POLYURETHANE-TYPE ADHESIVES CONTAINING NONAQUEOUS SOLUTIONS OF ACRYLATE POLYMERS

Abstract: Substrates of metal, glass, plastic and the like are effectively bonded together with an adhesive composition that is the reaction product of a solution of copolymer of an alkyl ester of an alpha , beta -ethylenically unsaturated carboxylic acid and a hydroxyalkyl ester of an alpha , beta -ethylenically unsaturated carboxylic acid in a polyahl having a molecular weight of 200 or greater such as polypropylene glycol and a low molecular weight polyahl such as ethylene glycol with an organic polyisocyanate such as 4,4'-methylenediphenyl diisocyanate.

Description: _ ^ _ POLYURETHANE-TYPE ADHESIVES CONTAINING NONAQUEOUS SOLUTIONS OF ACRYLATE POLYMERS This invention relates to polyurethane-type adhesives and their use in bonding of substrates. Polyurethane adhesives constitute a broad class of polymeric materials having a wide range of physical characteristics. These polymers are produced by the reaction of a polyisocyanate with a polyfunctional compound having active hydrogens in its structure. This active hydrogen compound is generally a liquid or solid capable of being melted at relatively low temperatures. Most commonly, the active hydrogen compound contains hydroxyl groups as the moieties providing the active hydrogen such compounds include polyols, such as polyols of polyesters, polyester amides, or polyethers, or mixtures of two or more such materials. For reasons of commercial availability and cost, the polyols most commonly employed in the preparation of polyurethane adhesives are polyethers having hydroxyl terminated chains and hydroxyl terminated polyesters. Although a wide variety of physical and chemical properties are obtainable by the proper selection of a polyisocyanate and the polyol as well as the conditions under which the polyurethane reaction is carried out, the resulting polyurethane compositions when used as adhesives often do not adhere well to various substrates, e.g., vinyl polymers, steel, aluminum and the like, and often exhibit poor lap shear strength and poor impact strength. Accordingly, it is highly desirable to provide a polyurethane adhesive exhibiting increased lap shear strength and/or impact strength. In one aspect, the present invention is an adhesive composition comprising the reaction product of (1) a true solution of (a) a copolymer of an alkyl ester of an α,β-ethylenically unsaturated carboxylic acid and a hydroxyalkyl ester of an α,β-ethylenically unsaturated carboxylic acid, the copolymer having a number average molecular weight (M n ) of at least 3500, in (b) a polyahl having a molecular weight of at least 200 (hereinafter called a high molecular weight polyahl, abbreviated as HMW Polyahl), (2) an organic polyisocyanate, and (3) a polyahl chain extender having a molecular weight less than 200, (hereinafter called low molecular weight polyahl, abbreviated as LMW Polyahl). The term "true solution" means a solution of the macromolecular copolymer in the HMW polyahl that is thermodynamically stable and reversible in the sense that the copolymer macromolecules are easily reconstituted after separation of solute from solvent. In the adhesive composition, the copolymer and the LMW Polyahl are present in an amount sufficient to provide the resulting adhesive with lap shear strength or impact strength in excess of that possessed by a similar adhesive which contains no copolymer. In another aspect, this invention is a method for bonding together two or more substrates. The method comprises applying the aforementioned adhesive composition to at least one of the substrates and then joining the substrates together such that the adhesive composition forms a layer between the substrates in contact with at least one surface of each substrate. Conditions are employed such that the adhesive composition reacts and cures thereby bonding the substrates together. Surprisingly, the adhesive compositions of the present invention exhibit significantly improved lap shear strength or impact strength as compared to conventional urethane adhesive compositions. Accordingly, the adhesive compositions of the present invention are particularly effective in bonding substrates of materials such as steel, plastic materials and aluminum. The HMW Polyahl acting as a solvent phase of the copolymer solution, includes any organic compound having at least two active hydrogen moieties, a molecular weight of at least 200 and a hydroxy equivalent weight of at least 50, preferably at least 100. Preferably the HMW Polyahl is a polymer having at least two active hydrogen moieties, a molecular weight of at least MOO and a total of at least 5 monomeric units such as, for example, propylene oxide and ethylene oxide. HMW Polyahls that are suitably employed in preparing the ethylenic addition polymerizable reaction product or adduct of this invention are also sufficiently lyophilic to enable polymers of the adduct to stabilize dispersions of lyophobic polymers in nonaqueous liquids. Preferably, the HMW Polyahl is sufficiently similar in composition to the continuous phase such that it is soluble in the continuous phase. For the purposes of this invention, an active hydrogen moiety refers to a moiety containing a hydrogen atom that, because of its position in the molecule, displays significant activity as defined by a Zerewitnoff test described by Woller in the Journal of The American Chemical Society, Vol 49, p. 3181 (1927). Illustrative of such active hydrogen moieties are -C00H, -OH, -NH 2 , =NH, -C0NH 2 , -SH and -C0NH-. Typical HMW Polyahls include polyols, polyamines, polyamides, polymercaptans, polyacids and the like, particularly as exemplified in U.S. Patent 4,394,491. Of the foregoing HMW Polyahls, the polyols are preferred. Examples of such polyols are polyol polyethers, polyol polyesters, hydroxy functional acrylic polymers, hydroxyl-containing epoxy resins, polyhydroxy terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds and alkylene oxide adducts of polyhydric thioethers including polythioethers, acetals including polyacetals, aliphatic and aromatic polyols and thiols including polythiols, ammonia and amines including aromatic, aliphatic and heterocyclic amines including polyamines as well as mixtures thereof. Alkylene oxide adducts of compounds which contain two or more different groups within the above-defined classes may also be used, such as, for example, amino alcohols that contain an amino group and a hydroxyl group. Also alkylene adducts of compounds that contain one -SH group and one -OH group as well as those that contain an amino group and a -SH group may be used. - Polyether polyols are most advantageously employed as the HMW Polyahl in the practice of this invention and are, for example, polyalkylene polyether polyols including the polymerization products of alkylene oxides and other oxiranes with water or 10 polyhydric alcohols having from two to eight hydroxyl groups. Exemplary alcohols that are advantageously employed in making the polyether polyol include ethylene glycol, 1,3-propylene glycol, 1 ,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2- 15 butylene glycol, 1,5-pentane diol, 1,7-heptane diol, glycerol, 1 , 1 , 1-trimethylolpropane, 1,1,1-tri- methylolethane, hexane-1 ,2,6-triol, α-methyl glucoside, pentaerythritol, erythritol, pentatols and hexatols. 0 Also included within the term "polyhydric alcohol" are sugars such as glucose, sucrose, fructose and maltose as well as compounds derived from phenols such as 2,2- (4, '-hydroxyphenyl)propane, commonly known as bisphenol A. Illustrative oxiranes that are 5 advantageously employed in the preparation of the polyether polyol include simple alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and amylene oxide; glycidyl ethers such as t-butyl glycidyl ether and phenyl glycidyl ether; and random or block 0 copolymers of two or more of these oxiranes. The polyalkylene polyether polyols may be prepared from other starting materials such as tetrahydrofuran and alkylene oxide tetrahydrofuran copolymers; j- epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have primary, secondary or tertiary hydroxyl groups and, preferably, are polyethers prepared from alkylene oxides having from two to six carbon atoms such as ethylene oxide, propylene oxide and butylene oxide. The polyalkylene polyether polyols may be prepared from any known process such as, for example, the process disclosed in Encyclopedia of Chemical Technology, Vol. 7, pp. 257- 262, published by Interscience Publishers, Inc. (1951), or in U.S. Patent 1,922,459. Also suitable are polyether polyols and processes for preparing them that are described in Shick, M. J., Nonionic Surfactants, Marcel Dekker, Inc., New York (1967) U.S. Patents 2,891,073; 3.058,921; 2,871,219 and British Patent 898,306. Polyether polyols that are most preferred include the alkylene oxide addition products of water, trimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol and blends thereof having hydroxyl equivalent weights of from about 100 to about 2000. Other HMW Polyahls suitable for use in the adhesive compositions of this invention are described in U.S. Patent 4,394,491; U.S. Patent 4,269,945 and U.S. Patent 4,396,729. The copolymer employed in the practice of this invention is a copolymer of an alkyl ester of an α,β-ethylenically unsaturated monocarboxylic acid and a hydroxyalkyl ester of an α,β-ethylenically unsaturated monocarboxylic acid. The copolymer of the invention is soluble in the polyahl components used in the adhesive composition. In addition to the alkyl ester and the hydroxyalkyl ester, the copolymer may also contain other ethylenically unsaturated monomers provided that such monomers do not render the copolymer insoluble in the polyahl or interfere with the reaction between the isocyanate moiety of the organic polyisocyanate and the active hydrogen moiety of the polyahl. Exemplary alkyl esters are the alkyl acrylates and alkyl methacrylates wherein alkyl has from 1 to 18 carbon atoms. Preferably, the alkyl ester is an alkyl acrylate such as butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, or other alkyl acrylates 10 or methacrylates wherein alkyl has from 1 to 16 carbon atoms, with butyl acrylate being the most preferred. Examples of preferred hydroxyalkyl esters are hydroxyethyl acrylate, hydroxypropyl acrylate, ,,- hydroxybutyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate, with hydroxyethyl acrylate being most preferred. Examples of suitable "other ethylenically 20 unsaturated monomers" are aliphatic conjugated dienes such as butadiene and isoprene; monovinylidene aromatic monomers such as styrene, α-methyl styrene, ar-methyl styrene, ar-(t-butyl)styrene; ar-chlorostyrene, ar- cyanostyrene and ar-bromostyrene; α,β-ethylenically 25 unsaturated carboxylic acids and anhydrides such as acrylic acid and methacrylic acid, maleic anhydride and the like; α,β-ethylenically unsaturated nitriles and amides such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N,N-dimethyl acrylamide, N- 30 (dLmethylaminomethyl)acrylamide, and the like; vinyl esters such as vinyl acetate; vinyl ethers; vinyl ketones; vinyl and vinylidene halides as well as a wide variety of other ethylenically unsaturated materials , c which are copolymerizable with the aforementioned mono- adduct, many of which have heretofore been employed in the formation of copolymer polyols as described in U.S. Patents 3,823,201 and 3,383,351. It is understood that mixtures of two or more of the aforementioned "other monomers" are also suitably employed in making the copolymer. Of the foregoing "other monomers", the monovinylidene aromatic monomers, particularly ar-(t- butyl)styrene are preferred. Most preferred copolymers are copolymers of from about 45 to about 95 weight percent of the alkyl acrylate or alkyl methacrylate or mixture thereof, from about 5 to about 55 weight percent of the hydroxyalkyl acrylate and up to about 50 weight percent of another monomer such as ar-(t-butyl)styrene, styrene, or vinyl toluene. The M n of the copolymer is preferably in the range from about 4,000 to about 40,000, more preferably from 4,000 to 20,000, most preferably from 4,000 to 18,000. The M n of the copolymer is determined by gel permeation chromatography. The true solution of the copolymer in HMW Polyahl is advantageously prepared by dispersing the monomeric components of the copolymer in the HMW Polyahl and effecting addition polymerization by conventional free radical initiation techniques. Usually, the HMW Polyahl is added to a reactor that is equipped with a conventional mixing means such as a simple mechanical stirrer. The polymerization is readily carried out by simultaneously adding at a steady or constant rate the monomeric mixture and a free radical catalyst to the HMW Polyahl under conditions sufficient to cause free radical addition polymerization and a uniform solution of the copolymer in the HMW Polyahl. Temperature of copolymerization is dependent upon the free radical initiator and is preferably in the range from about 25°C to about 190°C, most preferably from about 50°C to about 120°C, when an azotype catalyst is employed. Other polymerization processes, both continuous and batch, may be suitably employed. Examples of such other polymerization processes are described in U.S. Patent 3,383,351 or U.S. Patent 4,390,645. 10 Suitably, the concentration of polymerization catalyst is any amount sufficient to cause copolymerization of the monomers. Preferably, the concentration of catalyst is in the range from about 15 0.5 to about 5, more preferably from about 1 to about 3, weight percent based on the combined weight of the monomers. Catalysts suitably employed in the practice of 20 the polymerization are free radical type polymerization catalysts such as the peroxides, persulfates, perborates, percarbonates, azo compounds and the like. Examples of such catalysts include hydrogen peroxide, pr - di( -butyl)peroxide, t-butyl peroctoate, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobis(isobutyronitrile) as well as mixtures of such catalysts. Of the foregoing catalysts, azobis(isobutyronitrile) is preferred. 0 In addition to the foregoing catalysts, chain transfer agents such as mercaptans, e.g., dodecane- thiol, and carbon tetrahalides such as carbon tetrachloride may be employed in conventional amounts 5 to control molecular weight of the copolymerizate. Organic polyisocyanates which may be employed in the adhesive compositions of this invention include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Representative of these types are the diisocyanates such as m-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6- diisocyanate, hexamethylene-1 ,6-diisocyanate, te ramethylene-1 ,4-diisocyanate, cyclohexane-1 ,4- diisocyanate, hexahydrotolylene diisocyanate (and 10 isomers), naphthylene-1 ,5-diisocyanate, 1-methoxy- phenyl-2,4-diisocyanate, diphenylmethane-4,4- diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'- dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl- - t - 4,4'-biphenyl diisocyanate, and 3,3'-dimethyl- diphenylmethane-4,4'-diisocyanate; the triisocyanates such as 4,4' ,4'-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate and tolylene-2,4,6- triisocyanate; and the tetraisocyanates such as 4,4'- 20 dimethyl-diphenylmethane-2,2' ,5,5'-tetraisocyanate. Preferred, due to their availability and properties, are tolylene diisocyanate, 4,4'-methyldiphenyl diisocyanate and polymethylene polyphenylisocyanate, with diphenyl-methane-4,4'-diisocyanate and liquid 25 forms based thereon being most preferred. Also suitable are isocyanate terminated prepolymers such as those prepared by reacting polyisocyanates with polyols. Crude polyisocyanate may also be used in the practice of the present invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or crude diphenylmethylene -,r- diisocyanate obtained by the phosgenation of crude diphenylmethylenediamine. The undistilled or crude isocyanates are disclosed in U.S. Patent 3,215,652. The LMW Polyahls employed in the adhesive j . compositions of this invention as chain extruders include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol and the like, with ethylene glycol being most preferred. Low molecular polyamines such as ethylenediamine are also 10 suitable, particularly when aliphatic polyisocyanates are employed. In preparing the reaction product which constitutes the essential component of the adhesive 15 compositions of the present invention, the solution of copolymer in HMW Polyahl, the LMW Polyahl and the polyisocyanate are contacted in proportions and under conditions sufficient to provide the desired urethane reaction product. In general, the HMW Polyahl, the LMW 20 Polyahl and the polyisocyanate are employed in proportions sufficient to provide a stoichiometric or nearly stoichiometric ratio between the active hydrogen moieties of the HMW Polyahl, the LMW Polyahl and the p j- active hydrogen moiety of the copolymer with the isocyanate moieties of the polyisocyanate. The LMW Polyahl and the copolymer are employed in the composition in amounts sufficient to provide an improvement of lap shear strength or impact strength 30 over a polyurethane adhesive prepared from the reaction product of the HMW Polyahl and the polyisocyanate. Preferably, the composition comprises: (1) a copolymer polyahl solution portion that includes (a) 10 to 70 weight percent of the copolymer, most preferably 25 to 5 60 weight percent; (b) 30 to 88 weight percent of the HMW Polyahl, most preferably 40 to 75 weight percent; and (c) 2 to 20 weight percent of the LMW Polyahl, most preferably 5 to 15 weight percent, and, (2) a polyisocyanate portion having sufficient isocyanate moieties to react with essentially all of the active hydrogen moieties of the HMW Polyahl and the LMW Polyahl. Preferably, the polyisocyanate portion is present in sufficient amount to provide a mole ratio of isocyanate moiety to active hydrogen moiety in the range 0.8:1 to 2:1, most preferably from 1:1 to 1.2:1. The urethane reaction of isocyanate moieties and active hydrogen moieties is preferably carried out in absence of a urethane-type catalyst. However, when fast reaction time is desirable, e.g., less than 1 min. , the urethane reaction is carried out in the presence of a urethane-type catalyst which is effective to catalyze the reaction of the active hydrogen moieties with the isocyanate moieties. When such faster reaction times are desired, the urethane catalyst is used in an amount comparable to that used in conventional urethane-type reactions, preferably in an amount from about 0.001 to about 5 weight percent based on the weight of the reaction mixture. Any suitable urethane catalyst may be used including tertiary amines, such as, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1- methyl-4-dimethylaminoethyl piperazine, 3-methoxy-N- dimethylpropylamine, N,N-dimethyl-N' ,N'-methyl isopropyl propylenediamine, N,N-diethyl-3-diethyl- aminopropylamine, dimethylbenzylamine and the like. Other suitable catalysts are, for example, tin compounds such as stannous chloride, tin salts of carboxylic acids such as dibutyltin di-2-ethyl hexanoate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. In addition to the aforementioned ingredients j - used in the composition, the composition optionally ' contains other additives such as surface-active agents, stabilizers, fillers, pigments and the like. These optional components will be. employed in amounts to provide the desired function as is known by the skilled 10 artisan in urethane type adhesives. In utilizing the adhesive composition of the present invention to adhesively join two or more substrates, the composition is applied to the 15 substrates prior to or during the formation and curing of the desired reaction product. The substrates to be bonded are then placed in contact with the adhesive composition interspersed between them. The adhesive composition is permitted to react to form the desired 20 reaction product. Methods of application of the adhesive composition to the substrate and carrying out the reaction to form the desired reaction product are those generally used in conventional urethane adhesive pr - applications. Examples of substrates which are suitably bonded together in the practice of this invention are those of various metals, glass, plastic, wood, reinforced polymeric composites and rubber. It is further understood that substrates of different 0 composition such as metal to plastic, glass to plastic and the like can also be bonded using the adhesive compositions of the present invention. The following examples are given to illustrate 5 the present invention and are not to be construed as limiting the scope thereof in any manner. All parts and percentages are by weight unless otherwise indicated. Example 1 A. Preparation of Copolymer Solution in Polyahl Into a one-liter, three-neck flask equipped with a stirrer, thermometer, condenser, dropping funnel and a nitrogen source is charged 200 g of polypropylene 10 glycol (diol) having an average molecular weight of 400 as the HMW polyahl solvent component. The polypropylene glycol is previously dried over a molecular sieve. While maintaining a nitrogen purge of the reaction flask the flask is heated to 90°C and a 15 mixture consisting of 156 g of butyl acrylate, 44 g of 2-hydroxyethyl acrylate and 2 g of azobis(isobutyro¬ nitrile) is added dropwise to the reaction flask over a period of 2\ hours. After 3 hours, 0.2 g of the azo catalyst is added to the reaction mixture and at 20 subsequent j-hour intervals a similar amount of the azo catalyst is added until a total of 1 g of additional azo catalyst is added. The total polymerization time is 5J hours. The resulting reaction mixture is then p .- stripped under vacuum, but no volatile components are recovered. The resulting copolymer in polypropylene glycol solution is a clear homogeneous liquid having a viscosity of 2000 centipoises at 23-5°C (Brookfield Viscosity-Brookfield LVT Viscometer operating a #2 30 spindle at 6 rpm). The copolymer has a M n of 5315 as determined by gel permeation chromatography and a peak molecular weight (Peak) of 10,634 and a weight average molecular weight of 10,803. 35 B. Urethane Adhesive To 9 g of the aforementioned copolymer in one polypropylene glycol solution is added 1 g of ethylene glycol (previously dried), as the LMW polyahl chain • extender component, and the mixture is degassed under vacuum with stirring. While stirring the mixture, a portion of 11.73 g of carbodiimide modified 4,4'- methylenediphenyl diisocyanate (sold by Dow Chemical Company of Midland, Michigan, USA under the tradename Isonate * 143L) is added and the resulting mixture is again degassed with stirring. The resulting adhesive composition is then applied to tabs of cold rolled steel and aluminum, each tab having the following dimensions: 2.54 cm x 10.16 cm x 0.16 cm. The metal tabs are previously cleaned with perchloroethylene and oven-dried. The lap shear specimens are prepared by applying the adhesive mixture to the ends of one side of the metal tab and a few glass spheres having a diameter of 0.1 mm are placed on the adhesive. The adhesive joint is made with a 1.27 cm overlap and clamped. After a room temperature cure for about 24 hours, the tabs are then post-cured at 135°C for 60 minutes. Lap shear strength is then measured using an Instron testing machine at a crosshead speed of 0.127 cm/minute. The average lap shear strength observed for 4 specimens of cold rolled steel is 5,140 psi (35.5 mPa). This results is reported as Sample 1 in Table II hereinafter. The average lap shear strength for 4 specimens of aluminum is 3,436 psi (23.7 mPa). For purposes of comparison, similar lap shear samples are prepared for adhesive compositions that do not include the copolymer component of the invention. These compositions use a mixture of 90 parts of the aforementioned polypropylene glycol and 10 parts of ethylene glycol in combination with the aforementioned diisocyanate at the same ratio of NCO to OH employed hereinbefore. In essence, the only difference between the two compositions is the presence of the copolymer in the first composition and the absence of the copolymer in this composition. The average lap shear strengths for the resulting specimens are 3,400 psi (23.5 mPa) for cold rolled steel (reported as Sample C, in Table II) and 2,746 psi (18.9 mPa) for aluminum. Example 2 Following the procedure described in part A of Example 1, the following copolymer solutions are prepared at a concentration of 50 weight percent of copolymer in the polyglycol. The polyglycol used is the polyglycol of Example 1. **Not an example of the invention 1 BA - butyl acrylate HEA - hydroxyethyl acrylate AA - acrylic acid HPA - hydroxypropyl acrylate S - styrene MMA - methyl methacrylate tBS - t-butylstyrene LMA - lauryl methacrylate ^Brookfield Viscosity using a Brookfield LVT Vis- co eter and a #2 spindle at 23.5°C and rpm as indicated in parenthesis Number average molecular weight as determined by gel permeation chromatography (GPC) NM - estimated from gpc data as having M n in the range of 5,000-12,000 Using the procedures of Example 1 to prepare and test lap shear strength of adhesive compositions on cold rolled steel, the results given in Table II are obtained. Impact strength of the adhesive joints is measured and reported in Table II. Table II also includes the Example 1 Samples and results TABLE II Copolymer/Polyahl Component Adhesive Strength Lap Impact Shear in-lb (J) psi (mPa) I 4576 (31.6) 32 (3.6) 5140 (35.4) 23 (2.6) 3316 (22.9) 8 (0.9) 3400 (23.4) 12 (1.35) 690 ( 4.8) 5 (0.56) 5344 (36.9) 10 (1.13) 5000 (34.5) 40 (4.5) 4530 (31.3) 30 (3.4) Table II (Cont'd) Footnotes: *Not an example of the invention 1 Copolymer/polypropylene glycol as HMW Polyahl solvent wherein the copolymer and polypropylene glycol are as defined in Table I 2 Ethylene glycol as LMW Polyahl chain extruder. 3 4,4'-methyl diphenyldiisocyanate sold as Isonate ® 143L, liquid MDI NCO equivalents of 144.9 by The Dow Chemical Company of Midland, Michigan, USA. Laρ shear determined by method described in Example 1. Impact strength determined by the following drop impact test method: A Gardner Impact Tester is modified with a test specimen holder to accommodate standard 2.54 cm x 10.16 cm x 0.16 cm metal test specimens. Two test specimens indicated size are bonded together with the adhesive to form a cross-lap adhesive bond with a 2.5 cm (1 in.) overlap (bond area) and bond thickness of 0.01 cm (0.004 in.). The bonded test specimen is clamped into test specimen holder which is secured to the base of the Gardner Impact Tester in a position so that the drop impact rod impinges on the center of the impacter part of the specimen holder. The steel rod impact weight (1.812 kg) is dropped from different heights onto impacter secured to the bonded test specimen and impact strength in inch-pounds (joules) is measured. The results reported in Table II indicate that a significant improvement in lap shear strength and impact strength can be obtained over the control sample (Sample No. C- | ) with copolymers of BA/HEA containing from 10 to 22 percent HEA and at a concentration of 50 percent of copolymer in the polypropylene glycol. Run No. 3 in Table II exhibits lower impact strength and lap shear due to higher cross-linking in this particular formulation. Example 3 Following the procedure described in part A of Example 1 , the following copolymer solutions are prepared except that polypropylene glycols (diols) having different molecular weights are employed. Each of the copolymer solutions contain 50 percent copolymer and is combined with ethylene glycol at a weight ratio of 90:10 and then with Isonate * 143L at a NC0:0H ratio of 1.05. The resulting adhesive compositions are then tested for lap shear strength and impact strength by the methods described in Examples 1 and 2 and the results are reported in Table III. For purposes of comparison, the adhesive compositions containing the polypropylene glycol, ethylene glycol and Isonate * 143L but no copolymer are similarly prepared and tested and the results are reported in Table III. Similarly, several adhesive compositions are prepared using different amounts of ethylene glycol using the polypropylene glycol, copolymer and polyisocyanate used in Sample No. 2 of Table I. These compositions are also tested and the results are reported in Table III. TABLE III Copolymer/Polyahl Component, Adhesive Stren th Weight Ratio of Weight of Component (g) 9.0 9.0 9.0 9.0 9.0 9.0 I κ 9.0 I 9.0 8.0 8.5 9.0 9.5 10.0 As evidenced by the data of Table III, improved impact and lap shear strengths are exhibited by comparison of Run Nos. 1, 3 and 4 with Run Nos. C- j , Co and Ci | . A relatively small improvement is shown in comparison of Run No. 2 with Run No. C2« However, by using a different copolymer or different concentration of ethylene glycol, additional improvement may be observed when a polypropylene glycol having a molecular weight of 1200 is employed. In general, copolymer/- polyahl comparisons exhibiting either lap shear strength or impact strength at least 10 percent better than comparative compositions containing no copolymer are preferred examples of this invention. As evidenced by comparison of the adhesive strengths for Run Nos. 5-8 with Run No. C5, the presence of a LMW Polyahl such as ethylene glycol in amounts from 5 to 20 percent based on the total copolymer/polyahl component significantly improves the adhesive strength of the adhesive compositions. Example 4 Utilizing the procedures described in part A of Example 1 , a fourth series of samples were prepared and then tested for lap shear adhesive strength according to the procedures of part B of Example 1. In test samples the HMW polyahl solvent selected was of two molecular weights. The LMW polyahl selected as the chain extender was 1,4-butylene glycol. Also varied was the type of isocyanate employed. The results of these variations in terms of lap shear adhesive strength was reported in Table IV. Weight Ratio of Adhesive Sample Polyglycol Polyglycol to Strength No. MW copolymer Lap Shear, si (mPa) 5000" 65/35 2925 (20.2) C χ l 5000 100/0 2185 (15.1) 5000 65/35 4229 (29.2) 5000 100/0 2735 (18.9) 5000 65/35 2420 (16.7) • 3-4 5000 100/0 720 (5.0) 4 5000 65/35 2045 (14.1) 5 400 3 50/50 4250 (29.30) .fc. I -1-5 400 100/0 3535 (24.4) Samples designate "C" are controls that do not include copolymer but are otherwise identical to the referenced sample numbers. 2 VORANOL 4702 a polyether polyol having an Mw of 5000 and a triol functionality Polypropylene glycol of Example IA having an Mw 400 and a diol functionality. Copolymer composition: same as Sample 1 to Table 1,ratio of butyl acrylate/hydroxyethyl acrylate = 78/22. LMW polyahl chain extender is 1,4-butylne glycol Isocyanate selected for sample: All trademarks indicated are owned by Dow Chemical Company of Midland, Michigan USA. A = Isonate® 143-L (same as Example l)-liquid, diphenylmethane diisocyanate (MDI), HCO Equivalent = 149.9 B = Isonate® 181 - MDI polyether quasi-prepolylmer, NCO Equivalnet = .182 C = Isonate® 240 - MDI polyester quasi-prepolymer, NCO Equivalent = .225 D = PAPI® 580 - polymer MDI, NCO Equivalent = 137. Inspection of Table IV shows that lap shear adhesive strength of the samples of the invention is improved over the comparison samples that do not include the copolymer. The data shows that use of a higher molecular weight polyglycol solvent phase i.e. 5000 may produce relatively lower lap shear values than the values reported in the earlier examples above that used a 400 molecular weight polyglycol. Compare Examples 4 and 5 of Table IV lap shear embodiments of the invention are typically characterized as possessing more flexibility and hence improved impart strength. These reaction products are particularly useful at lower temperature. The data in Table IV also show the influence that selection of the isocyanate exerts on lap shear adhesive strength. For example, samples 1 and 3 differ only in types of isocyanate used and yield lap shear values of 2925 psi (20.2 mPa) and 4229 psi (29.2 mPa) respectively. As suggested above both adhesive products may be useful, a choice between them depending upon the environmental conditions of use. Both samples show improved lap shear when compared to conventional adhesives not employing the copolymer polyahl solution of the invention.

Claims: CLAIMS; 1. An adhesive composition, comprising: a reaction product of (1) a true solution that comprises: (a) 10 to 70 weight percent of a copolymer having a molecular weight of at least 3500 that comprises 45 to 95 weight percent of an alkyl ester of an α,β-ethylenically 5 unsaturated carboxylic acid and 5 to 55 weight percent of a hydroxyalkyl ester of an α,β-ethylenically unsaturated carboxylic acid, 10 (b) 30 to 88 weight percent of a polyahl having a molecular weight of at least 200, and (c) 2 to 20 weight percent of a polyahl chain _. - extender having a-molecular weight less than 200, and; (2) an organic polyisocyanate in an amount sufficient to react with essentially all of the active hydrogen moieties of the polyahls of (b) and (c), the 0 5 copolymer and polyahl chain extender present in amounts effective to substantially increase the lap shear strength or impact strength over that of a comparable adhesive containing no copolymer. 2. The composition of Claim 1 wherein the alkyl ester is an alkyl acrylate or alkyl methacrylate or a mixture thereof, and hydroxyalkyl ester is a hydroxyalkyl acrylate. 3. The composition of Claim 1 wherein the copolymer comprises an alkyl ester that is an alkyl acrylate or alkyl methacrylate wherein alkyl has from 1 to 4 carbons and a hydroxyalkyl ester that is hydroxyalkyl acrylate or methacrylate and alkyl is ethyl or propyl; the polyahl is a polyalkylene glycol having a molecular weight of 250 to 5000; and the polyahl chain extender is ethylene glycol or propylene glycol, the resulting copolymer having a molecular weight of 4000 to 40,000 and is soluble in the polyahl. 4. The composition of Claim 3 wherein the alkyl ester is butyl acrylate, the hydroxyalkyl ester is hydroxyethyl acrylate, the polyalkylene glycol is polypropylene glycol, the chain extender is ethylene glycol and the polyisocyanate is 4,4'-methyldiphenyl diisocyanate or a liquid mixture containing a predominant amount of said diisocyanate. 5. The composition of Claim 1 wherein the copolymer-polyahl solution comprises (a) 25 to 60 weight percent of the copolymer, (b) 40 to 75 weight percent of the polyahl having a molecular weight of at least 200, and (c) 5 to 15 weight percent of the polyahl having a molecular weight less than 200, and; the polyisocyanate is selected such that the ratio of isocyanate moieties of the polyisocyanate portion to active hydrogen moieties of the polyahl portion are about stoichiometric. 5 6. The composition of Claim 1 wherein the copolymer comprises 45 to 95 weight percent of an alkyl acrylate or alkyl methacrylate or mixture thereof, 5 to 55 weight percent of a hydroxyalkyl acrylate and up to 10 50 weight percent of a t-butylstyrene, styrene or vinyl toluene monomer. 7. The composition of Claim 1 wherein the polyahl chain extender is ethylene glycol, propylene ' 5 glycol, butylene glycol, diethylene glycol or dipropylene glycol. 8. The composition of Claim 1 wherein the extender is ethylene glycol. 20 9. The composition of Claim 1 wherein the polyahl chain extender is 1,4-butylene glycol. 10. The composition of Claim 1 wherein the ? r polyisocyanate is an isocyanate terminated prepolymer that is the reaction product of an organic polyisocyanate and a polyol. 11. A process for making an adhesive 3 composition of the polyurethane type that is the reaction product of a polyahl component and a polyisocyanate component, said process comprising combining (1) a polyahl component that comprises a true solution of 5 (a) 10 to 70 weight percent of a copolymer having a molecular weight of at least 3500 that comprises 45 to 95 weight percent of an alkyl ester of an α,β-ethylenically unsaturated carboxylic acid and 5 to 55 weight percent of a hydroxyalkyl ester of an α,β-ethylenically unsaturated carboxylic acid, (b) 30 to 88 weight percent of a polyahl having a molecular weight of at least 200, and (c) 2 to 20 weight percent of a polyahl chain extender having a molecular weight less than 200, and; (2) an organic polyisocyanate in an amount sufficient to react with essentially all of the active hydrogen moieties of the polyahls of (b) and (c), the copolymer and polyahl chain extender present in amounts effective to substantially increase cured lap shear or impact adhesive strength over that of a comparable adhesive containing no copolymer.

Inventors: SAUNDERS FRANK L, SAUNDERS, FRANK, L.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1987
Main classification: C08L75
IPC codes: C08G18, C09J175