, fiberglass reinforced polyester substrate or Arctic Cat, Inc. cold pressed FRP

or Mercury Marine FRP, adhesion strength as high as 610 psi with 98% fiber tear was observed. The adhesive also possessed excellent sag resistance by showing no slump when dispensed on a vertical surface. It had a bondability time of 5.75 minutes and developed a strength of 127 psi after 30 minutes at room temperature. (Table 1) Table 1. Adhesion Performance of Acrylated Polyurethane / Polyurethane Hybrid Adhesive Adhesive Ex.6 4606 Polyisocyanate Ex. 1 4495 Curative Ex. 5 4600 Mix Ratio, wt 191100 Bondability, min 5.75 Vertical Cardboard no slump Button Sag, inch 0.10 Heat Rise, °C/min 101/6.7 Green Strength 30 min @ RT 127(510) 40 min @ RT 149(100/0) Crosspeel, psi(%FT): ARCTCO FRP Plaque After 7davsRT 281(100/0) 163(100/0) 276(100/0) 267(100/0) 610(90110) Average 319(98/2) ARCTCO FRP Hull Part 7d@RT 225(100/0) 235(100/0) 227(100/0) 230(100/0) 279(100/0) Avg 239(100/0) ARCTCO Cold Press 7dRT 332(25/0) 276(95/5) 176(90/0)

Adhesive Ex.6 4606 267(40/0) 191(90/05 248(6811) Mercury Marine 7d@RT 268(100/0) 375(100/0) 225(100/0) 335(100/0) 307(100/0) 302(100/0) :SFess-Strain: Ultimate Tensile, psi 2420 Ultimate elongation, % 46 EXAMPLE 7 This example 7 illustrates the adhesion performance of an unsaturated polyurethane and polyurethane prepolymer hybrid adhesive on FRP.

Table 2. Performance of a Prepolymer / Acrylated Polyurethane / Polyurethane Hybrid Adhesive S PxpOIj 6imer:-:--;::-:: w g:t --- >S~ 4211 Ashland Pliogrip 9400, 25.68 I I Luperco ATC. % 6.42 4324 PeP 550, % 2.42 ET 3500, % 9.97 DETDA, % 2.47 Example 3, Usatuated 44.23 Polyurethane, % DAP, % 5.44 Aerosil 200, % 2.72 Mol Sieves 5A, % 0.34 DMA, % 0.25 Dabco T1 % 0.041 Mix Ratio, wt 47.3/100 Bondability, min 7 Button Sag, inch <0.25 were ARCTCO mBI Original 182(100/0) 320(100/0) 245(100/0) 262(100/0) 259(1 00/0) 254(100/0) 254(10010) Cold Press 487(40/0) 375(50/0) 425(70/0) 479(75/0)

456(57/0) Stress Strain: Ultimate Tensile, psi 2600 Ultimate Elong, % 64 EXAMPLE 8 This example 8 illustrates the adhesion performance of an unsaturated polyester, unsaturated polyurethane and polyurethane hybrid adhesive on FRP.

Table 3. Performance of a Unsaturated Polyester / Acrylated Polyurethane / Polyurethane Hybrid Adhesive PolyNCO: 4323 Rubinate 9310, % 10.90 Mistron RCS, % 0.87 Aerosil 200, % 0.26 Mol Sieves 5A, % 0.086 Luperco ATC, % 5.19 CURATIVE: 4338 PeP 550, % 2.54 ET 3500, % 10.45 DETDA, % 2.58 UPU in Example 3, % 0 38.04 UPE in Example 4, % 19.02 DAP, % 6.62 Aerosil 200, % | 2.48 Mol Sieves 5A, % 0.41 DMA, % 0.50 DabcoTl, % 0.049 Mix Ratio, wt 20.9/100

Bondability, min 9 Heat Rise, °C/min not done Button Sag, inch 0.25 Squeeze out TF Trimmability yes Green Strength 30' 117(0/100) 45' 258 30170 Crosspeel, psi(%FT): ARCTCO FRP Plaque 289(100/0) 227(10010) 235(100/0) 345(100/0) 254(1000) 270(100/0) ss-Strain: Ultimate Tensile, psi 2160 Ultimate Elongation, % = 20 Example 9 This example 9 illustrates the formulation of polyols with peroxide to form Part A and unsaturated polymer and polyisocyanate to form Part B.

Table 4. Performance of Polyol-Peroxide / Acryiated Polyurethane- Polyisocyanate Hybrid Adhesives. PeP 550, 20.02 13.33 10.01 Curative 4002 35.16 23.44 17.58 LD'490 9: 3 C 8 DMA, ram 0.10 0.10 0.10 0.10 0.07 0.07 UPU Exam le 3 50.00 66.67 75.00 50.00 66.67 75.00 C(I 9310, 29.98 20.00 14.99 14.84 9.89 7.42 Open Time, min 2 4 10 4.5 6 10-30 ~ N Out Tack-free TackJree 81 o ARCTCO F; F O O O O v v C W O O O g O t 324(10190) 1" t 340(01100) 355(30/70) or N 0 N 290(10/90) ;ii $ 392(100/0) 363(100/0) 429(10010) q 256(25/75) 171(100/0) 368(100/0) 240(100/0) 4fim)0/0 N 328(18182) O N æ U 375(10010) 0 » ~ O ~ O O O ~ g N 0 > N 0 n

Curative 4002 is prepared by reacting the polyols PolyTHF250 (275.00 pbw) and TMP (35.76 pbw) with Mondur MRS polyisocyanate (133.00) before the addition of Luperco ATC (443.76 pbw).

Example 10 This example 10 illustrates the use of benzoylperoxide (BPO) / dimethylaniline (DMA) or methylethylketone peroxide (DDM9) / cobalt naphthenlate to cure unsaturated polymer and polyurethane hybrid adhesives.

Table 5. Peroxide Curing of Hybrid Adhesives <:,--,-,.-:;,:-,,:- MMq PLIOGRIP 9400,9 26.24 19.69 19.69 UPU Example 3, g 66.67 50.00 50.00 DMA, g 0.10 6% Cobalt Naph* g 0.72 0.60 Methyl Ethyl Ketone 1.80 1.50 Peroxide, g Luperco ATC, g 5.0 UPE Example 4, g 25.00 25.00 PeP 550, g 7.09 5.31 5.31 Mix Ratio, wt 3.1/1.0 2.0/1.0 Bondability Time, min 22 >120 77 Crosspeel, psi(%fl): ARCTCO FRP Plaque 7dRì>RT 7dRì)RT 7diZRT 360(100/0) 337(60/40) 299(95/5) 181(100/0) 250(40/60) 266(95/5) 326(100/0) 19dRT 291(100/0) 397(100/0) 310(100/0) 313(95/5) 316(100/0) 273(75/25) 292(96/4)

*OM Group, Inc., Outokumpu Chemicals. Mooney Chemicals Inc.

Vasset S.A. Cleveland, Ohio.

Example 11 This example 11 illustrates the use of diallyl phthalate (DAP) to achieve flexibility in unsaturated polymer / polyurethane hybrid adhesives. Ultimate elongation values as high as 85% as measured in the stress-strain test of the neat adhesives were observed.

Table 6. Diallyl phthalate (DAP) as an Effective Promotor of Flexibility for Unsaturated Polymer / Polyurethane Hybrid Adhesives 'ti-ti-- ,----- -,,- - 4228 PG 9400. % 24.15 Rubinate 9310, % ~ 8.85 UPU Example 3, % 59.69 DAP, % 6.24 Mistron RCS, % none Aerosil 200, % 2.73 Mo Sieves 5A, % 0.39 Luperco ATC, % DMA, % 0.090 4198 PolyTHF 250* % 6.29 PeP 550, % 6.53 PeP 550, % 6.53 Trimethylolpropane, % 0.40 Rubinate 9310, % 2.56 Mondur MRS, % Mistron RCS, % 1.76 UPUExam 3 % 61.37 -- DAP, % 6.93 DMA, % 0.092 1.76 Luperco ATC, % 1 11.00

Mix Ratio, wt ~ 33.5/100 | 350/100 Bondability, min 29 28 Green Strength 20' 190(2/98) 30' 326(75/25) ARCTCO FRP Plaque 7dRT 7daRT 251(100/0) 264(75/25) 386(100/0) 264(75/25) 386(100/0) 314(100/0) 282(100/0) 213(25175) 240(10010) 396(40/60) 432(1 00/0) Avg .............................. x - 297(60/40) 318(10010) Ultimate Tensile, psi 3350 3120 Ultimate Elongation, % 59 85 *Polytetramethylene ether glycol, MW 250.

Review of the Table 6 data shows that diallyl phthalate was very effective for promoting high ultimate elongation values of 59 to 85% for both unsaturated polyurethane I polyurethane prepolymer and unsaturated polyurethane I polyisocyanate adhesives.

Example Ila This example illustrates the use of an epoxy resin such as Epon 826 to achieve flexibiiity in unsaturated polymer / polyureaurethane hybrid

adhesives. Ultimate elongation value of 63% as measured in the stress- strain test of the neat adhesive was observed.

Table 6a. Epoxy Resin as an Effective Promotor of Flexibility for Unsaturated Polymer I Polyurethane Hybrid Adhesives ADHESIVE 4637 Pol NCO 4631 Rubinate 9310, % 10.32 Molecular Sieves 5A, % 0.21 EPON 826, % * 3.19 Aerosil R972, % 1.26 Luperco ATC, % 6.38 CURATIVE 4595 Pep 550, % 2.62 ET 3500, % 10.76 DETDA, % 2.66 UPU in Example 3, % 34.64 Methyl Methacrylate, % 15.40 DAP, % 3.85 Cabosil TS720, % 7.57 Molecular Sieves 5A, % 0.38 StanTone 6783, % 0.15 DMA, % 0.54 Flu eco ATC, % 0.054 Mix Ratio, wt 27/100 Bondability, min 5 Vertical Cardboard Very good non sag Hear Rise, °C/min 91/5.5 Green Strength 20' 305(90/0/0) 30'241(15/85/0) Crosspeel, psi(%FT) 4dRT ARCTCO FRP Plaque 373(100/0) 310 (100/0) 307 (100/0) 145 (100/0) 275 (100/0) 282 (100/0) ARCTCO FRP Hull, white 4dRT 278(100/0)

294(100/0) 277 (100/0) 182(100/0) 212(100/0) 250(100/0) ARCTCO Cold Press 7d@RT 290(30/0) 214(50/0) 120(0/0) 384(50/0 242(31/0) Mercury Marine FRP 4d@RT 326(100/0) 291(100/0) 355(100/0) 285(100/0) 393(100/0) 330(100/0) .Stress Strain: Ultimate Tensile, psi - 3640 Ultimate Elongation, % 63 *EPON 826 epoxy resin is the product of epichlorshydrin and bisphenol A available from Shell.

Example 12 This example 12 illustrates the humidity resistance of the unsaturated polymer I polyurethane hybrid adhesives. Tables 7, 8 and 9 show adhesives retaining as much as 100% of the adhesion to FRP after exposure to 100% relative humidity at 100°F (38°C) for 4 and & weeks.

Table 7. Formulations of Unsaturated Polyurethane Polymer /Polyurethane Hybrid Adhesives. Bw~ wrs s= Paff A Polyisocyanate + Unsaturated Prepolymer ~ Polyurethane Rd/asociiaS 4216 4205 4141 Rubinate 9310, % 11.95 UPU Example 3, % 40.26 53.30 Mistron RCS, % 14.85 15.58 Aerosil 200, % - 0.77 Mol Sieves 5A, % 0.33 0.23 DMA, % 0.097 0.10 PLIOGRIP 9400, - 19.27 Lu ercoATC,% - 0.73 W w 4158 4158 4198 4128 UPU ExamPle 3, % ~ 48.99 PeP550, % 5.21 DMA, % 0.073 PolyTHF 250, % 9.71 ~ ~ ~ 6.32 TMP, % 0.61 0.40 Rubinate 9310, % 2.57 Mondur MRS, % 3.65 Mistron RCS, % 2.28 1.77 X 25.72 Luperco ATC, % 16.25 ~ 11.05 Mix Ratio, wt 208/100 ~353/100 25/100 Bondabiiity, min 3 6 25 Heat Rise, "C/min 141/6 157/7 39110 Squeeze out Tack Free TF TF Trimmability yes/<8 min yes/<10 min yes Green Strength 10' 227(2/98) 9' 20' 335(70/30) 90(0/90) 12' 227(10190) o 'x'- '-'- - Ultimate Tensile, 2060 3270 psi 20 23 Ultimate Elongation, % Table 8. Humidity Resistance of Unsaturated Polyurethane Polymer/Polyurethane Hybrid Adhesives from Table 7 Adhesive 4233 4221 4159 Chemistry Polyisocyanate / Unsaturated Prepolymer/ Unsaturated Polyurethane Polyurethane Crosspeel, psi(%FT/CF): ARCTCO FRP 7d@RT 7d@RT 7d@RT Plaque 352(100/0) 305(95t510) 254(60/40) 498(98/2) 317(100/0) 320(100/0/0) 296(35/65) 389(90110) 280(10010) 238(100/0/0) 264(80/20) 393(85115) 293(10010) 262(100/0/0) 394(90110) 299(90110) 218(100/0) 247(95/5/0) 333(65/35) 320(100/0) 292(100/0) 274(100/0) 344(79/21) ARCTCO FRP 278(9515) Plaque 226(10010) 2 weeks 338(100/0) 100%RH/100°F 242(100/0) Tested wet / 202(10010) warm 257(9911) ARCTCO FRP 450(100/0) 275(10010) 353(1000) Plaque 381(100/0) 300(100/0) 371(100/0) 4 weeks 386(100/0) 318(100/0) 313(100/0) 377(100/0) 402(100/0) 294(100/0) 100%RH/100°F 244(100/0) 296(100/0) 314(100/0) Tested wet/ warm 368(100/0) 318(100/0) 329(100/0) Avg ARCTCO FRP 326(100/0) 290(100/0) 223(100/0) Plaque 341(100/0) 285(100/0) 229(100/0) 8 weeks 415(100/0) 274(100/0) 320(100/0) 355(50/50) 392(1000) 253(100/0) 100%RH/100°F 400(70/30) 310(100/0) 168(100/0) Tested wet/ 367(84/16) 310(100/0) 239(100/0) warm

Table 9. Humidity Resistance of Adhesive 4606 in Table 1, Example 6 l r FRP Plaaue ARCTCO RP Plaaue Avg 272(100/0) 284(100/0) standard deviation 14(810) 22(0/0) ARCTCO white FRP 225(100/0) 235(100/0) Plaaue 52(5/o) 27(010) ARCTCO FRP Hull 429(100/0) 294(100/0) pp1-ts 90(2810) 124(210) ARCTCO white 226(100/0) 206(100/0) 55(13/0) 38(010) ARCTCO Cold Press 342(88/0) 307(82/0) 34(10/0) 26(27/0) Mercury Marine 278(100/0) 294(100/0) 31(1110) 18(010) Review of Tables 7, 8 and 9 reveals that some adhesives of this invention provide laminates having humidity resistance whether the adhesives are Part A polyisocyanate plus unsaturated polyurethane:- Part B polyol plus peroxide or Part A polyisocyanate plus peroxide - Part B polyol plus unsaturated polyurethane.