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Title:
HIGH SERVICE TEMPERATURE POLYURETHANE ELASTOMERS
Document Type and Number:
WIPO Patent Application WO/1999/016808
Kind Code:
A1
Abstract:
The invention is polyurethane compositions useful in high temperature service environments comprising: (A) i) one or more polyols having hydroxyl functionality of 3.0 or greater and a weight average molecular weight of 2000 to 6000 wherein the polyols are the reaction product of an initiator or mixture of initiators having an average functionality of 4 or greater and one or more alkylene oxides; or ii) a) one or more polyols having hydroxyl functionality of 3.0 or greater and weight average molecular weight of greater than 6000 wherein the polyols are the reaction product of an initiator or mixture of initiators having an average functionality of 4 or greater and one or more alkylene oxides, and b) one or more cross-linkers having an equivalent weight of 200 or less; (B) an organic isocyanate; and (C) a catalyst for the reaction of an isocyanate with an active hydrogen containing compound; wherein the ratio of isocyanate moieties to active hydrogen containing moieties is from 0.9:1.0 to 1.5:1.0. The compositions of the inventioncan be processed at relatively low temperatures to form high heat service temperature compositions useful as adhesives, sealants, encapsulants, gaskets or elastomers. Such formulations have relatively low viscosities at low and ambient temperatures. Further, the cured compositions of the invention demonstrate the ability to withstand temperatures of 140 °C or greater and more preferably 155 °C or greater without significant deterioration in properties.

Inventors:
Roser, Jean-luc (7 rue des Rosiers St. Julien en Genevois, F-74160, FR)
Sood, Rajinder L. (Chemin du Treizou Trelex, CH-1270, CH)
Storione, Antonio (Chemin du Petit Bois Chatelaine Geneva, CH-1219, CH)
Application Number:
PCT/US1998/019589
Publication Date:
April 08, 1999
Filing Date:
September 18, 1998
Export Citation:
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Assignee:
THE DOW CHEMICAL COMPANY (2030 Dow Center Midland, MI, 48674, US)
International Classes:
C08G18/08; C08G18/22; C08G18/48; C08G18/66; C08G18/76; C09D175/08; C09J175/04; C09J175/08; (IPC1-7): C08G18/48; C08G18/66; C08G18/76; C09D175/08; C09J175/04; C09J175/08
Foreign References:
US4242490A
US5229427A
DE4236562A1
EP0380088A2
Attorney, Agent or Firm:
Sims, Norman L. (Patent Dept. P.O. Box 1967 Midland, MI, 48641-1967, US)
Download PDF:
Claims:
WHAT IS CLAIMED IS :
1. Composition useful in preparing a polyurethane elastomer comprising A) i) one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of 2000 to 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides ; ii) a) one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of greater than 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides, and b) one or more crosslinkers having an equivalent weight of 200 or less ; B) one or more organic isocyanates ; and C) one or more catalysts for the reaction of isocyanate containing compounds with active hydrogen containing compounds ; wherein the ratio of isocyanate moieties to active hydrogen containing moieties is from 0. 9 : 1. 0 to 1. 5 : 1. 0.
2. The composition of Claim 1 wherein the ratio of isocyanate groups to active hydrogen containing groups is from 1. 0 : 1. 0 to 1. 10 : 1. 0.
3. The composition according to Claim 1 or 2 wherein the isocyanate is an aromatic isocyanate, an oligomerized aromatic isocyanate or a polymerized aromatic isocyanate.
4. The composition according to any one of Claims 1 to 3 wherein the isocyanate is an aromatic isocyanate, an oligomerized aromatic isocyanate or a polymerized aromatic isocyanate derived from diphenyl methane diisocyante.
5. The composition according to any one of Claims 1 to 4 wherein the initiator for the polyol is sorbitol, a mixture of sucrose and glycerin, an adduct of an epoxy resin and a glycol, or an adduct of novolac resin and one or more alkylene oxides.
6. The composition according to anyone of Claims 1 to 5 wherein the weight average molecular weight of the polyol is from 8000 to 16000 and the functionality of the polyol is 3. 2 to 4. 8.
7. An elastomer comprising the reaction product of the composition according any one of Claims 1 to 5.
8. An adhesive or sealant composition comprising a polyurethane composition according to any one of Claims 1 to 6.
9. A process for encapsulating a substrate comprising a) placing the substrate in a mold ; b) filling the mold with a composition according to any one of Claims 1 to 6 ; and c) exposing the composition to curing conditions.
10. A process for coating a substrate which comprises a) contacting a substrate with a composition according to any one of Claims 1 to 6 ; b) curing the composition.
Description:
HIGH SERVICE TEMPERATURE POLYURETHANE ELASTOMERS This application relates to polyurethane compositions useful as adhesives, coatings, sealants and elastomers, especially cast polyurethane elastomers.

High service temperatures are required for many applications for polyurethane compositions. High service temperature is directly related to the thermal stability of the polyurethane, which is usually expressed in terms of the specific temperature, temperature ranges, or time-temperature limits, within which the polymer can be used without it experiencing significant degradation of key performance properties. It is known that conventional polyether based polyurethane compositions can withstand continuous use temperatures of 100 to 120°C. The use of polyurethane compositions in automotive applications, such as under the hood, and electrical encapsulation or bonding applications often require higher service temperatures of 140 to 155°C. As polyether based polyurethane compositions provide processing cost advantages over other polyurethanes it is desirable to have high service temperature polyether based polyurethane compositions. Such high service temperature applications include elastomers used in electrical castings, adhesives and coatings, encapsulants and gaskets.

Cast elastomers may be used for a wide variety of applications including tires and wheels, for example forklift tires, roller-skate and roller-blade wheels, running shoes, brake diaphragms, snowplow blades, grain buckets, drilling pipe thread protectors, grain and coal shoots, classifier shoes, hydraulic seals, wheel shocks, bowling ball cover stock, shaft couplers, sheet goods, rod stock, mining screens, conveyor belts, coated conveyor belts, gears, pipeline rigs, boat fenders, bump liners, helicopter blade sleeves, bumper pads, die cut pads (paper box industry), large rollers for steel and paper mills, copier rolls, encapsulated gate valves, encapsulated transponders (cattle tags), encapsulated concrete mixer blades, drive belts, dead blow hammers, sprockets, overrings, crane shock absorbers, sound dampening pads potting compounds and for coatings and encapsulated parts which are used in high heat environments, such as in the engine compartment of automobiles.

Polyurethane cast elastomers are typically made by contacting the raw materials such as a polyisocyanate, a polyol, and often a chain extender in a mold coated with a mold release, and the contacted material is allowed to cure to form an elastomeric polyurethane piece.

Polyurethane rigid foam utilizing highly functional rigid polyols, have been disclosed as useful in the insulation of hot water/steam pipes for district heating, see Pots, et al., Developments In Rigid Polyurethane Foams for Insulation of District Heating Pipes,

Polyurethanes World Congress, 1984. It is recognized that higher heat resistance is not normally obtained using conventional polyurethane chemistry except through the modification of the chemical structure by adding heterocyclic groups such as isocyanate, poly (urethane-oxylazolidone-isocyanate), or polyimide groups. See Frisch, et al., New Heat Resistant Isocyanate Based Foams For Structural Applications, Polyurethanes World <BR> <BR> <BR> Congress, 1991 and Frisch, et al., Novel Heat Resistant Isocyanate Based Polymers, 33'"<BR> <BR> <BR> <BR> <BR> <BR> Annual Polyurethane Technical Marketing Conference, September 30-October 3rd 1990.

There are some limitations with this chemistry and soft elastomer products having such properties are difficult to obtain. The open literature has reported the development of heat resistance elastomers having been achieved through the use of specific cross-linkers, such as p, p' diphenol, quinol and hydroquinone di (beta-hydroxyl ethyl) ether (HQEE), see Frisch supra. It has also been reported that high heat resistant elastomers can be prepared from paraphenylene diisocyanate and naphthalene diisocyanate, Hepburn Polyurethane Elastomer 2nd Edition, 3 : 67, 1964 and Plumer, et al. Paraphenylene Diisocyanate Based Thermoplastic Polyurethane Provide High Thermal Stability, Polyurethanes Expo 1996. The high temperature elastomer systems described in such references exhibit the drawback of being solid or containing compounds solid at room temperature and therefore require processing above their melting points, usually above 100°C.

Conventional polyether based poiyurethane elastomers can withstand continuous use temperatures of up to 100°C to 120°C. European community legislative changes relating to vehicle pass by noise have reduced the allowed noise emission. This requires engine encapsulation and reduced air flow within the engine compartment resulting in higher working temperatures for all materials used in the engine compartment.

Elastomers, gaskets and electrical encapsulating applications now require higher working <BR> <BR> <BR> <BR> temperatures, up to 140°C with a peak application temperature of up to 155°C. Until now no heat resistance soft cast elastomers based on conventional polyether based polyurethane systems have been available.

What are needed are polyurethane formulations capable of forming polyurethanes which can be used in high temperature service environments and which do <BR> <BR> <BR> <BR> not degrade when exposed to temperatures of 120°C or greater, preferably 140°C to 155°C and which formulations are easy to process at about ambient temperatures. In other words, formulations which are low in viscosity and easy to handle at low temperatures. What are also needed are high temperature resistant elastomers which can be prepared by casting techniques at or near ambient temperatures.

The invention is polyurethane compositions which upon cure are useful in high temperature service environments wherein the compositions comprise A) i) one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of 2000 to 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides ; or ii) a) one or more polyols having hydroxyl functionality of 3. 0 or greater and weight average molecular weight of greater than 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides, and b) one or more crosslinkers having an equivalent weight of 200 or less ; B) one or more organic isocyanates ; and C) one or more catalysts for the reaction of an isocyanate with an active hydrogen containing compound ; wherein the ratio of isocyanate moieties to active hydrogen containing moieties is 0. 9 : 1. 0 to 1. 5 : 1. 0.

In another embodiment the invention is a polyurethane elastomer prepared from the compositions of the invention.

In another embodiment the invention is adhesive and sealant compositions prepared from the polyurethane compositions of the invention.

In yet another embodiment the invention is a process for preparing a high temperature elastomer. The process comprises first contacting in a mold i) one or more low viscosity organic isocyanates and one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of 2000 to 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides ; ii) one or more low viscosity organic isocyanates and one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of greater than 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or more alkylene oxides and one or more a cross-linkers having an equivalent weight of 200 or less ; or iii) one or more isocyanate functional prepolymers prepared from one or more low viscosity organic isocyanates and one or more polyols having hydroxyl functionality of 3. 0 or greater and a weight average molecular weight of greater than 6000 wherein the polyols are the reaction product of one or more initiators having an average functionality of 4 or greater and one or

more alkylene oxides with one or more cross-linker having an equivalent weight of 200 or less. The process further comprises curing the contacted materials to form a solid polyurethane elastomer.

The formulations of the invention can be processed at relatively low temperatures to form high heat service temperature compositions useful as adhesives, sealants, encapsulants, gaskets and elastomers. Such formulations have relatively low viscosities at low and ambient temperatures. Further, the cured compositions of the invention demonstrate the ability to withstand temperatures of 140°C or greater and more preferably 155°C or greater without significant deterioration in properties. Elastomers of the invention can be used in electrical castings, encapsulating electrical device castings used in under the hood applications in automobiles and other environments where long term exposure to high heat environments is anticipated. The adhesives are especially useful in high heat environments.

Figure 1 illustrates a comparison of the hardness retention of Shore A 60 elastomers of the invention to conventional elastomers.

Figure 2 illustrates a comparison of the strength retention of Shore A 60 elastomers of the invention with conventional elastomers.

Figure 3 illustrates a comparison of the tensile strength with ageing of Shore A 95 elastomers of the invention to conventional Shore A 95 elastomers.

Figure 4 illustrates a comparison of the tensile elongation of Shore A 90 elastomers of the invention to conventional elastomers.

Figure 5 illustrates the effect of the amount of C4 diol on the tensile strength of the cast elastomer of the invention under ageing at 140°C in dry heat.

Figure 6 illustrates tensile strength performance of cast elastomers after ageing at various antioxidant levels.

Figure 7 illustrates tensile elongation for Shore A 90 elastomers at various antioxidant levels after ageing at 140°C in dry heat.

Figure 8 illustrates the effect of 1, 4 butane diol concentration on the Shore A properties of cast elastomers of the invention.

Figure 9 illustrates the effect of 2-ethyl-1, 3-hexanediol content on elongation of cast elastomers of the invention.

In order to prepare high temperature resistant polyurethane elastomers at relatively low temperatures, the selection of certain polyols as the isocyanate reactive materials is important. In one embodiment the polyol is a polyether polyol having a weight average molecular weight of from 2000 to 6000 and a functionality of 3. 0 or greater. In this embodiment the resulting elastomers are fairly hard with low elongation. In another embodiment, the polyol is a polyether polyol having a weight average molecular weight of 4000 or greater and more preferably 6000 or greater and most preferably of 8000 or greater. Preferably the polyether polyol has a weight average molecular weight of 16, 000 or less, more preferably 14, 000 or less, and even more preferably 12, 000 or less. In this second embodiment the polyols are used in conjunction with a cross-linking material as described hereinafter. In this embodiment the resulting elastomers are softer and have better elongation then the elastomers prepared from the polyols of the first embodiment described.

In order to achieve a polyether polyol having a functionality of 3. 0 or greater and more preferably 3. 2 or greater, which are capable of being handled at or near ambient temperatures, the choice of initiator is important. The initiators useful in this invention are initiators having a functionality of 4 or greater and are preferably liquid. Among preferred initiators are sorbitol, a mixture of sucrose and glycerin, methyl glucoside, a hydrolyzed adducts of epoxy resin and a glycol, adducts of alkylene oxides and novolac resins, a mixture of sucrose and trimethyl propane, and blends of sucrose and ethylene diamine.

Preferably the polyols have a functionality of 3. 0 or greater, more preferably 3. 2 or greater and most preferably 4. 8 or less. Functionality as used with respect to Polyols is adjusted functionality taking into account the amount of unsaturation in the polyol. The adjusted functionality is calculated according to Formula 1 iroHl 56. 1 ri i fi' I unsat + unsat 56. 1 I, I + wherein OH is the hydroxyl number, milligrams of KOH/g ; unsaturation is expressed in milliequivalents per gram and f is the nominal functionality which is the functionality of the initiator (for example a diol has a nominal functionality of 2. Alternatively, adjusted functionality can be adjusted according to formula 2. 9 in Herrigton et al Dow Polyurethanes Flexible Foams, p 2. 8, 2d edition 1997.

The polyols preferably are prepared by the reaction of the initiator with an alkylene oxide. Such processes are well known to those skilled in the art. Such methods are described for example in US Patents 4, 269, 945 ; 4, 218, 543 and 4, 374, 210. Suitable alkylene oxides useful in this invention are described in US Patent 5, 603, 798 at column 4, lines 32 to 34. The preferred alkylene oxides include ethylene oxide, propylene oxide and butylene oxide with ethylene oxide and propylene oxide being most preferred. The cross- linkers utilized in this invention include any cross-linker which is known and which has an equivalent weight of 200 or less. Cross-linkers as used herein refers to compounds which are also commonly referred to as chain extenders. Such cross-linkers are low molecular weight compounds having two active hydrogen atoms which react with isocyanate moieties.

Preferred cross-linkers are C3 to Clo alkylene diols, C 3 to C, Ocycloalkyiene diols, hydroquinone di (beta-hydroxyl ethyl) ether, ethoxylated bisphenol A, 4, 4'-Methylene bis (2- chloroaniline), 4, 4'-Methylenebis (3-chloro-2, 6-diethylaniline), 3, 5-dimethylthio-2, 4- toluenediamine, 3, 5-dimethylthio-2, 6-toluenediamine, trimethylene glycol di-p- aminobenzoate and 1, 4'bis (P-hydroxyethoxy) benzene. Examples of C3-Cro alkylene diols are 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 2, 2, 4-trimethyl- 1, 3-pentanediol and 2-butyl-2-ethyl-1, 3-propanediol. The cross-linking agents are present preferably in an amount of 1 percent by weight or greater and more preferably 5 percent by weight or greater based on the total weight of the formulation. Preferably the crosslinking agent is present in an amount of 30 percent by weight or less based on the total weight of the total formulation, and more preferably 15 percent or less.

Suitable polyisocyanates for use in preparing the elastomers include any aliphatic, cycloaliphatic, araliphatic, heterocyclic or aromatic polyisocyanate, or a mixture thereof. Preferably the polyisocyanates used have an average isocyanate functionality of at least 2. 0 and an equivalent weight of at least 80. Preferably, the isocyanate functionality of the polyisocyanate is at least 2. 0, more preferably at least 2. 2, and is most preferably at least 2. 4 ; and is preferably no greater than 4. 0, more preferably no greater than 3. 5, and is most preferably no greater than 3. 0. Higher functionalities may also be used, but may cause excessive cross-linking, result in a formulation which is too viscous to handle and apply easily, and can cause the cured elastomer to be too brittle. Preferably, the equivalent weight of the polyisocyanate is at least 100, more preferably at least 110, and is most preferably at least 120 ; and is preferably no greater than 300, more preferably no greater than 250, and is most preferably no greater than 200. Examples of polyisocyanates useful in this invention are disclosed in Bhat US Patent 5, 603, 798 at Column 3 lines 14 to 60. Preferably the

isocyanate used is an aromatic isocyanate, an oligomerized aromatic isocyanate or a polymerized aromatic isocyanate and carbodiimide modified version of such isocyanates.

More preferably the isocyanate is diphenyl methane diisocyanate, pure, in oligomerized or in polymerized form. Preferably the isocyanate is in the form of a liquid having a low viscosity, containing carbodiimides linkages and 2, 4' isomers.

The ratio of isocyanate moieties to active hydrogen containing moieties in the formulation is preferably 0. 9 or greater more preferably 1. 0 or greater. Preferably, the ratio is 1. 5 or less, more preferably 1. 25 or less and most preferably 1. 1 or less. In one embodiment, where there is a large excess of isocyanate groups, the formulation may further contain a trimerization catalyst to encourage the formation of isocyanate moieties.

This embodiment lowers the elasticity of the elastomer and improves the heat resistance. In such embodiment the isocyanate index is preferably from 1. 25 to 2. 0 and more preferably from 1. 25 to 1. 50.

The formulations of the invention include catalyst for the reaction of active hydrogen containing compounds with isocyanate moieties. Such catalysts are well known in the art and include the stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate, and stannous laureate ; dialkyltin dicarboxylates, such as dibutyl tin diiaurate and dibutyl tin diacetate ; dibutyl tin sulfides ; organomercurial catalysts, such as phenyl mercury ester of C, Ocarboxylic acid ; tertiary amines ; hydroxyamines ; titanates ; potassium acetate ; bismuth salts and tin mercaptides. The amount of catalyst employed depends on it's efficiency, the desired reaction profile, is preferably from 0. 005 to 5 percent by weight of the composition, and more preferably from 0. 01 to 2 percent by weight. Other known polyurethane catalysts include those disclosed in Taylor et al, US 4, 442, 235 Column 7, lines 11 to 46. Preferred catalysts useful herein are tin mercaptides, dibutyl tin dicarboxylates, dibutyl tin sulfide, phenyl mercury ester of C, o carboxylic acid ; a dibutyltin dimaleate/ethylenediamine complex, dibutyltin dimaleate, dioctyltin dimercaptide, N-hydroxy-alkyl quatenary ammonium carboxylate, tris (dimethylaminomethyl), triethylene diamine and potassium acetate.

Other commonly used components in polyurethane elastomer formulations may be used in the formulations claimed herein. Such materials include fillers, such as hollow glass spheres ; pigments ; accelerators ; flexibilizers ; plastizers ; combustion modifiers ; water scavengers and viscosity reduction agents. Preferably the compositions contain water scavengers such as zeolites. The amount of water scavengers preferably used in the formulations are preferably 1. 0 percent by weight of the formulation or greater, more

preferably 1. 5 percent by weight or greater. Preferably the amount of water scavenger used is 3. 0 percent by weight of the formulation or less and more preferably 2. 0 percent by weight or less.

In another embodiment antioxidants are preferably used. Such antioxidants are well known in the art and include hindered phenols such as octadecyl 3, 4-di-tertiarybutyl- 4-hydroxydrocinnamate or butylated hydroxytoluene ; phosphites, such as tris dipropyleneglycol phosphite ; and aromatic amines, such as alkylated diphenyl amine.

Preferably such antioxidants are used in an amount of 0. 01 percent by weight or greater based on the weight of the formulation, more preferably 0. 04 percent by weight or greater, even more preferably 0. 25 percent by weight or greater, and most preferably 0. 50 percent by weight or greater. Preferably the antioxidants are used in the amount of 1. 0 percent by weight or less. In one embodiment if a high level of antioxidant is used the thermal stability of the cured elastomers prepared from the formulations is improved. The preferred antioxidant package is a mixture of tris dipropyleneglycol phosphite and octadecyl 3, 4-di- tertbutyl-4-hydroxydrocinnamate.

The polyurethane elastomers of this invention may be prepared by conventional one shot processes. In such processes, all of the reactants are combined and then poured into a mold or injected into a mold. The reactants then react to form a hardened mass. It is preferable to degas the reaction mixture or components prior to placing them in an appropriate mold. Typically the mold is coated with a mold release compound to allow removal of the hardened mass from the mold. Such mold release compounds are well known in the art. In another embodiment the formulations of the invention are contacted with a substrate to coat or encapsulate the substrate with or in the formulation and then the coated or encapsulated substrate is exposed to conditions such that the formulation cures.

In the embodiment where a substrate is encapsulated, the substrate to be encapsulated is placed in a mold or box, held in place in a desired position, the formulation is introduced into the mold or box to surround the substrate and the formulation is exposed to curing conditions. Any substrate which can be protected by a polyurethane elastomer coating or encapsulant may be used. Examples of such substrates include plastics, metal, electrical devices, computer chips. Preferred plastics include ABS rubbers, polyurethanes, polyamides, nylon, polyolefins and polycarbonates. Preferred metals include aluminum.

The elastomers of the invention may be formed at temperatures of 15°C or greater, more preferably 20°C or greater and most preferably 25°C or greater. Preferably the elastomers

are formed at a temperature of 100°C or less, more preferably 40°C or less. The elastomers of the invention are preferably formed at or near ambient temperatures.

After formation the elastomers of the invention may be subjected to curing conditions. Such curing conditions include curing at 80°C or greater for 1 hour or greater and may be subjected to post-curing at 80°C or greater and preferably 100°C or greater for 12 hours or greater and preferably 24 hours or greater.

In another embodiment the elastomers of the invention may be made by a prepolymer process in which some or all the polyols are prereacted with excess polyisocyanate to form a prepolymer. Thereafter, the prepolymer is reacted with the cross- linker to form the elastomer.

The elastomers of the invention can be used in high temperature environments. Preferably the elastomers of the invention can withstand temperatures of 155°C for 10 days with no deterioration in properties. More preferably such elastomers can withstand 12 weeks at 140°C without any deterioration in properties. Preferably such elastomers can last 12 weeks at a temperature of 100°C in salt water with less than 30 percent loss in properties. Preferably the elastomers of the invention having a Shore A of 95 exhibit tensile strengths of 8 N/mm2or greater, preferably 12 N/mm2 or greater and most preferably 15 N/mm2or greater. Preferably such elastomers of the invention exhibit elongations of 100 percent or greater and more preferably 150 percent or greater.

At a Shore A of from 50 to 65 the tensile strength is preferably 4 N/mm2 or greater and most preferably 5 N/mm2 or greater, while the elongations are preferably 200 percent or greater and more preferably 250 percent or greater. Preferably the formulation is a liquid or a low viscosity blend. Suitable viscosities can vary according to the formulation and the ingredients (such as fillers). The polyols used in the process preferably have a viscosity of from 1000 to 2500 centipoise (cPs), the isocyanates used preferably have a viscosity of from 30 to 500 cPs. The blend of polyols with the isocyanates preferably have a viscosity of 500 to 2500 cPs at 25°C without fillers.

In one embodiment the invention is an adhesive composition comprising the polyurethane compositions of the invention. More particularly the adhesive composition can comprise a polyurethane prepolymer as described herein which is formulated with a catalyst which promotes the curing of the prepolymer by atmospheric moisture. Useful catalysts are well known in the art and include dialkyltin dicarboxylate, dialkyltin dimercaptide, dimorpholinodiethyl ether, and (di (2- (3, 5-dimethylmorpholino) ethyl) ether, etc. Other known

polyurethane catalysts include those disclosed in Taylor et al, US 4, 442, 235 Column 7, lines 11 to 46. The catalyst may be present in an amount of from 0. 01 to 2. 0 percent by weight with from 0. 05 to 0. 4 percent by weight being preferred. The preferred dialkyl tin dicarboxylates include 1, 1-dimethyltin dilaurate, 1, 1-dibutyltin diacetate, 1, 1-dimethyl dimaleate and dibutyl tin sulfide. Where the catalyst is an organotin catalyst it is preferably present in an amount of 5 parts per million or greater based on the weight of the adhesive, more preferably 60 parts per million or greater and most preferably 120 parts by million or greater. The organotin catalyst is preferably present in an amount of 1. 0 percent or less based on the weight of the adhesive, more preferably 0. 5 percent by weight or less and most preferably 0. 1 percent by weight or less. The one part adhesive may further comprise additional adhesive components well known in the art.

For formulating adhesive compositions, the prepolymer may be combined, with fillers, additives, ultraviolet stabilizers, and antioxidants known in the prior art for use in adhesive compositions. By the addition of such materials, physical properties such as viscosity, flow rate, sag, and fire resistance can be modified. However, to prevent premature reaction with the moisture sensitive groups of the polymer, the filler should be thoroughly dried before admixture therewith. Exemplary filler materials and additives include such as carbon black, titanium dioxide, clays, calcium carbonate, surface treated silicas, and PVC powder. This list, however, is not comprehensive and is merely illustrative. The fillers are preferably present in an amount of 1 percent by weight or greater based on the amount of the adhesive. The fillers are preferably present in an amount of 300 percent by weight or less based on the adhesive, more preferably 200 percent by weight or less and even more preferably 150 percent by weight or less.

The adhesive composition may also contain one or more plasticizers or solvents to modify rheological properties to a desired consistency. Such materials should be free of water, inert to isocyanate groups, and compatible with the polymer. Such material may be added to the reaction mixtures for preparing the elatomers or to the mixture for preparing the final adhesive composition, but is preferably added to the reaction mixtures for preparing the elastomers, so that such mixtures may be more easily mixed and handled.

Suitable plasticizers and solvents are well-known in the art and include dioctyl phthalate, dibutyl phthalate, a partially hydrogenated terpene commercially available as"HB-40", trioctyl phosphate, trichloropropylphosphate, epoxy plasticizers, toluene-sulfamide, chloroparaffins, adipic acid esters, xylene, 1-methyl-2-pyrrolidinone and toluene. The amount of plasticizer used is that amount sufficient to give the desired rheological properties and disperse the

components in the adhesive composition. Preferably the plasticizer is present in an amount of 0 percent by weight or greater, more preferably 5 percent by weight or greater and most preferably 10 percent by weight or greater based on the adhesive composition. The plasticizer is preferably present in an amount of 45 percent by weight or less, more preferably 40 percent by weight or less and most preferably 20 parts by weight or less based on the adhesive composition.

In another embodiment the adhesive, can be a two part composition in which one part comprises a low viscosity isocyanate as described before and the other part contains the polyols, and optionally the chain extender as described before. The two parts may be formulated with the other optional ingredients as described herein. The catalyst used may be a poiyurethane curing catalyst as described herein, a catalyst for moisture curing as described herein, or a mixture thereof. The catalyst is preferably blended into the polyol part of the composition.

The adhesive compositions of this invention may be formulated by blending the components together using means well-known in the art. Generally the components are blended in a suitable mixer. Such blending is preferably conducted in an inert atmosphere and in the absence of atmospheric moisture to prevent premature reaction. It may be advantageous to add any plasticizers to the prepolymer so that such mixture may be easily mixed and handled. Alternatively, the plasticizers can be added during blending of all the components. Once the adhesive composition is formulated, it is packaged in a suitable container such that it is protected from atmospheric moisture. Contact with atmospheric moisture could result in premature crosslinking of the polyurethane prepolymer.

The adhesive compositions of the invention can used to bond porous and nonporous substrates together. The adhesive composition is applied to a substrate and the adhesive on the first substrate is thereafter contacted with a second substrate. In the embodiment wherein the adhesive is a two part adhesive the two parts are combined prior to contacting with the substrate. Thereafter the adhesive is exposed to curing conditions. The substrates which may be adhered together include one or more of glass, plastic, metal, fiberglass or a composite substrate, such substrate may optionally be painted. Generally the one component adhesives of the invention are applied at ambient temperature in the presence of atmospheric moisture. Exposure to atmospheric moisture is sufficient to result in curing of the adhesive. Curing may be further accelerated by applying heat to the curing adhesive by means well known in the art including convection heating, or microwave heating.

The following examples are provided to illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

Polyol A is a sorbitol initiated polyol having a molecular weight of 12, 000, a polyether chain of 85 percent propylene oxide units and 15 percent of ethylene oxide units and a hydroxyl functionality of 4. 12.

Polyol B is a sucrose/glycerine (8 to 3 ratio) initiated polyol having a molecular weight of 8, 000, a polyether chain of 90 percent propylene oxide units and 10 percent of ethylene oxide units and a hydroxyl functionality of 3. 34.

Polyol C is a bisphenol adduct based on DER* 331 epoxy resin and a monoethylene glycol initiated polyol having polypropylene oxide chain with a ethylene oxide cap (90/10 percent) having a molecular weight of 4000 and a functionality of 3. 57.

Polyol D a sorbitol initiated polyol having a molecular weight of 2, 160, a polyether chain of propylene oxide units and a hydroxyl functionality of 4. 5.

VORANOL* CP 6055 polyol is a 6000 MW polyether triol glycerine initiated with 14. 5 percent of the polyether groups derived from ethylene oxide and 85. 5 derived from propylene oxide.

VORANOL* CP 4702 polyol is a 4800 MW glycerine initiated polyether triol with 17 percent of the polyether groups derived from ethylene oxide and 83 percent derived from propylene oxide.

VORANOL* EP 1900 polyol is 4000 MW polyether based reactive diol.

SONATE* M340 Isocyanate is based on carbodiimide modified MMDI and MMDI prepolymer.

* DER, ISONATE and VORANOL are trademarks of The Dow Chemical Company Antioxidants used include sterically hindered phenols, phosphites and substituted aromatic amines.

A molecular sieve, 3A, is used as water a scavenger.

The formulated polyol was prepared by mixing all necessary ingredients with a stirrer at least for 5 min. at 2000 rpm. The formulations contained a catalyst with the amount adjusted for a pot life of around 10 min. The blend was stored at ambient temperature. Re-homogenisation was carried out before use and further blending with the isocyanate component.

A known quantity of the polyol blend (between 150g to 200g) was weighed into a plastic beaker and placed under vacuum until bubbles disappeared indicating that all dissolve gases were removed.

This process was repeated for the isocyanate. Both components were mixed together for at least two minutes using a wood spatula to avoid bubbles. The resulting mix was poured into another plastic beaker mixing was continued for 1 minute. The mixture was poured into a hot (80°C), 2mm spaced plate mould, with the surface adequately prepared with a water based release agent. The reaction was carried on by curing at 80 °C for 1 H.

The cast elastomer sheet was removed from the mould, post-cured for 24 hours at 100°C, and then stored for 7 days at 20°C, 65 percent relative humidity before testing.

All samples used for evaluation of mechanical properties, and evaluation of the retention of those properties under dry heat ageing, were cured and stored under the same conditions as described before.

In preparation for the dry heat ageing evaluations test bone pieces (DIN EN ISO 527 ; Shape # 5) were cut out of the 2 mm thick elastomer sheet, placed on a Teflon tray and placed in an oven with temperature controlled within +/-3°C of the set point.

The following mechanical properties are tested using the listed tests : Tensile strength and Elongation DIN EN ISO 527 (Shape # 5, speed 200 mm/min) The elongation is calculated by measuring the elongation between the jaws, DIN EN ISO 527, corrected by multiplication factor 0. 66 ; Shore A and Shore D were performed according to DIN 53505.

Tear strength were performed according to DIN 53515 without initial cut.

Examples 1, 2 and Comparative Example A and B Elastomers having a Shore A hardness of 60 to 65 were prepared from Polyol A (Example 1), Polyol B (Example 2) VORANOL CP 6055 polyol (Comparison Example A) and a mixture of VORANOL CP 4702 and VORANOL EP 1900 (Comparison Example B) using the procedure described above. The formulation used for Examples 1, 2 and Comparison A was 88. 35 weight parts polyol, 5. 0 weight parts 1, 4-butane diol, 5. 0 weight parts 2-ethyl, 1, 3 hexane diol, 0. 15 weight percent Formrez UL 32 Tin catalyst, 1. 5 weight parts Molecular sieve 3A water scavenger, and 37. 35 weight parts of sonate M 340 isocyanate. The formulation for comparison Example B was the same except the polyol mixture comprised 58. 96 weight parts of VORANOL CP 6055 polyol and 30. 3 weight parts of VORANOL EP 1900 polyol, the amount of 1, 4-butane diol was 9. 09 weight parts, and the amount of Isonate M 340 isocyanate was 42. 81 weight parts.

The prepared elastomers were aged at 155°C for 0, 10, 15, 20, 30 and 40 days. The tensile elongation, tensile strength and Shore A hardness were tested at the designated aging times the results are compiled in Table 1.

TABLE 1 Test Comparative Comparative Example 1 Example 2 Example A Example B Retention of mechanical performances Ageing at 155°C Shore A 0 day ageing 63 67 60 57 10 days ageing 59 57 3 32 15 days ageing 62 56 destroyed 20 20 days ageing 63 60 12 30 days ageing 62 40 days ageing 56 Tensile Elongation in % 0 day ageing 260 273 450 650 10 days ageing 340 356 0 700 15 days ageing 315 347 720 20 days ageing 295 280 500 30 days ageing 270 40 days ageing 270 Tensile strength in N/mm2 0 day ageing 4. 5 5. 8 6. 2 8. 1 10 days ageing 4. 3 3. 9 0. 5 2. 9 15 days ageing 5. 6 4. 5 2 20 days ageing 7. 1 6. 5 0. 5 30 days ageing 7. 4 40 days ageing 6. 5 Major variations in Shore A performance are seen under ageing for the different formulations. The formulation based on Polyol A is stable whereas the formulation based on the comparative polyol were not stable. Figure 1 shows the performance differences in hardness retention, and Figure 2 illustrates performances differences in strength retention.

Examples 3 to 6 and Comparative Example C Shore A 95-97 elastomers prepared as described above were used under dry heat ageing conditions at 140°C for up to ten weeks. The formulations and results are compiled in Table 2.

TABLE 2 Comparative Example 3 Example 4 Example 5 Example 6 Example C Parts by Parts by Parts by Parts by Parts by Ingredients WT WT WT WT WT polyol A 84. 32 83. 75 polyol B 84. 53 polyoi C 84. 02 VORANOL CP 6055 84. 53 1, 4 butanediol 14. 33 14. 37 14. 28 14. 37 1, 3 propanediol 14. 3 Tin catalyst 0. 02 Thorcat 534, mercury 0. 25 0. 25-0. 25 0. 25 catalyst Molecular sieve 3A, 0. 84 1. 5 1. 68 1. 7 0. 85 Weston 430 Phosphite 0. 25 A. O. Isonate M 340 60. 56 61. 69 63. 86 70. 34 60. 11 Retention of mechanical Properties Shore A 0 week ageing 92 93 97 94 2 weeks ageing 94. 5 88 97. 5 92 4 weeks ageing 94 87 97 90 6 weeks ageing 93 86 97 88 8 weeks ageing 93 87 97. 5 10 weeks ageing 92. 5 Tensile Elongation % 0 week ageing 229 168. 4 200 217 287 2 weeks ageing 245 231 204 234 173 4 weeks ageing 255 217 184 237 55 6 weeks ageing 216 228 147. 8 238 20 8 weeks ageing 217 195 106 235 10 weeks ageing 181 163 95 203 Tensile strength N/mm2 0 week ageing 18. 2 16. 1 17. 6 21. 6 16. 1 2 weeks ageing 16. 7 16. 4 13. 6 20. 5 8. 5 4 weeks ageing 17. 2 15. 2 12. 7 20 6. 1 6 weeks ageing 15. 8 16 11. 4 18. 9 3. 2 8 weeks ageing 16. 7 16. 1 10. 6 19. 7 10 weeks ageing 15. 8 15. 5 10. 7 19. 1

Figure 3 illustrates tensile strength performance, and Figure 4 illustrates tensile elongation of Example 3 and Comparative Example C.

Examples 7 to 9 and Comparative Examples C and D Elastomers were prepared as described above using the formulations described in Table 3. Ageing tests were conducted on the formulations. Exampies 7, 8, Comparative Examples C and D are aged at 140°C and Example 9 is aged at 150°C. The results are compiled in Table 3.

TABLE 3 Comparative"Shore A 98" Example 7 Example 8 Example C Example D Example 9 Parts by Parts by Parts by Parts by Parts by Ingredients WT WT WT WT WT polyol A 80. 85 79. 35 polyol D 98. 2 VORANOL CP 6055 84. 53 VORANOL EP 1900 83. 82 1, 4 butanediol 17 19 14. 37 14. 25 no Formrez UL 32 at 2%, 0. 15 0. 3 Tin catalyst Thorcat 534, mercury 0. 2 0. 25 0. 25 catalyst Molecular sieve 3A, 1. 7 1. 5 0. 85 1. 68 1. 5 water scavenger Weston 430 Phosphite 0. 5 A. O. Isonate M 340 70. 33 78 60. 11 60. 05 45. 84 Retention of Mechanical Properties Tensile Elongation in % 0 week ageing 229 147 287 517 120 2 weeks ageing 245 157 173 70. 5 112 4 weeks ageing 255 153. 6 55 51 96 6 weeks ageing 216 117 20 35 92 8 weeks ageing 217 111 destroyed Tensile strength in N/mm2 0 week ageing 18. 2 23. 3 16. 1 17. 6 16. 8 2 weeks ageing 16. 7 21. 5 8. 5 3. 8 17. 2 4 weeks ageing 17. 2 20. 8 6. 1 3. 7 15. 5 6 weeks ageing 15. 8 20. 9 3. 2 4. 4 18. 9 8 weeks ageing 16. 7 20. 7

Formulations having different levels of crosslinker were prepared and tested for ageing. (Example 3, 7, 8) The tests demonstrate that improved heat resistance may be obtained by using at least some quantities of crosslinker in the formulation, although Shore A and elongation are stable during ageing test at 140°C. Figure 5 shows the impact of 1, 4 butane diol (C4diol) content on tensile strength in a cast elastomer under ageing at 140°C.

Example 11 Elastomers based on Polyol A using the same formulation as in Example 3 with an antioxidant package of tris dipropyleneglycol phosphite and 500 ppm butyiated hydroxytoluene, were prepared and tested for heat ageing.

The elastomers demonstrate good retention of physical properties over extended periods (12 weeks-140°C). Additional heat ageing tests further demonstrated that the temperature-time limit, defined by 50 percent loss of mechanical performance, can be extended with antioxidants.

Example 12 Samples of elastomers of the invention were prepared using phosphite and hindered phenol antioxidants. The tensile strengths and elastomers were examined in Shore A 90 elastomers. The data shows that"phosphite"based antioxidants when added at a minimum level of 0. 25 percent on total elastomer formulation brings outstanding improvement. Figure 6 illustrates tensile strength performance, and Figure 7 illustrates tensile elongation for Shore A 90 elastomers under 140°C dry heat ageing test.

Examples 13 Elastomers were prepared according to the procedures disclosed hereinbefore using polyol A with various amounts of 1, 4 butane diol as the chain extender.

The elastomers were tested for Shore A hardness, elongation, tensile strength and tear strength. The results are compiled Table 4.

TABLE 4 13 14 15 16 17 18 19 20 21 Experimental polyol A 98. 35 95. 35 93. 35 90. 85 88. 35 85. 85 84. 05 81. 35 79. 35 C4 diol 0 2. 5 5 7. 5 10 12. 5 14. 3 17 19 Molecular sieve 1. 5 1. 5 1. 5 1. 5 1. 5 1. 5 1. 5 1. 5 1. 5 Gatalyst at 2% in polol 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Isocyanate / M-340 8.6 17.6 26.6 35.6 44.6 53.6 60.5 70.3 77.1 Shore A 46 52 66 78 86 91 94 96 96 Elongation % 57 85 115 15 185 205 203 195 187 Tensile strength N/mm2 0.7 1.3 2.9 6.3 10.0 13.8 17 19.8 20.6 Tear strength N/cm 12.

Fig 8 demonstrates the impact of 1, 4 butane diol content on Shore A. Fig 9 demonstrates the impact of 1, 4 butane diol content on Elongation