UNITED STATES PATENT OFFICE 2,430,479 BONDING of LAMINATES by MEANS of SOCYANATES Burt Carlton Pratt and Henry Shirley Rothrock, Wilmington, Del, Assignors to E

Patented Nov. 11, 1947 2,430,479

UNITED STATES PATENT OFFICE 2,430,479 BONDING OF LAMINATES BY MEANS OF SOCYANATES Burt Carlton Pratt and Henry Shirley Rothrock, Wilmington, Del, assignors to E. I. du Pont de Nemours & Company, Wilmington, Del, a cor poration of Delaware No Drawing. Application July 23, 1941, Serial No. 403,766 14 Claims. (Cl 154-140) 2 This invention relates to a process for combin amino groups is probably a urea linkage. The ing a plurality of different polymeric materials. bond with a polymer having carboxyl groups is It is at times desirable to modify a polymeric probably an amide linkage. When the polyiso material by combining therewith a second poly cyanate is reacted with a plurality of polymeric Ineric material either in apparently honogeneous 5 materials containing active hydrogen, as in the admixture or in appreciably heterogeneous rela process of the present application, the reaction tion. An example of the first class is the admix is probably complex and depends upon the rela ture of resins with cellulose derivatives in Coating tive reactivity of the hydrogens in the polymers. Compositions. An example of the Second class is To what extent the improvement in properties is the coating of regenerated cellulose film with a O due to chemical bonding (cross-linking) of dif moistureproofing coating, The polymeric mate ferent polymers and to what extent it is due to rials are combined in an effort to alter advan physical forces is not known, tageously the properties of at least one, e. g., Because of the large number of applications to the durability, moisture resistance, etc, or for which the reaction between a diisocyanate and purposes of economy. In many instances this 5 two different polymeric materials, each contain combining of the two different polymeric mate ing active hydrogen as determined by the Zere rials has been unsatisfactory because of inade witinoff method, may be put, the method of car quate bonding of the two different polymeric rying out the reaction can be varied widely. In materials. One method of carrying out the process of this This invention has as an object an improve 20 invention, the surface of one of the polymeric ment in the bond between two different polymeric materials is coated or sprayed with a solution of, materials. A further object is improved adhesion for example, hexamethylene diisocyanate in dry of one polymeric material to another. Another toluene, and the solvent allowed to flash off after object is a new material containing a polymeric which the other polymeric material is placed on material combined with at least one other differ 25 this surface and the two are then heated together ent polymeric material. under pressure. Under these conditions a firm These objects are accomplished by the follow bond is formed due apparently to reaction of the ing invention wherein an Organic compound hav isocyanate groups with both polymeric materials. ing a plurality of -XFCFY groups, wherein X is 30 In some cases it is desirable to incorporate the -C or N and Y is O, S, or NR wherein R is hydro diisocyanate in a Solution of a polymeric material gen or a monovalent hydrocarbon radical, is re containing active hydrogen and then apply this acted with two or more different separately ob Solution to the surface of another polymeric ma tained polymeric materials reactive with terial containing active hydrogen and heat the -X=C=Y groups, i. e., containing active hydro 35 Coated material to cause reaction or further re gen as determined by the Zerewitinoff method. action. In some instances it is desirable to inti (Zerewittinoff, Ber, 40, 2023 (1907); Ber., 41, 2236 mately mix the two polymeric materials before (1908) ; Kohler, J. Am. Chem. Soc., 49, 3181 reacting with the diisocyanate, Again in other (1927).) instances, it is preferable first to react one A preferred subgenus of this invention is that 40 of the polymeric materials partially with the wherein the active hydrogen containing, Sepa poly-X=C=Y compound, then to apply this rately obtained, polymeric materials are reacted material to the surface of One of the materials to with a compound having a plurality of -N-CFZ be united and then to place the other polymeric groups, wherein Z is a chalcogen (J. Am, Chem. material on top of this after which the assembly Soc., 63, 892 (1941)) of atomic weight less than 45 is heated. This method is particularly satisfac 33. This subgenus includes the polyisocyanates, tory when one of the polymeric materials to be the polyisothiocyanates and mixed isocyanate united with another polymeric material is already isothiocyanates having at least one of each of preformed. The method most suitable for any these groups. For convenience of disclosure, the particular case is easily chosen by anyone skilled invention will be discussed below largely in terms 50 in the art. of the polyisocyanates. The more detailed practice of the invention is The bond established between the polyisocyan illustrated by the following examples, wherein ate and a polymeric material having hydroxyl parts are given by weight. There are of course groups is probably thru a urethane linkage. The many forms of the invention other than these bond with a polymer having hydrogen bearing 55 specific embodiments, 2,430,479 3 4. acetic acid at 65-70° C. for 4 hours. The alde Eacample I hyde-neoprene reaction product was isolated by This example illustrates how an improved bond coagulation with alcohol followed by washing with of a cellulosic yarn to natural rubber can be se alcohol and milling to constant weight in an in cured by employing a diisocyanate and an active 5 ternal mixer. hydrogen containing rubber. Five parts of the aldehyde-neoprene was dis Two parts of trioxane-modified natural rubber Solved in 90 parts of toluene at room temperature was dissolved in 65 parts of toluene at room tem With mechanical stirring. When the solution was perature with mechanical stirring. When the homogeneous, 5 parts of hexamethylene diiso solution was homogeneous, after several hours of O cyanate was added. A high tenacity regenerated stirring, 33 parts of hexamethylene diisocyanate cellulose yarn was treated with this solution, was poured into the Solution. The Solution was dried, and wound as in Example I. This treated then placed in a shallow tank of convenient width yarn was then vulcanized to rubber and tested and length and 1,100-denier, high-tenacity, re for bond strength. The bond strength value of generated cellulose yarn, produced in accordance the modified yarn to rubber was about 560 as with the process disclosed in Parker U. S. Patent compared with 100 for the untreated yarn. The 2,133,714, was led through the solution by means increased weight of the yarn was 17%. of suitable guides and then into a drying chamber Eacample III maintained at 140 C. and provided with air cir culation. The excess Solution was permitted to This example illustrates the bonding of cellu drain back into the tank, The yarn did not come lose acetate to aldehyde-modified rubber by in contact with any support unitl it had travelled means of a diisocyanate and the utilization of through the chamber a distance of approximately this bonding to secure adhesion between cellulose 5 feet wherein it was at least partially dried. acetate and rubber. Additional passes through the chamber were made 25 A rubber-coated fabric was sprayed with a so by passing the yarn over suitable rollers. The lution containing 95 parts of toluene, 5 parts of yarn was drawn through the chamber mechani aldehyde-modified rubber, prepared from tri cally at a speed of 15 ft./min, and wound on a oxane and rubber by the general procedure re bobbin. The increased weight of the yarn result ferred to in Example I, and 5 parts of hexa ing from the above treatment amounted to 40% 30 nethylene diisocyanate. A coat of plasticized of the initial weight of the yarn. The yarn was cellulose acetate was then applied to this base then vulcanized to rubber and the strength of and the product thus obtained baked for A hour bond of yarn to rubber tested in the following at 150° C. Exceptionally good adhesion of the ale. topcoat to the rubber was thus obtained. When The yarn or cord is first combined with the the cellulose acetate coating was applied directly trioxane-modified rubber by means of the to the rubber, the adhesion was very poor. The poly-X-C=Y compound. The modified cord material prepared employing the diisocyanate is then laid on the surface of a thin coat of un also exhibited much greater resistance to whiting vulcanized rubber calendered onto a cotton back on Scrubbing. ing. The rubber and cord are then placed in a 40 Eacample IV press and vulcanized at the temperature and This example illustrates the bonding of alkyd pressure necessary to completely vulcanize the resin to regenerated cellulose by means of a di rubber. Shins are used which allow the over isocyanate. flow of a very small amount of rubber during A transparent sheet of regenerated cellulose vulcanization. During the vulcanization, the was coated with a composition consisting of 24 cords become embedded in the surface of the parts of drying oil modified alkyd resin having rubber. The bond of the cord to the rubber is an acid number of 33, 1.4 parts hexamethylene measured individually on a Scott tension testing diisocyanate, 0.4 part cobalt naphthenate drier, machine. In this test the cord is peeled from 0.01 part benzoyl peroxide, and 25 parts toluene. the rubber stock at a uniform rate and the bond 50 The coated sheet was then immediately placed strength read in terms of grams required to cause in a 90° C. oven for 14 minutes. The coated this separation. Sheet was clear and essentially tack free. It ex As a basis of comparison the bond strength hibited no whitening or loosening of the coating value of 100 was assigned to an unmodified re on soaking in water overnight. generated cellulose cord, i. e., one which had not been treated with diisocyanate and trioxane Eacample V modified rubber, values higher than this indicat This example illustrates the bonding of nitro ing improved bond strength, and lower values cellulose to regenerated cellulose by means of an indicating poorer bond strength. On this basis, alkyd resin and a diisocyanate. cotton cords of similar size and construction gave 60 A solution of nine parts of a drying oil modified bond strength value of 150. The bond strength alkyd resin and one part of hexanethylene di value of the modified cord to rubber in this ex isocyanate in 190 parts of toluene was coated on ample was 420. Trioxane-modified rubber alone a regenerated cellulose sheet and topcoated with is of little value as a bonding agent for cellulose a moisture-proofing lacquer of the following con cord and rubber. (55 position: nitrocellulose 50, paraffin wax (M. P. Eacample II 60 C.) 3, danmar (dewaxed) 7, dicyclohexyl This example illustrates the bonding of an phthalate 30, dibutyl phthalate 10, toluene 245, active-hydrogen containing neoprene to cellulosic ethyl acetate 450, and ethyl alcohol 35. The sheet yarn by means of diisocyanate and the bonding of regenerated cellulose was passed continuously of the modified yarn to rubber. 70 through the bath of the aforementioned composi An aldehyde-modified neoprene was prepared tion (top coating) maintained at 35° C., the ex by reacting 100 parts neoprene (polymerized cess coating material being then removed by chloroprene) with 50 parts paraformaldehyde in scraping and the coated sheet dried (the volatile 900 parts carbon tetrachloride solution in the solvent removed) at a temperature above the presence of 10 parts zinc chloride and 90 parts 75 melting point of the Wax. 2,480,479 5 After 24 hours' immersion in water, this coat without the diisocyanate had a breaking strength ing still adhered to the base sheet, whereas a of 120 lbs./sq. in. The improved adhesion ob similar sheet in which the alkyd resin sub-coat tained by this process is of value in the formula containing no diisocyanate showed complete tion of plywood using alkyd resins and diso loosening of the top coat. Also, the diisocyanate cyanates as bonding agents. treated sheet showed a heat-seal of 120 grams whereas the untreated sheet had a heat-Seal of Eacample X 80 grams (on coatings with an equal degree of This example illustrates the use of a diso thermal plasticity, heat seal bond strength is a cyanate for bonding nylon to leather via a thin direct measure of adhesion). O film of polyvinyl butyral. A thin coat of a solution of 10% polyvinyl Eacample VI butyral (containing free hydroxyl groups) and This example illustrates the use of a diiso 1% dibutyl phthalate in ethyl alcohol was ap cyanate in improving the adhesion of cellulose plied to strips of Sole leather (on the rough side) nitrate to cellulose. and also over the nylon side of a nylon coated A solution of 5 parts of decamethylene diiso 5 fabric. The nylon had previously been rough cyanate in 95 parts of toluene was applied to a ened with emery cloth before the application of sheet of regenerated cellulose. After removal of the above solution, he polyvinyl butyral sur the toluene by evaporation, the diisocyanate faces were then treated with a 20% solution of treated sheet was top-coated with the moisture hexamethylene diisocyanate in dry xylene, some proofing lacquer described in Example W. The 20 diisocyanate penetrating to the leather and nylon sheet was dried to remove lacquer solvent at a below. The nylon coated and leather coated temperature above the melting point of the wax. pieces were then clamped together ( the butyral The coated sheet thus obtained was not adversely treated sides touching) and placed in a 75 C. affected by 24 hours' immersion in water, whereas 25 oven for A2 hour. The bond thus obtained was a similar sheet coated with the nitrocellulose so strong that on attempting to pull the lamina lacquer alone showed loosening of the coating tion apart it did not fail at the bond but the in six hours' innersion in Water. leather pulled apart. A control prepared in ex Eacomple VII actly the same manner but without the hexa methylene diisocyanate failed at the bond. This example illustrates the bonding of nitro 30 cellulose to regenerated cellulose employing poly Eacample XI vinyl butyral and a diisocyanate, This example illustrates the use of a diisocy A solution of eight parts of polyvinyl butyral anate-modified partially hydrolyzed polyvinyl (10% free hydroxyl groups) and two parts of 35 acetate resin as an adhesive in the preparation meta-phenylene diisocyanate in 90 parts of tol of laminated wood. uene was applied to regenerated cellulose film Thin maple strips were coated with a 10% and the solvent removed by heating. A top coat solution of 78% hydrolyzed polyvinyl acetate in of moisture-proofing lacquer was applied as in alcohol, the solution allowed to evaporate and the preceding example. The coating was still the coated portion then coated with a 20% solu intact after 24 hours' immersion in water, whereas 40 tion of hexamethylene diisocyanate in dry toluene, a similar coating containing no diisocyanate was some diisocyanate striking through to the wood. removed in less than 6 hours. The strips were then laminated at 120° C. for 10 Eacample VIII minutes at 100 lbs./sq. in. pressure. Testing of This example illustrates the bonding of par 4. strips prepared in the above manner by suspend tially hydrolyzed vinyl acetate to regenerated ing them under a shearing stress of 5 lbs./sq. in. cellulose employing a diisocyanate. in an oven or in water, raising the temperature Ten parts of partially hydrolyzed polyvinyl and noting the temperature at which the lamina acetate (containing 20% free hydroxyl groups), tion failed, showed that the diisocyanate treat 1 part paraffin Wax and 1 part of hexamethylene 50 ment raised the temperature at which the lami diisocyanate in 100 parts dry dioxan were coated nation failed. on regenerated cellulose film and dried at 100 C. The coating exhibited better adhesion and an Temperature at Failure chorage than a similar coating from which the Hexamethylene Diisocyanate treatment diisocyanate was omitted. 5 in oven In Water Eacample IX o F. o F. No------30 128 This example illustrates the improved adhesion Yes------350 183 of alkyd resins for wood when employing a dil isocyanate. A 94% hydrolyzed polyvinyl acetate, which nor A coconut oil modified alkyd resin having the mally cannot be used as an adhesive because it composition: 60% glyceryl phthalate, 40% coco will not give good laminations, gives an excellent nut oil, prepared using 2% excess glycerol, was bond when modified with a diisocyanate. Im applied on maple blocks and allowed to dry and proved adhesion for wood is likewise obtained then coated over with hexamethylene diiso 65 using a diisocyanate in conjunction with poly cyanate containing 0.2% cobalt napthenate as vinyl acetals or polyvinyl ketals, e. g., such as catalyst. The diisocyanate penetrated the resin can be prepared from polyvinyl alcohol. In addi coating, some reaching the wood below. The tion to the decrease in thermoplasticity and in blocks so treated were then heated together, with crease in water resistance indicated by the tests their treated surfaces in contact, under pressure O carried out as described above, all laminations to 75° C. for a hour after which they were al involving the use of diisocyanate are character lowed to stand for 2 days at room temperature ized by improved strength both dry and wet, without any pressure being applied. After this time the breaking strength was 285 lbs./sq. in. Ecample XII A control prepared under similar conditions but s This example illustrates the binding together 2,430,479 7 8 of polyester-amides with cellulose acetate and Eacample XV with leather using a diisocyanate. A low molecular weight polyester-amide was This example illustrates the effect of a diiso made by heating a mixture containing 195.5 parts cyanate on a mixture of cellulose nitrate and an of ethylene glycol, 109.9 parts of ethanolamine, oil modified alkyd resin. 723.1 parts of adipic acid and 100 parts of water Cellulose nitrate (2.9 parts) was dissolved in for two hours at 170° C.A8 mm. followed by 6 15 parts of dry butyl acetate. To 5 parts of this hours at 170° C./2 mm. Eight hundred and Solution was added 7.3 parts of an alkyd resin forty (840) parts of the homogenized mixture containing coconut oil, diethylene glycol phthal (acid number 29.8) was mixed with 42 parts of O ate, and glycerol phthalate. After solution was hexamethylene diisocyanate and 2 parts of cobalt effected, 5 parts of a 20% solution of hexamethyl naphthenate and heated for a period just long ene diisocyanate in Xylene and 0.4 part of a 10% enough to get the reaction started. At this point, solution of benzoyl peroxide in toluene was added. two separate portions of the mixture were treated Films of this solution were flowed on metal plates as follows: s and baked at 100° C. for one-half hour. The film (a) One portion containing 300 parts of the obtained was hard, tough and insoluble in buty) mixture was dissolved in 454 parts of chloroform acetate whereas a control prepared under similar and then mixed in a Werner and Pfleiderer mixer conditions but without the hexamethylene diiso with 200 parts of cellulose acetate which had been cyanate was soft and readily soluble in butyl swollen in 800 parts of acetone. The solvents soon 20 acetate. evaporated and the homogenized mixture was In the process of this invention, there may be heated at 200° C. with mixing for approximately used to link together the plurality of dissimilar One hour. The product thus obtained was a polymeric materials having a plurality of active tough, high molecular weight polymer which hydrogens any organic compound having a plu could be milled Or plate pressed into strong, 25 rality of -XFCFY groups, wherein X is -C or smooth sheets. N and Y is O, S or NR, where R is hydrogen or a (b) The second portion likewise containing nonovalent hydrocarbon radical. The con 300 parts of the mixture was dissolved in 454 pounds having a plurality of -X=C=Y groups parts of chloroform and then mixed in a Werner include the polyisocyanates, the polyisothiocya and Pfleiderer mixer with 200 parts of leather 30 nates, the polyketenes, the polythioketenes, the scrap which had been soaked in 454 parts of polygetenimines, and the polycarbodiimides, i. e., chloroform. The Solvent soon evaporated leav Organic compounds having a plurality of -X= ing a homogeneous mixture which was cured at CFY groups selected from the class consisting 200 C. over a period of approximately one hour. of the isocyanate, isothiocyanate, ketene, thio The final product was a tough, elastic na SS which 35 ketene, keteninnine and carbodiimide groups in could be milled into thin sheets on a rubber mill. cluding not only those compounds, all the -X= These sheets were plate pressed to smooth, tough C-FY groups of which are the same but also those films resembling leather. compounds wherein there is more than one type of-X-C=Y group. Eacample XIII 40 The preferred compounds are those having a This example illustrates the binding of poly plurality of -N-CFZ groups wherein Z is a esteramides to polyvinyl alcohol using hexameth chalcogen of atomic weight below 33. These are ylene diisocyanate. preferred because of their greater availability, A mixture containing 195.5 parts of ethylene lesser cost, greater ease of preparation and be glycol, 109.9 parts of ethanolamine, 723.1 parts of cause of their reactivity. adipic acid and 100 parts of water was heated for Exemplary -X-FCFY compounds include two hours at 170° C. at atmospheric pressure foll polymethylene diisocyanates and diisothiocya lowed by six hours at 200° C. under 2 mm. The nates such as ethylene diisocyanate, trimethylene product at this stage was a soft, fluorescent wax diisocyanate, dodecamethylene diisocyanate, hex like solid having an acid number of 10.4. Seven 50 amethylene diisocyanate, tetramethylene diiso hundred parts of this was mixed with 35 parts of cyanate, pentamethylene diisocyanate, and the hexamethylene diisocyanate and reacted at 200 corresponding diisothiocyanates; alkylene diiso C. in a Werner and Pfleiderer nixer for about 30 cyanates and diisothiocyanates such as propyl minutes. At this stage 140 parts of polyvinyl ene-1,2-diisocyanate, 2,3-dimethyltetramethylene alcohol was added and the reaction Was continued 55 diisocyanate and diisothiocyanate, butylene-1,2- for an additional hour at 200° C. or until the diisocyanate, butylene-1,3-diisothiocyanate, and product became quite tough. butylene-1,3-diisocyanate; alkylidene diisocya nates and diisothiocyanates such as ethylidene di Eacaniple XIV isocyanate (CH3CH(NCO)2) and heptylidene di This example illustrates the effect of a diiso 30 isothiocyanate (CH3(CH2)5CH(CNS) 2): cycloal cyanate on a mixture of urea-formaldehyde resin kylene diisocyanates and diisothiocyanates such and alkyd resin. as 1,4-diisocyanatocyclohexane, cyclopentylene A urea-formaldehyde resin, prepared from di 1,3-diisocyanate, and cyclohexylene-1,2-diiso methylol-urea and isobutanol (2.5 parts) and a thiocyanate; aromatic polyisocyanates and poly castor oil modified alkyd resin (1.75 parts) were isothiocyanates such as m-phenylene diisothio dissolved in 5 parts of dioxan. To the resulting cyanate, p-plenylene diisocyanate, p-phenylene solution was added 1.5 parts of a 20% solution of diisothiocyanate, l-methyl-phenylene-2,4-diiso hexannethylene diisocyanate in xylene and 0.05 cyanate, naphthylene-1,4-diisocyanate, oo'-tolu part of a 10% solution of benzoyl peroxide in tol ene diisocyanate, diphenyl-4,4'-diisothiocyanate uene. Films of this solution were flowed on metal O and diisocyanate, benzene-1,2,4 triisothiocyanate, plates and baked for 2 hour at 127° C. after 5-nitro-1,3-phenylene diisocyanate, xylylene-1,4 which they were hard and tough. A film similar diisocyanate, xylylene-1,3 diisocyanate, 4,4'-di to the above but without the hexamethylene di phenylenennethane diisocyanate, 4,4'-diphenyl isocyanate was inferior with respect to toughness enepropane diisocyanate and xylylene-1,4 diiso and hardness. 5 thiocyanate; aliphatic-aromatic diisocyanates 2,430,479 9 10 and disothiocyanates such as phenylethylene di carbons, carbamates, and amines prepared by any isocyanate (C5HaCH(NCO) CH2NCO); diisocya of the methods known in the art may be em nates and diisothiocyanates containing hetero ployed. The original resin may contain variable atoms such as SCNCH2OCHNSC, proportions of formaldehyde condensed with one or a mixture of monomeric materials and can be SCNCH2CH2OCH2CH2NSC low, medium, or high molecular weight. and SCN(CH2)3-S-(CH2)3NSC; 1,2,3,4-tetra Nitrogen-containing polymeric materials are isocyanatobutane, butane-1,2,2 triisocyanate, 1 especially useful, for example: Polyester-amides isocyanato, 4-isothiocyanatohexane, and 2-chlo Such as the condensation product of ethanol ro-1,3-diisocyanatopropane. 10 anine, adipic acid, and ethylene glycol, or the The preferred diisocyanates, diisothiocyanates condensation product of hexamethylenediamine, and mixed isocyanate-isothiocyanates have the adipic acid, and ethylene glycol, or, in general, general formula ZCN R NCZ in which R is a polymers formed by condensing a polyamine, divalent hydrocarbon radical and Z is a chal polybasic acid and polyhydric alcohol. Low or cogen of atonic Weight less than 33, 5 high molecular weight polyamides such as poly Examples of other types of -X=C=Y com hexamethyleneadipamide, polydecannethylere pounds which may be used include carbon sub adipamide, 6-aminocaproic acid polymer, and the oxide CO2, carbon subsulfide C3S2, diethylenedi like may be used. Protein and protein-like ma ketene terials such as gelatin, casein, zein and leather; CH-CH 20 guns such as copal, Congo, kauri, shellac and / Y dammar; and polymerized or gelled drying oils O=C=C C=C=O of the linoxyn type are also suitable. N M Ether resins, for example, those prepared by CH-CH reacting organic polyhalides with polyhydric and compounds of formulae: 25 phenols as described in U. S. Patent 2,060,175, and polymeric derivatives of acrylic, methacrylic o-c-f-(CH-i-c=o or fumaric acid may also be used as resinous materials to which a different resinous material may be bonded. 30 Active hydrogen-containing vulcanizable mate rials may be employed including aldehyde treated natural and Synthetic rubbers, for example, those disclosed in U. S. Patents 1,915,808 and 1,640,363 and British Patent 486,878, rubber di(hydroxy 35 phenyl), and hydroxylated rubbers, e.g., the per and acetylated rubbers and hydrolyzed peracetylated O O rubbers described in U. S. Patent 1,988,448. The term "rubber' unless otherwise modified, is used ché–C-(CH-c-e-c H in its generic sense to include natural rubber, b=0 (=o 40 balata, gutta percha, modified rubber, neoprene, In the practice of the present invention, the and the various butadiene and substituted buta poly-XFCFY compound is reacted with a plu diene polymers and interpolymers. rality of polymeric materials having active hy In the practice of this invention, any combina drogen containing groups. The presence of ac tion of two or more different polymeric materials tive hydrogen containing groups is determinable containing active hydrogens may be used. The by means of the Zerewittinoff test. (“Analyse materials referred to above are given only by way und Konstitutionsermittlung Organischen Wer Of example. gindunger,' by Hans Meyer, Finfte Auflage, It is not always necessary that the pages 371-375.) These materials contain groups poly-X-C-Y such as -OH, -NH2, -NRH, -COOH, -SH 50 or groups which react similarly under the re compound be homogeneously mixed with one or action conditions. Among the polymeric ma-. more of the polymeric materials being bonded. terials that may be bonded together by using one Thus, in some instances (e. g., Examples IX-XI) or more of the poly-X-FC-Y compounds re the desired effect can be obtained by coating the ferred to above may be mentioned hydroxylated 5 5 surface of one polymeric material with another Organic materials such as cellulose; starch; dex polymeric material and then spraying or other trin; wood; cellulose derivatives containing hy wise treating the coating with the poly-X-C-Y droxyl, amino or other active hydrogen-contain compound or a solution thereof, the solubility of ing groups including among others cellulose the -X=C=Y compound in the coating being esters such as acetate, propionate, butyrate and 60 sufficient to permit some of the -X=C=Y con nitrate; cellulose mixed esters; cellulose ethers pound to strike through to the Surface of the Such as methyl- or ethyl cellulose; carboxylated polymeric material below the coating. cellulose; and regenerated cellulose. Polyvinyl The quantity of the poly-X=CFY compound alcohol and polyvinyl alcohol derivatives such as used depends upon the system of polymeric ma partially hydrolyzed polyvinyl acetate or poly 65 terials with which it is to be used. In Some cases, vinyl propionate; polyvinyl acetals; and poly the surface of one of the polymeric materials is vinyl ketals can be used. Polyhydric alcohol simply coated or sprayed with the poly-X=C=Y polybasic acid condensation products (alkyd compound alone or with a solution thereof in an resins) with free hydroxyl or carboxyl groups, inert solvent, and the other polymeric material which resins may or may not be oil-modified, O applied and the two heated under pressure. In may also be used. the cases where the poly-X-CFY compound is Resins resulting from the condensation of reacted with a mixture of two or more polymeric formaldehyde with such materials as phenols, materials, the proportion of the poly-X-CFY amides (including ureas and sulfonamides), alde compound may be varied widely. In most cases, hydes, ketones, aromatic ethers, aromatic hydro 5 however, the preferred amount of reagent will 2,430,479 11 12 range from 0.5 to 15% of the weight of the poly meric material' is used in its usual sense as meric materials. applying to products which contain a plurality The temperature used in the process of this of identical or closely related structural units and invention depends upon the reactivity of the which can be formed from or degraded into con -X=C=Y compound towards the polymeric ma pounds having the same or almost the same terials. In many cases reaction can be brought chemical composition as the structural units in about at room temperature. In most cases, how the polymer. As contrasted with monomeric ever, temperatures of 75-200° C. are used to materials, polymeric materials have a high no greatest advantage. When the process is used to lecular weight. laminate two or more articles, e. g., sheets, it is O The expression "different and separately ob desirable to use heat and pressure. tained' as applied to the polymeric materials is As indicated in Examples IX and XII above, used to indicate that the polymers have a differ the reaction between the poly-XFCFY Con ent chemical composition, rather than a mere pound and the plurality of different, active hy difference in molecular weight, and that they drogen containing polymeric Substances may be s are separately formed. Thus ethyl cellulose as carried out with the assistance of catalysts, for ordinarily prepared is not considered to constitute example, the metallic catalysts known as "metal "different and separately obtained' polymeric lic driers' in the drying oil art, e. g., cobalt, materials even though some of the molecules of manganese, lead, iron, vanadium, copper, Cerium, the ethyl cellulose may contain more ethyl chronium, uranium, nickel and tin Salts of high 20 groups than others and all molecules do not molecular weight organic acids, such as oleic, acquire their ethyl groups simultaneously in the stearic, lineoleic, myristic and other long chain ethylation reaction. fatty acids, naphthenic, and other alicyclic acids. The products of this invention will be referred The amount of metallic drier used is from 0.001 to as "reaction products' of the reactants en to 5%, preferably from 0.01 to 1.0%, based on 25 ployed but this term is not intended to be lin the weight of the -X=CFY compound. ited to products in which all the reactants, i. e., When one of the polymeric materials to be the poly-X=C=Y compound or compounds and treated is in the form of films, yarns, cords, fab the different and separately prepared polymeric rics or other base materials, the process is Con materials are all chemically united into a single veniently carried out by immersing the base 30 molecular aggregate or Species. material in a solution containing One or more The above description and examples are in other polymeric materials and the poly-X=CFY tended to be illustrative only. Any modification compound or compounds, regulating the quantity of or variation therefrom Which conforms to the of solution adhering to the base material by spirit of the invention is intended to be included means of squeeze rolls, scrapers, or other Suitable 35 within the scope of the claims. devices, or by merely allowing the excess to drain What is claimed is: off followed by solvent removal either sponta 1. A reaction product of a plurality of different neously or at elevated temperatures. In Some and separately formed, active hydrogen-contain cases, it may be preferable to apply separately ing polymeric materials, with an organic com the polymeric material or materials and the 40 pound having as the sole reacting groups a plu poly-X=C=Y compound. For example, one rality of -X=C=Y groups, wherein X is se polymeric structure may first be treated with lected from the class consisting of -C and N, another polymeric material, dried to remove the and Y is selected from the class consisting of O, solvent, and then treated with the poly-XFCFY S and NR, where R is selected from the class compound from solution or in vapor or gaseous 45 consisting of hydrogen and monovalent hydro form. Treatment of one of the polymeric mate carbon radicals, rials with the poly-X=C=Y compound first and 2. A reaction product of a plurality of different and then with the other polymeric material is and separately formed, active hydrogen-contain also a method of carrying out the invention, ing polymeric materials with an organic con The present invention is of value in that it 50 pound having as the sole reacting groups a plu affords a means whereby a plurality of different, rality of -N=C=Z groups, wherein 2 is a chal separately obtained polymeric materials can be cogen of atomic weight below 33. bonded together or combined in such a manner 3. A reaction product of a plurality of differ that the bond between the materials is stronger ent and separately formed, active hydrogen than has hitherto been possible to obtain with 55 containing polymeric materials with an Organic the same materials. While we do not wish to polyisocyanate wherein the isocyanate groups are be bound by our explanation for this result, we the Sole reacting groups. believe that the polymeric materials are chemi 4. A reaction product of a plurality of differ cally linked (cross-linked) by means of the ent and separately formed, active hydrogen-con poly-X=C=Y compound. Reference to the 60 taining polymeric materials with an Organic di process as a means for uniting a plurality of isocyanate wherein the isocyanate groups are the different polymeric materials is intended to cover sole reacting groupS. the process whether the "uniting' is chemical, 5. A reaction product of a plurality of different physical or partly chemical and partly physical. and separately formed, active hydrogen-contain The invention is useful in the preparation of 5 ing polymeric materials with hexamethylene di laminated articles from Wood, paper, cloth, Syn isocyanate. thetic resins and the like. It is useful for coat 6. A reaction product of a plurality of different ing preformed polymeric materials such as films, and separately formed, hydroxyl-containing poly fabrics, cords, etc. with other polymeric products meric materials with an organic compound hav in order to obtain improved adhesion and dura O ing as the sole reacting groups a plurality of bility. The process is also useful in bonding to -N=C=Z groups, wherein Z is a chalcogen of gether an intinate mixture of two or more differ atomic weight below 33. ent polymeric materials before they are fabri 7. Process for uniting a plurality of differ cated into articles. ent and separately formed polyneric materials In the specification and claims the term "polyr s containing active hydrogen, which comprises re 2,430,479 13 14 acting the same with an organic compound hav -C and N, and Y is selected from the class con ing as the sole reacting groups a plurality of sisting of O, S, and NR, wherein R is selected -X=C=Y groups, wherein X is selected from from the class consisting of hydrogen and mono the class consisting of -C and N, and Y is se valent hydrocarbon radicals. lected from the class consisting of O, S, and NR, 13. Process for uniting an active-hydrogen con wherein R is selected from the class consisting taining polymeric material to the surface of an of hydrogen and monovalent hydrocarbon radi article containing a different active-hydrogen cals. containing polymeric material, which comprises 8. Process for uniting a plurality of different coating said surface with an organic compound and separately formed polymeric materials con O having as the sole reacting groups a plurality of taining active hydrogen which comprises re -N=C=Z groups, wherein 2 is a chalcogen of acting the same with an organic compound hav atomic weight less than 33 and then applying to ing as the Sole reacting groups a plurality of the coated surface said first mentioned polymeric -N=C=Z groups, wherein 2 is a chalcogen of material. atomic weight less than 33. 5 14. Process for uniting an active-hydrogen con 9. Process for uniting a plurality of different taining polymeric material to the surface of an and separately formed polymeric materials con article of a different active-hydrogen contain taining active hydrogen which comprises react ing polymeric material, which comprises incor ing the same with an organic polyisocyanate porating in said first mentioned polymeric ma wherein the isocyanate groups are the sole re 20 terial an organic compound having as the sole acting groups. reacting groups a plurality of -N=C=Z groups, 10. Process for uniting a plurality of different wherein Z is a chalcogen of atomic weight less and separately formed polymeric materials con than 33, applying the resulting composition to taining active hydrogen which comprises react the surface of said article, and heating the com ing the same with an organic diisocyanate where 25 position while in contact with said article. in the isocyanate groups are the sole reacting BURT CARLION PRATT. groups. HENRY SHIRLEY ROTHROCK. 11. Process for uniting a plurality of different and separately formed polymeric materials con REFERENCES CTED taining active hydrogen which comprises react 30 The following references are of record in the ing the same with hexamethylene diisocyanate. file of this patent: 12. Process for uniting an active-hydrogen con taining polymeric material to the surface of an UNITED STATES PATENTS article of a different active-hydrogen containing Number Name Date polymeric material, which comprises bringing the 35 2,046,378 Hauk ------July 7, 1938 two polymeric materials together in the presence 2,047,226 Rigby ------July 14, 1936 of an organic compound having as the sole re 2,241,321 Schlack ------May 6, 1941 acting groups a plurality of -X-C=Y groups, 2,284,896 Hanford ------June 2, 1942 wherein X is selected from the class consisting of 2,282,827 Rothrock ------May 12, 1942

Certificate of Correction Patent No. 2,430,479. November 11, 1947. BURT CARLTON PRATT ET AL. It is hereby certified that errors appearin the printed specification of the above numbered patent requiring correction as follows: Column 3, line 21, for unit' read until; column 6, line 58, in the table, second column thereof, for '350' read 350-; column 8, line 31, for “polygetenimines' read polyteteninines; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office. Signed and sealed this 20th day of January, A. D. 1948.

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THOMAS F. MURPHY, Alaedobandonniesdoner of Patents. 2,430,479 13 14 acting the same with an organic compound hav -C and N, and Y is selected from the class con ing as the sole reacting groups a plurality of sisting of O, S, and NR, wherein R is selected -X=C=Y groups, wherein X is selected from from the class consisting of hydrogen and mono the class consisting of -C and N, and Y is se valent hydrocarbon radicals. lected from the class consisting of O, S, and NR, 13. Process for uniting an active-hydrogen con wherein R is selected from the class consisting taining polymeric material to the surface of an of hydrogen and monovalent hydrocarbon radi article containing a different active-hydrogen cals. containing polymeric material, which comprises 8. Process for uniting a plurality of different coating said surface with an organic compound and separately formed polymeric materials con O having as the sole reacting groups a plurality of taining active hydrogen which comprises re -N=C=Z groups, wherein 2 is a chalcogen of acting the same with an organic compound hav atomic weight less than 33 and then applying to ing as the Sole reacting groups a plurality of the coated surface said first mentioned polymeric -N=C=Z groups, wherein 2 is a chalcogen of material. atomic weight less than 33. 5 14. Process for uniting an active-hydrogen con 9. Process for uniting a plurality of different taining polymeric material to the surface of an and separately formed polymeric materials con article of a different active-hydrogen contain taining active hydrogen which comprises react ing polymeric material, which comprises incor ing the same with an organic polyisocyanate porating in said first mentioned polymeric ma wherein the isocyanate groups are the sole re 20 terial an organic compound having as the sole acting groups. reacting groups a plurality of -N=C=Z groups, 10. Process for uniting a plurality of different wherein Z is a chalcogen of atomic weight less and separately formed polymeric materials con than 33, applying the resulting composition to taining active hydrogen which comprises react the surface of said article, and heating the com ing the same with an organic diisocyanate where 25 position while in contact with said article. in the isocyanate groups are the sole reacting BURT CARLION PRATT. groups. HENRY SHIRLEY ROTHROCK. 11. Process for uniting a plurality of different and separately formed polymeric materials con REFERENCES CTED taining active hydrogen which comprises react 30 The following references are of record in the ing the same with hexamethylene diisocyanate. file of this patent: 12. Process for uniting an active-hydrogen con taining polymeric material to the surface of an UNITED STATES PATENTS article of a different active-hydrogen containing Number Name Date polymeric material, which comprises bringing the 35 2,046,378 Hauk ------July 7, 1938 two polymeric materials together in the presence 2,047,226 Rigby ------July 14, 1936 of an organic compound having as the sole re 2,241,321 Schlack ------May 6, 1941 acting groups a plurality of -X-C=Y groups, 2,284,896 Hanford ------June 2, 1942 wherein X is selected from the class consisting of 2,282,827 Rothrock ------May 12, 1942

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THOMAS F. MURPHY, Alaedobandonniesdoner of Patents.