CA2279315A1 - Unsaturated polymer polyurethane structural adhesive - Google Patents

Abstract

This invention is a structural adhesive and a laminate of untreated substrates adhered together with a structural adhesive which combines a two part polyurethane adhesive with a two part free radical curing adhesive. The adhesive is especially useful in the manufacture of personal watercraft built to withstand rough waves and made of fiberglass reinforced plastic.

Description

UNSATURATED POLYMER POLYURETHANE STRUCTURAL ADHESIVE
This invention relates to adhesives useful on fiberglass reinforced polyester (FRP) substrates used to make personal watercraft which must s withstand rough treatment by waves.
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 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 problems 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 glass is then bbnded~together with a resin, usually unsaturated polyesters cured at room temperature by free radical chemistry 2o 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 WO 98/33845 PC"T/US98/01793 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 s functionality, hereafter referred to as an °unsaturated 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 1 peroxide cured adhesive is very brittle, since there is no strength reinforcement in the adhesive such as the glass fibers used to build the io 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 is was also demonstrated by exposing the bonds in 100% relative humidity environment at 100°F (38°C) for eight weeks. Testing of bond strength after such exposure typically showed greater than 230 psi.
Examples of unsaturated polymers) for such adhesives include the same type of unsaturated polyesters used to construct watercraft as well as 2o 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 endcapping 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 hydroxyiethyl 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 simultaneously io 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.
is 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 curing.adhesive for bonding personal watercraft . ;_ without surface preparation is formed by combining the unsaturated polymer 2o 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 polyol/polyamine 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 s Model 200 from EMCZ, 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 io 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 ail 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 is 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 (formerly known as Arctco) or Mercury Marine, Hartford, Wl. ~ ~ :' 2o 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'-dimethoxy-4,4'-biphenyl diisocyanate, s 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3' dimethyl-4,4'-diisocyanato Biphenyl methane) or their polymerized versions or mixtures thereof. The most preferred isocyanate in the practice of this invention is polymeric Rubinate 9310 available from ICI, Sterling Heights, Michigan or Isonate 143 L
io 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 pofyol 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, is polyethylene oxide polypropylene oxide ether diol, polytetramethylene ether glycol, polythioether diol, polyester diol, polyepsiion 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 20-20 112 or Poly G 20-56, repectivefy.
The component selected to cure the polyisocyanate in the unsaturated polymer polyurethane adhesive of this invention includes 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 2s 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 andlor 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 / propoxylated s 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 io Corporation, Organic Division, Houston, Texas; Pluracol P-355 po(yol, 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; Thanol R470X polyol, available from Texaco Chemical Co., Bel(aire, Tex., a propoxylated derivative of is diethanolamine with a functionality of about 4 and a hydroxy number of 500;
Thanol SF-265 polyol, also available from Texaco Chemical Co., a propoxyfated derivative of triethanolamine with a functionality of about 3 and a hydroxyl number of 600; Voranol 230-660 polyol, a polyether trio! of 85.4 equivalent weight based on the propoxylation of glycerin, available from Dow 2o 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 inveritiori Vare the following aromatic 2s 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) so di(methylthio) toluene diamine 1,3,5-methyl-2,6-diaminobenzene toluene diamine derivatives containing halogen groups, cyano groups, alkoxy) alkylthio, alkenyl or carbonylic moieties m-phenyiene diamine s p-phenylene diamine 4,4'-methylenedianiline 4,4'-diaminodiphenyl sulfone 2,6-diamino-pyridine 4,4'-methylene bis(3-chloroaniline) io 4,4'-methylene bis(3-chloro-2,6-diethylanifine) 4,4'-methylene bis (3-chloro-2,5-diethylaniline) 3,3'-di-isopropyl-4,4'-diaminodiphenylmethane 3,5,3', 5'-tetraethyl-4,4'-diaminodiphenylmethane propylene-di-4-aminobenzoate is isobutyl4-chloro-3,5-diaminobenzoate bis (2-aminophenyl) disulfide bis (4-aminophenyl) disulfide di (alkylated amino) benzene secondary diamine bis (alkylated aminophenyl) methane secondary diamine 20 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.
2s 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 1,4-3o diazabicyclooctane) and suitable organo metallic catalysts such as those _7_ 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 s 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.
io The preferred optional thickening agents are: aluminum silicates, carbon black, talcs (magnesium silicates), calcium carbonate, calcium silicates, barium sulfates, graphite, or mixtures of fillers. The preferred filler ingredient is Aerosil 200 or Aerosil 8972 fumed silica from Degussa Inc., New York, N.Y.; and Cabosil TS 720 fumed silica from Cabot Corporation, Cab-O-Sil is 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 #7 2o 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 2s Chemicals, Inc, Little Rock) Arkansas.
The customer combines Part A and Part B in the desired ratio, usually 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 EMC2) Sterling Heights, 3o Michigan. The adhesive is applied to the first substrate by conventional _g_ 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 s 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 io 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 is 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 crosspee! 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 2o until it is separated from the bottom strip. Adhesion strength values over 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 s 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 glassfiber reinforcing the substrate.
io 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 fine. Fiber tear accompanying is 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 2o herein are expressly incorporated by reference.

This example one describes the preparation of a polyisocyanate I peroxide Part A to be cured by a polyol I polyamine I unsaturated polymer Part B.
s Formulation:
Polyisocyanate 4495 Rubinate 9310 polydiphenylmethane diisocyanate 11.92pbw io Moisture scavenger Molecular Sieves 5A powder 0.18 Cabosil TS720 treated fumed silica 0.88 Luperco ATC 50% Benzoyl Peroxide 5.29 18.27 i s Procedure Rubinate 9310 was charged into a 22-li#er flask. With an efficient, high shearing stirrer and under a riitrogen blankets Molecular sieves 5A powder was added, followed by Cabosil TS720. Then) Luperco ATC was added to 2o 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.

This example 2 describes the preparation of another poiyisocyanate /
peroxide Part A, a polyol is reacted with the polyisocyanate before the addition of peroxide.
io Formulation:
Polyisocvanate 4627 PolyG 20-112 ethylene oxide capped polypropyline ether glycol (MW 1000) i5 50.OOpbw Moisture scavenger Molecular Sieves 5A powder 3.86 Rubinate 9310 polydiphenylmethane diisocyanate 158.40 Mistron RCS Talc 46.31 Aerosil 8972 hydrophobic fumed silica 11.58 Luperco ATC 50% Benzoyl peroxide 115.78 385.93 Procedure Polypropylene ether glycol (PPG) (MW 1000), PofyG 20-112 was dehydrated in a vessel at 100-105°C and at a vacuum of less than 1 mm Hg) s er 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 poiyol 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
io nitrogen blanket was introduced before the addition of Mistron RCS and then Aerosil 8972. 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 is vacuum was achieved degassing was continued for 30 minutes before discharge. The product was stored under a nitrogen blanket.

This example 3 describes the preparation of an unsaturated polyurethane 20 (UPU) to be blended with a polyol and/or a polyamine to form Part B.
Formulation:

Unsaturated Polyurethane (UPU) Methyl Methacryiate, MMA 48.0 pbw s Hydroquinone, HQ 0.008 p-Benzoquinone, BQ 0.008 Hydroxyethyl Methacrylate, HEMA 9.6 Rubinol F428 ethylene oxide capped triol (Hydroxyl29.3 No 28) Rubinate M polydiphenylmethane diisocyanate 11.5 Dibutyl tin dilaurate 0.68 MMA 0.86 99.96 ~o 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 is 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.

2o This example 4 describes the preparation of another unsaturated polymer similar to the unsaturated polyester (UPE) cfiemistry used to bind glass fibers for the manufacture of watercraft.
Unsaturated Polyester UPE

WO 98/33845 PCT/t1S98/01793 Diethylene glycol 467.2 pbw Dipropylene glycol 31.1 Malefic anhydride 99.3 Isophthalic acid 536.3 Styrene 538.0 Monotertiary butyl hydroquinone0.193 Methanol 0.772 Procedure Diethylene glycol and dipropylene glycol were charged and heated to 140°C
under an inert blanket. Malefic anhydride and isophthaiic acid were added and heat to 210°C. The reaction continued until a viscosity at 28%
styrene of io 13-15 stokes. Styrene and monotertiary butyl hydroquinnone dissolved in methanol were added. The product was cooled to 170°C and discharged.

This example 5 describes the preparation of a polyol I polyamine I
~s 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) 20 2.67 pbw ET 3500 Propoxylated glycerin (OH# 48, MW 3500) 10.98 Ethacure 100 Diethyltoiuene diamine 2.72 2s Example 3 unsaturated polyurethane 43.59 Methyl methacryfate (MMA) 8.38 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 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 zo 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.

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, so fiberglass reinforced polyester substrate or Arctic Cat, Inc. cold pressed FRP

or Mercury Marine FRP, adhesion strength as high as fi10 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 I Polyurethane H brid Adhesive .~::::::::::.: .... ::::::::::::~::...:>:::
:::: :.: .~::.~:: ::::: _:;.,...:;:,:,:::::"::::::::::::
,.;.:...: .:>::~::;..,::::.:::.-.. ::.:~:::::::.:::~:::
......... .. . ... :.~~: ~::.:::.::::.::::
......; .,"; ,.,..:..:.:,.:::::::<:::::.::.:....:.:.
.::: .::::::.:: :. :......;.:::,:.::>:>,::_.A:.:....
::...:..::.:.::::>: ::x'~i::i:?:::3i:::.::.~:.,.'...
.: . .:., .~...: . :iJb::::::i:::v:.::::...::.::.;
::.:::::.:..:: . .::. ... 480fi~:
v:: :v.:.'r.:w: . :......... . ....::.:
. , n . ...:. ::.',.,.:::~;.?:ii :::::::,::::::Rdh~swe.
E~c~:...6. ...:

Pol isoc anate Ex. 4495 Curative Ex.S 4600 Mix Ratio, wt 19/100 Bondabilit , min 5.75 Vertical Cardboard no slum Button Sa , inch 0.10 Heat Rise, C/min 10116.7' Green Strength 30 min @ RT

127(5/0) 40 min@RT

Crri~speel, Psr~'~F'T)=

ARCTCO FRP Plaque After 7days(c~RT

281 (100/0) 163(10010) 276( 10010) 267(100/0) Average 319{9812) ARCTCO FRP Hull Part7d@RT

225(1 OOIO) 235( 100/0) 227( 10010) 230( 100/0) Avg 239(100/0) ARCTCO Cold Press 7d RT

332(25!0) 276(95/5) 176(9010) WO 98/33845 PCTlUS98101793 :4s :::.~~: .;;...::
. . . : . . v:. Ex: .. 06:::.

esrve rah 267(4010) 248(6811 ) Mercury Marine 7d RT i 268(10010) 375(10010) 225( 10010) 335( 100/0) 302( 100/0) S~ess Strain Ultimate Tensile, 2420 psi Ultimate elongation, 46 %

This example 7 illustrates the adhesion performance of an unsaturated polyurethane and polyurethane prepolymer hybrid adhesive on FRP.

Table 2. Performance of a Prepolymer / Acryiated Polyurethane Polyurethane Hybrid Adhesive .::~..,..:. :...-..:::.:...::....,.....:;.::::::....::.:...;:...:.:...:.:;:;.:;...:
;.~.::: ... :: ::...:::;:...:;::>:::<:.:,:::
. . ::.: .................,..
.... ..............:..:.::.:.>.::::::;::.:..
,..~... .... .... :.::.:::...:.:.:;.....::..:......::>::
.. :>;:
:... >.:.::::::.~ . :.:.~::::.<:.......::.:::.:4333.::,:::.~:.~::::::~:
::~.~..:...::.:.:.:..::::........
...: ;.:. .
.:;.:.....:::::::.:.:.::::::::::.:::::::.:...........
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:~1 ~:::
:. ::
::::::, ::
: :::
. ~:
~
;
~
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~YA

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. ......
:.::::::::::::::: .
., .
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: :::::..: .:
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:: : :
... :
:. : .::
........: :. .::.:....~:::.~.~:::.:.:::,..~..
:::.:::::.,.:.:.:~:::::::::.:.:._.:.:
.:.~ :.:: :.: :.:::::::::::,.
..:: . :.::::::::.:.:
.:: :.::. :.. :.
:.:...:..:. ,:..... ::...: ::.::::::::.
:.:::::.:.:::::::::.~::.:.:::::::.
~.....::~.: :.::::. .........nn..........
:>..:...:..:.....:.:...:. ......................
...:............:......n........:
... : ........k........:::.:::::..::::::
... ..v:.. :::::n~ :::......................., ::; w::.~:::::: .:...... ...............:.....;
...... ....i ::n.: :::~;:.~:::::n~:::n::::
:::::.~:.~: w::::..;:.~~:%:.
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... ... :::::Y.~/:::::.~::::n~::....:.: :j::'':.:
...y.........................:' ... .............
.. ..: : ....................~................. .
:::.,;'.:~.:~:::.~.~:::::.:::::~:::::.::.'::::::::::":::::._:.::.:::.......::..
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.....::,:: :. _:::..
~,: .:;:::.::>..::.::::~,:::<;.:;:.~::?:'<:<::. 4211 ', :F~ne .oi mer . .
::: :::::;:::

Ashland Pliogrip 25.68 9400, Lu erco ATC, % 6.42 :: :: . :: ::....::...::..::;::::.:::::::::::::::::..:..4324 ~tlR~t .LVE....:
:.:.: .... .

PeP 550, % 2.42 ET 3500, % 9.97 DETDA, % 2.47 Example 3, Usatuated44.23 Pol urethane, 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 Bondabiiit , min 7 Button Sa , inch <0.25 yros 't sr ~ ::.::>:
:...: ....~.p t'.......<:...

ARCTCO 7d RT

Original 182(100/0) 320( 100/0}

245(100/0) 262( 100/0) 254(100/0) ARCTCO 7d~RT

Cold Press 512(50/0) 487(40/0) 375(50/0) 425(7010) 479(7510) 456(5710) .. :... ~....::..:;,.:::~:::::::~~:vv~
:Stress.~trat r ii:;,:':%;:;:;fvujf:v :
' ' ' J
.

...7......:..
._......:.........1 ::::,.
.
.
F...............
........,.

Ultimate Tensile, 2600 psi Ultimate Elong, 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 l Acrylated Polyurethane l Polyurethane Hybrid Adhesive ... ~. . . :.
;:::p ' w } r :::::::
:::::.... ~c~hes~ue : ~w~ ...4344 .:: .
Ex..B . ..,:::::::::

~: 4323 ~t31. '~~iQ..: ::. ::::

Rubinate 9310, % 10.90 Mistron RCS, % 0.87 Aerosil 200, % 0.26 Mol Sieves 5A, % 0.086 Lu erco ATC, % 5.19 ~Ct~R,q~'f~'E 4338 PeP 550, % 2.54 ET 3500, % ~ ~ 10.45 DETDA, % 2.58 UPU in Exam le 3, % 38.04 UPE in Exam le 4, % 19.02 DAP, % 6.62 Aerosil 200) % 2.48 Mol Sieves 5A, % 0.41 DMA, % 0.50 Dabco T1, % 0.049 Mix Ratio, wt 20.9!100 Bondabilit , min Heat Rise, C/min not done Button Sa , inch 0.25 S ueeze out TF

Trimmabilit es Green Strength 30' 117(01100) 45' 258 30/70 Crosspeel, psi(/FTj:

ARCTCO FRP Plaque 7dCc~RT

289(10010) 227(100/0) 235(10010) 345( 100/0) 270(10010) Stress Strair~v 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 / Acrylated Polyurethane-Polyisocyanate Hybrid Adhesives.

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r' ~ ~ ~ C ~ C
'f . : O p f~O ~.~. ~ O O m o'o M O O O ' ~ N r ":: ~ ~'cDO ~ U r M
e0 'v ~ t i O cp ; o ' :
: O O N c0 r. N u7 rwn N
k M
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:
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:

. f... N !"9 . f~ M
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;
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i :'~.

., h ~,:'.:::
",i4 ~.iu O CO ~ ~" O ~ O O O_ y V ~ \
~'~'~""'N

4_ O O O O O N O \
~ O \
.- O

'rr;>?<:f;t ' r p O ~ v ~ ~.r O .- U Z7 cn O O N
:::..: ~' :<', 'd . tnN ~ ~
';4~s;::.; O ~ O cep CV N '-:~ ' $ ''' E- ~
<.:.. N c :
.
,~;ii:fl,jj ~

Y,,i.;;i.'.
i 'y3 rvry; ..
.' ::
:,"fl.~C' 't~::.:::> ;
f' i. ::
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'~

;. a aif':~71w:
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s,.v fif f r:~:
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N U ~ ~ ~ "" .
; o - ~ ;, :.~
~~

'' ~ ~ ~-~ ~ Q v::
~.~'>, a ' ~ ~ ,,sO
C~ ~
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v:li~

r ~ p X N '~ N v'' : O U '"
~, :
.;7_ '~::':

yKai:'f,':
.<::: Q = ~ U
. '.4:.. a~
iv ...,~::~~ ~ a.'~ a c ~~<' ~

a v>'~<~::::U ,~D ~ ~ O ~ ~J:,:
a. :::
w :

:.,, .
x,,.....~,:' .
....
:::
::

*Curative 4002 is prepared by reacting the polyols PoIyTHF250 (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) I cobal#
naphthenlate to cure unsaturated polymer and polyurethane hybrid adhesives.

Table 5. Peroxide Curing of Hybrid Adhesives . .~..-... :.........:..... .... ..:................i . ~w~n! . .::........:....?:...::::..::::.:~
:.....:....: :..,y: .::.
r vsi::-. i:

':;':, ....\";:.: .,....f...:'=:.::.::;:::.':.'::
. :i{x:..;, atiia:.N; :na ;
ia:xt.rti.: ;:: i t' . Y%:.~1...............
:~..kYi:>i'ri. rJ:.Yw ....
" 9r... . i N:R,..::~.:
: r ,~::.., ,n Vita.:.
X%' ,:2' .,:
.. N.. ..
::;'#::,.. ...,ke :Y ':a'. ! r . ? ':.
...;,~~v ~ , .yfi...:%f::;ij::'x...
. . .6aif.'vf.... , '~ : ~/ o-at:''-".::%f::
..t . . .a.
: . -; i:.;::. :.. r: . f i' $?:i~t''' .i:' .: :':4,'. l.;i ( . ' . . , ::'~ . 't: . ::.. .r.., '' i;'.~'.~''..
.. p, ' '$'..'~, ....~. . . . ,E ~' :4. ny:$':
.. ?a i ,..i,. s.'~i,.
:.a..Z $ , 'Y..... :: ~, Y.:' 4y i>:::'tS:':>iv;
A..:.. ' : t. :
1 ': ,~:.i$i: ':~w :n:i~ ,ia7~..
:O .~:>. .: ~ ' ~ . H:i'. . , ~:...
,...:f .;y ! :.: iv:
; . . ., t:..~.
~ v. r.'.. . ,..,4 - . . :O~ :,y. yy . :: ' :X;'v;;... ~
,.... : ~
~~i ~ . , ~ . ~::' ! h v 'S:P.', :i.. . }: -. ' J.'?,tiv...
. ' >: :: . . '.
':. .c< : ' ';a; ..G: :~i. rh . : i~
: . i~~n~' '~s'~~~'?ny.: ~7Y
. ,,.j..:. .. ><2:< .. ~ .
: . ~, ::x .~.:: . i.Gy.,~:~s:n~>y.':.v 1:~ %;,.,'. :' .2'...)..,.:..,a.,i~,. ' R..,iy:'uf''Yi.';;.' > .,.: r . .,:i ' . '~M. : ~ ~. ..,.: . .. "..,": ~y/~~
~ : .:..'t<t ::::n,:
~ : ..'~:.i ~x ': vo-i::.:::., i5 . ~r...x,.f.-,. . 'ia:>'' '7 ~ ..~: .x. :::
E a., . ~~r'~'..;:
~ :.. -a.. , ." /~ ":">'':
' . i::
~~ t: it:: . : mn.:.~~..:::'~:
% . . k x\:: :
<Si :i:i ,i' ~'' :ah :: :i5.T ~
, ~:
$:~

s : .t . ..: : .
it ia. y 0:41 u a o-: :a. : nn::
o' . f: F: .. .. ..,w h .' ,... .,. : :
O' i:-::. ..a :..:. : ... :.....a~:::;:, "t~fi :., .. ,:y~,. a, ....', :::..:::_~
' . . . . . :::x::: iu ....i ~ sv. ,C:.... .. :. .. .1 :
:~ ?: . . .?.. iX i tti4::::>::
. ,,.,E'., . ii:4::.....:
x ,...': riv .
n . . . ,. ..
:: . , ..
~?::M .".v.. ..
' ', ' :, :
' v ~ H>1 , ' ::' '?

'?.
:???

. .s ... .. ................
.., n . . ... . x....n.... ..... .. .... .
. ...:. . .. .. : .. .
.tt:.. ...... ,.:%4.~ . .
::. . ,. ....
~ "y. .f.. . r'...:t?'.:?. . ...... .
~:. .::::.. .
.:. ...........
........:..............................
n ..v..
.:: .
:..Y .
.. .
. ~ :
....................

PLtOGRIP 9400, 26.24 19.69 19.69 g UPU Example 3, 66.67 50.00 50.00 g p~ g - - 0.10 6% Cobalt Naph* 0.72 ~ 0.60 -g Methyl Ethyl Ketone1.80 1.50 -Peroxide, g Luperco ATC, g - - 5.0 UPE Example 4, 25.00 25.00 g PeP 550, g 7.09 ~ 5.31 5.31 Mix Ratio, wt 3.1 /1.0 2.0/1.0 Bondability Time, 22 >120 77 min 'Crosspeel, psi(/F7):

ARCTCO FRP Plaque 7_d(a~RT 7~RT B~RT

360(100/0) 337(60/40) 299(95/5) 181 (100/0) 250(40/60) 266(9515) 326(100/0) 19d RT 291 (100!0) 397(100/0) 310(100/0) 31_ 3(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 dialiyl phthalate (DAP) to achieve s flexibility in unsaturated polymer / polyurethane hybrid adhesives. Ultimate eiongation values as high as 85% as measured in the stress-strain test of the neat adhesives were observed.
Table 6. Diaflyl phthalate (DAP) as an Effective Promotor of Flexibility for io Unsaturated Polymer I Polyurethane Hybrid Adhesives ':::.:::. .:.. : , ..::. ~423~..~:
.::- .:,. - ~ ... ... .::....413::...... :.:..
:::::::::.... . ~dhes~~te..:::....:... ... .
::.: . .- .

.:..: .,. :. .,:.:::::::::.. 422 :::::::::. :.~:::::::::.
:::. .
p~~~ ..~ ; . ::::::::.::<:::::::::::::::~:::::
<::~:
. o Cfl~... .....
. . .. .. .

PG 9400, % 24.15 Rubinate 9310, % 8.85 UPU Exam le 3, % 59.69 DAP, % 6.24 Mistron RCS, % none Aerosil 200, % 2.73 Mol Sieves 5A, % 0.39 Lu erco ATC, % 0.92 DMA, % 0.090 C~l~~ ~~lF' 4198 Pof THF 250* % ~ 6.29 PeP 550, % 6.53 Trimeth l01 ro ane, 0.40 %

Rubinate 9310, % 2.56 Mondur MRS, Mistron RCS, % 1.76 UPU Exam le 3, % 61.37 ---DAP, % 6.93 DMA, % 0.092 1.76 Luperco ATC, % 11.00 Mix Ratio, wt 33.51100 3501100 Bondabiiity, min 29 Green Strength 20' 190(2198) 30' 326 75125 :.:;;..,...;::,:...:.:::....:<:......:
.:.r..:;.::;>:.:
<~
.: :
~:f; :
~
r ..
:
.: :.
'.,t .,Y,.::
. : :::! : 'i',' . . ...... ! ...
.... ..
.

. 7d RT
.. .. ....,...
ARCTCO FRP Plaque 7_ dCcDRT 251 (1 OOIO) 264(75/25) 386(10010) 314(100/0) 282(10010) 213(25175) 240(10010) Avg 297(60140) 318(100/0) :i.y:::::.;:::::":::::::::.'~::::::'::':::".';:::::::::::'i:":::k::4:::

.s, .....f.'.'.................
, ~ . , .,.;.. .
.... V.s'.
-::~':'~t:.i:..'::.%ii'i~"::y:jj;:~Y..:.:::W
.:::':h:::iC:4i:'!.'~..:i'.:ii . .. :....:.:n ', .~~ ~:.'..:..:.~fi:7Ji<:.<:iy~.'...:
"... :. r: .:.
' ....
::::
f ~ s ~ :
~.
~~ ' ~

...
....
.. ...... .........
... . . .... .......
.. ...
..v .......
j...., ........... ' ....... ... ...s......
.... ......... .
........~..... ..
ins...::::
....
...:.... Y......., s...:~ ::::
........n.........n...n.......

...... 3350 3120 Ultimate Tensile, psi Ultimate Elongation,59 85 %

"Polytetramethylene ether glycol, MW 250.
Review of the Tabfe 6 data shows that diallyl phthalate was very effective for promoting high ultimate elongation values of 59 to 85% for both unsaturated polyurethane l polyurethane prepolymer and unsaturated polyurethane / polyisocyanate adhesives.
Example 11 a io This example illustrates the use of an epoxy resin such as Epon 826 to achieve flexibility 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 / Polyurethane Hybrid Adhesives Pol NCO 4631 Rubinate 9310, % 10.32 Molecular Sieves 5A, % 0.21 EPON 826, % ' 3.19 Aerosii 8972, % 1.26 Lu erco ATC, % 6.38 Pe 550, % 2.62 ET 3500, % 10.76 DETDA, % 2.66 UPU in Exam le 3, % 34.64 Meth I Methac late, % 15.40 DAP, % 3.85 Cabosil TS720, % 7.57 Molecular Sieves 5A, % 0.38 StanTone 6783, % 0.15 DMA, % 0.54 Lu erco ATC, % 0.054 Mix Ratio, wt 271100 Bondabilit , min 5 Vertical Cardboard Ve ood non sa Hear Rise, C/min 91/5.5 Green Strength . 20' 305(90/0/0) 30' 241 1518510 Crosspeel; psi (%FT) 4dRT
.ARCTCO FRP Plaque ' 373 (100/0) 310 (10010) 307 ( 10010) 145 (10010) 275 (100/0) ARCTCO FRP Hull, white 4dRT

294( 100/0) 277 (10010) 182( 100/0) 250 '10010 ARCTCO Cold Press 7d cL'DRT

290(30/0) 214(50/0) 120(0/0) Mercury Marine FRP 4d@RT

326( 7 0010) 291 ( 10010) 355( 100/0) 285(1 ooro) Stress Strain:

i 3640 Ultimate Tensile, s _ 63 Ultimate Eion ation, /a *EPON 826 epoxy resin is the product of epichlorshydrin and bisphenol A
available from Shell.
Example 12 s 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 8 weeks.
io Table 7. Formulations of Unsaturated Polyurethane Polymer /Polyurethane Hybrid Adhesives.

....:..... :.:...................:... .:::::::::::::.;.rrrr:::.:._ ... ...,~:~ :,: .:
.:...:-:~...:..::: .....a,~~.::...::
.. .::at:.::
.. . yes: ;. :;.vtn,t:...:
.............:....;::::::::~..; :v.
:::::: .~::::: :.::..:
~:::.~:::: .. :'' : .... .. 3 r .;
:: .,.-::::,,:.::..;..t~ .\...... M:i:.
:A: .... .. :.:t:.t...rrr . . . ..::.
,'/ r\ . .
:: v > .:.c.. r ~rft . ..."
::yli .:
'.'.Xo; : ;) :::..~.
r . . , ;.:u ...:~:.r . .....c .:u:::..::n '.:.. .:
. ' LE'2r . M. : a2:
r:. ~ 'I,( . .t::. ~:r.:CS'.
. .. u.. '~4:N4' :::::::'. . L:F'~.. .. .. .f..
'::. ...r.. .. ' . .
.. /
. :r Yl: .... :' i~r:
. v:::::
:S . .r i:a; : rir:::u ' ,.:.5 r.. . ....s.:.:
\\'s .y;n: r?r'.S'" i:
'-::': tp.: \F:fu ...............n:::.
~ . tr'.::,y ~uv? ......................., /f. ~ ..........r...
::\v'v': . tn .::4: .:
1s ., .......~t ~~~5:'.~G::::. .... .......
. . ~
a .:....t.....r..,S,.,.;:~~~.yt;., ......'?,:,.:::::::::::r...;:::............
v.v:::: ::.:..:............
sLrr.:'.: ........L....::.......s t..
~~~~~~.::
:w:r::::::.

Part Polyisocyanate Prepolymer A + Unsaturated ' Pol urethane . ;:r: .:::: 4141 . .. :.: : 4216 4205 fue. . .::.:::
.:.:..:.:::.:::
l rsoc adi~te Rubinate 11.95 7.91 9310, %

UPU 40.26 53.30 Exam le 3, %

Mistron 14.85 15.58 RCS, %

Aerosil - 0.77 200) %

Mol 0.33 0.23 Sieves 5A;
%

DMA, 0.097 0.10 %

PLIOGRIP - - 19.27 9400, Lu - - 0.73 erco ATC, %

::.:..:: 4128 :-:::.::::::::. 4158 4 998 :, .
..
:
>:
._::
_:::::::::::~::::;:::::::::::::::
F':~'::$::::::::::::::::::::::::>:.., UPU 48.99 Exam 1e 3, %

PeP550, 5.21 %

DMA, 0.073 %

Pol 9.71 6.32 THF
250, %

TMP, 0.61 0.40 %

Rubinate - 2.57 9310, %

Mondur 3.65 --MRS, %

Mistron 2.28 1.77 25.72 RCS, %

Lu 16.25 11.05 erco ATC, %

Mix 208/100 353/100 25/100 Ratio, wt Bondabilit 3 6 25 , min Heat 141/6 15717 39110 Rise, Clmin S Tack Free TF TF
ueeze out Trimmability yes/<8 min esls10 es min Green 10' 227(2/98) 9' Strength 20' 335(70/30) 90(0/90) 12' . 227 ...................................
..............
y.....
:::::::..:
..;...
;~::::..._::..;~::.
.....
:~.
~~
.
.:::
~.
:~.,.::....

~
..~.
....
.
, .
.
..:::.a;..;:Ar.
:
~~:.~~~:::.::::.:
v.
#
.
v 'v . 2060 3270 Ultimate 20 23 Tensile, Ps~
Ultimate Elongation, Table 8. Humidity Resistance of Unsaturated Polyurethane PoiymerlPotyurethane Hybrid Adhesives from Table 7 esrve ~ 4221. v ... 4159 _ . ., .:A 4233 dh _ _ Prepolymerl Unsaturated _ Polyisocyanate _ l Unsaturated Chemistry Pol urethane Pol urethane 5Y's ARCTCO FRP 7d RT 7, dT ART 7d(a~RT

Plaque 352(10010) 305(951510) 254(60/40) 498{9812) 317{10010) 320(10010/0) 296(35165) 389(90110) 280{100/0) 238(10010/0) 264(80/20) 393(85115) 293(10010) 262(100/0/0) 394{90110) 299(90110) 21810010 2471951510) 333(65135) 320!10010) 292(10010) 274(10010) 344(79121) ARCTCO FRP 278(9515) Plaque 226( 100/0) 2 weeks 338(10010) 100%RHI100F 242{100/0) Tested wet 202(10010) /

warts 2 57(99/1 ) ARCTCO FRP 450(10010) 275(10010) 353(1000) I
I

Plaque 381(10010) 300(10010) 371(100/0) '~

4 weeks 386(10010) 318(100/0) 313(100/0) 377(100!0) 402(10010) 294(10010) 100%RHI100F
244(10010) 29610010 31410010 sted wet 368(10010) 318(10010) 329(10010) I
e a r m w _;1 _ Avg i ARCTCO FRP 326(100!0) 290(10010) 223(10010) Plaque 341 (100/0) 285(10010) 229(10010) 8 weeks 415(10010) 274(10010) 320(10010) 355(50150) 392(1000) 253(10010) 100%RHI100F

400(70130) 310100/0 16810010 Tested wet warm 367(84!16) 310(100/0) 239(10010) St~BgT~TE ~~I~fT ~~~~E ~~~

Table 9. Humidity Resistance of Adhesive 4606 in Table 1, Example 6 _ wwww!wy . ww"wwwwwwww"wwlwws!, ..,~ ..~ ~:. ~.a~:.>:i::~"
;:::,t~.. ;.
r'G .. .n.~ 5:: ~~'. ~ : '.f ''i r.. .~.~:G. .:.
$;~ '.:~::~$ .~'.
~::.:%~.. .:~;:Y~ .~','>~'fi:,.p :.:..4.; .
...y .
s .~.... ~:.k~ ;..;: :':.;C'~~.r~.".ln''° ..'L.~.. . .G..?
'':~~,~q~~,' . ~':kk.:;..<.f ..k~4.~:~.~~" .~~.,r. Y.'..,i,~ . '~ y :.k ~ . .:
iJ;yJ.i: n~ i.~~:~~. ' r :yaY52 : rY : \ . ~.~:'.%7k~: .
. t . ~. .. .;:~',~:. :.y ~ i< ' . , :r ~;: :t7 " ~ ~'~ ~ ~ ~ . 9;. :
sk. ~ '~;~'.'~.~~'....~~,~v>.~...: .' ~ . : .., : . ri x!r~ .:: !:.. .
. ;'i . :: ... :.V.r~~: : . . :<;:Z:~..~'.~:~.~y .'~:ks h, ,~', '.~~,~~:h~:..
?~,~.C.';k..~ : '~'~...~:.~..fi~5:3,>.;,.'..,.~,'.rw~
'C n 9x '~.~..k. .~ ~ ~ ~ . .e N ~, ,6;s2~~ ': ~ yr, .~'~'~ ~., f ~'/. .
~.~....;; .. ~ :
'.> '. > ..v);r,:-:Y ,:~;~~;..Vy:.yi '~ :i ~,.~.:~::::4a.~.:
~,; ~~~ 'h ~~ ~~'..:~.... .:
'~ .. .; ~ : x,~. ~nr, ~ . . ~ ~ s~,.~ :. :..::.f~x% -::$:t~,.::~:..
k:::.~',.,;,. :.;:y~,.;r~.ø",.~"..',..; ..:..: .~,:. .:. '..: :::.... ~......
..........:.:..........: ..........
k:.:.::.. .~...: ::.~.::''~..~...:..:.. ::?~......:::.'~'o. ~: ~~r: :.. ,.,., ..:: :.!..:....:...... .. .......:.
ARCTCO FRP Plaaue Avg 272(100/0) 284(100/0) standard deviation 14(8ro) 22(0/0) ARCTCO white FRP 225(100/0) 235(100/0) Pia ue s2(5/o) 27{0/0) ARCTCO FRP Hull 429(100/0) 294(100/0) Parts 9o(2g/o) 124(vo) ARCTCO white Hull 226(/00/0) 206(100/0) Parts ss(13ro) 38{0/0) ARCTCO Cold Press 342(88/0) 307(82/0) 34(10/0) 26(27/0) Mercury Marine 278(100/0) 294(100/0) 31(11/0) 1g(~/0) s 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 poiyol plus unsaturated to polyurethane.

Claims (28)

I Claim:

1. A two component structural adhesive composition for substrates requiring no surface pretreatment and curable at ambient temperatures comprising either:
a) a first component mixture of polyisocyanate and peroxide and a second component mixture of polyol or polyamine or combinations thereof, and unsaturated polymer.
b) a first component mixture of polyisocyanate and unsaturated polymer, a second component mixture of polyol and peroxide.

2.The adhesive of claim 1 wherein said peroxide. is benzoyl peroxide.

3. The adhesive of claim 1 further comprising diallyl phthalate.

4. The adhesive of Claim 1 wherein said polyisocyanate is polymeric methylene diphenyl polyisocyanate, said polyol is a mixture of propoxylated pentaerythritol and propoxylated glycerin, said polyamine is diethyl toluene diamine, and said unsaturated polymer comprises unsaturated polyurethane or unsaturated polyester or combinations thereof.

5. The adhesive of Claim 1 wherein said substrates are selected from the group of fiberglass reinforced plastic, metal and wood.

6. The adhesive of Claim 1 wherein said substrates are fiberglass reinforced plastic.

7. A laminate of two substrates having no surface pretreatment adhered together by the cured residue of a two component adhesive mixed before application to one of said substrates, said adhesive comprising polyisocyanate, polyol or polyamine or mixtures thereof, unsaturated polyurethane or unsaturated polyester or mixtures thereof, and peroxide.

8. The laminate of claim 7 wherein said polyisocyanate and said peroxide are provided in a first component mixture and said polyol or polyamine and said unsaturated polymer provided in a second component mixture.

9. The laminate of claim 7 wherein said polyol and said peroxide are provided in a first component mixture and said polyisocyanate and said unsaturated polyurethane or said unsaturated polyester are provided in a second component mixture.

10. The laminate of claim 7 displaying, when disrupted, tearing of said fiber glass reinforced plastic substrate and continuing integrity of said cured adhesive residue.

11. The laminate of Claim 7 wherein said polyisocyanate is polymeric methylene diphenyl polyisocyanate, said polyol is a mixture of propoxylated pentaerythritol and propoxylated glycerin, said polyamine is diethyl toluene diamine, and said unsaturated polymer comprises unsaturated polyurethane or unsaturated polyester or combinations thereof.

12. The laminate of Claim 7 wherein said substrates are selected from the group of fiberglass reinforced plastic, metal and wood.

13. The laminate of Claim 7 wherein substrates are fiberglass reinforced plastic.

14. The method of making a laminate of a first untreated substrate and a second substrate adhered together with a structural adhesive comprising a peroxide curable unsaturated polymer in combination with a polyurethane or polyureaurethane, such adhesive having room temperature curable property, variable open time, sag resistance on a vertical surface, tack free squeeze-out along the bondline, trimmable squeeze-out along the bondline, fast green strength development, at least 20% ultimate elongation, humidity resistance, and low temperature resistance, comprising the steps of applying to said first substrate an adhesive composition comprising a mixture of a first component a) polyisocyanate and peroxide and a second component b) unsaturated polymer and polyol or polyamine or mixtures thereof.

15. The method of claim 17 wherein the equivalent ratio of polyisocyanate: polyol plus polyamine is 0.8 to 1.8:1.

16. The method of claim 17 comprising 15 to 50 parts by weight of said first component and 50 to 85 parts by weight of said second component.

17. The method of claim 17 wherein said first component comprises polyisocyanate and unsaturated polymer and said second component comprises polyol and peroxide.

18. The method of Claim 17 wherein the equivalent ratio of polyisocyanate:polyol is 0.8 to 1.8:1.

19. The method of Claim 17 wherein said polyisocyanate is polymeric methylene diphenyl polyisocyanate, said polyol is a mixture of propoxylated pentaerylthritol and propoxylated glycerin, said polyamine is diethyl toluene diamine, and said unsaturated polymer comprises unsaturated polyurethane or unsaturated polyester or mixtures thereof.

20. The method of Claim 17 wherein said substrates are selected from the group of fiberglass reinforced plastic, metal and wood.

21. The method of Claim 17 wherein said substrates are fiberglass reinforced plastic.

22. An adhesive composition for substrates requring no surface pretreatment comprising polyisocyanate, peroxide, polyol, unsaturated polymer, and optionally polyamine.

23. The adhesive of Claim 25 wherein said peroxide is tertiary butyl perbenzoate.

24. The adhesive of Claim 25 wherein said substrates are selected from the group of fiberglass reinforced plastic, metal and wood.

25. The adhesive of Claim 25 wherein said substrates are fiberglass reinforced plastic.

26. The adhesive of Claim 1 further comprising epoxy resin.

27. The laminate of Claim 7 wherein said adhesive further comprises epoxy resin.

28. The method of Claim 14 wherein said adhesive further comprises epoxy resin.