Abstract:
A powder adhesive composition for bonding an elastomer to metals or other rigid substrates comprising a powdered film forming polymer having a liquefaction temperature above room temperature and is capable of forming rubber tearing bonds between an elastomer and a substrate. The adhesive composition is shelf stable and free flowing at room temperature to allow for ease of storage and electrostatic spray application, yet melts or flows at elevated temperatures to form a film on a coated substrate prior to elastomer bonding.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    The present application claims priority under 35 U.S.C. § 119(e) from U.S. Provisional Patent Application Ser. No. 60/939,911, filed May 24, 2007, entitled “POWDER ADHESIVES FOR RUBBER TO METAL BONDING”, the disclosure of which is incorporated herein by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to adhesive compositions for bonding elastomers to various substrates. More particularly, the present invention relates to powdered adhesives for bonding vulcanizable elastomers to metallic substrates, methods for bonding vulcanizable elastomers using such adhesives, and the bonded articles produced thereby. 
       BACKGROUND OF THE INVENTION 
       [0003]    Bonding of rubber vulcanizates to substrates, particularly metal, is conventionally obtained by two-coat primer-overcoat adhesive systems or one-coat primerless systems. In order to provide acceptable bonding, adhesive compositions must exhibit excellent bonding demonstrated by or characterized by retention of rubber on the substrate after bond destruction, adequate sweep resistance i.e., ability of the uncured adhesive coating on the substrate to remain undisturbed against the force of injected green rubber into the mold cavity, good storage stability of the wet adhesive and durable adhesion under extreme environmental conditions, typically measured by the hot tear test (ASTM D-429) or boiling water and salt spray tests (ASTM B-117-97, for example). 
         [0004]    While solvent-based adhesives generally provide good adhesion, they also possess many undesirable qualities from the viewpoint of health, safety, and environmental quality. The solvents are usually toxic, requiring special handling by those who come into contact with the solvents, with the adhesives containing the solvents, or with the fumes generated by either. In addition, the volatility of both the solvents and their fumes presents the risk of fire or explosion during manufacture, packaging, shipping, and use of solvent-based adhesives. Additionally, environmental concerns, especially as reflected in and enforced through governmental laws and regulations, further detract from the desirability of using solvent-based adhesives. 
         [0005]    These problems can be avoided through the use of water-based adhesives, such as those described in U.S. Pat. No. 4,483,962 to Sadowski. Sadowski discloses aqueous adhesive systems which employ a terpolymer latex formed by the emulsion polymerization of 2,3-dichloro-1,3-butadiene and a mixture of at least two different unsaturated monomers copolymerizable therewith. While such water-based adhesives are effective rubber to metal bonding agents for some applications, they can be troublesome to apply to substrates, are less effective bonding agents for certain substrates and generally cost more than their solvent-based counterparts. 
         [0006]    It would therefore be desirable to provide an adhesive which will produce rubber tearing bonds under common testing conditions such as boiling water, hot tear, and salt spray, without the environmental concerns raised by the use of solvents and the processing limitations encountered with aqueous systems. 
         [0007]    Unfortunately, to formulate a powder adhesive composition an additional set of problems must be overcome that do not arise with solvent or aqueous adhesives. Solvent-based adhesives employ film formers comprising polymeric materials that can be dissolved in a solvent. The adhesive film is formed by applying the solvent dissolved film former, then drying to evaporate and remove the solvent. Likewise, aqueous adhesives often use a latex film former which is dried to produce an adhesive film, however many of the polymers employed in these latexes will not film-form out of solution. 
         [0008]    It is to these perceived needs that the present invention is directed. 
       SUMMARY OF THE INVENTION 
       [0009]    In a first aspect of the present invention, a powder adhesive is provided comprising at least one film forming resin or polymer component that does not sinter nor alter its bonding properties during storage, yet can flow sufficiently when heated and form a cohesive film to allow the coated metal substrate to be handled after cooling without removal or damage of the coating. The powder adhesive must be shelf-stable and free-flowing at room temperature while also melting at elevated temperatures so as to form a continuous film on the surface of a substrate. 
         [0010]    For a powdered adhesive, it is necessary to have a film forming polymer that has a liquefaction temperature within a certain temperature range. This liquefaction can arise from exceeding a glass transition temperature (Tg) or a melting point temperature. The liquefaction temperature must be above room temperature so that the powder is stable for storage and shipping and is free flowing. However, the liquefaction temperature must be low enough so that the film can form on the substrate without setting off the chemical reactions that are intended to occur only after the vulcanizing elastomer is in contact with the adhesive, or thermally damaging the polymer or the substrate. 
         [0011]    If the powder formulation is being melt-mixed, the reactions should occur well above the temperature used for the melt processing. Furthermore, the film former must be compatible both with the reactive crosslinker (if used) and with the elastomer to be bonded. 
         [0012]    Furthermore, either the film forming polymer or the crosslinking agents or both must be capable of chemically reacting with the elastomer. Thus, the number of requirements that needed to be met simultaneously in a powder adhesive has increased the complexity of the problem and excludes most of the materials in the form commonly employed in elastomer bonding. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0013]    The present invention provides powder adhesives which effectively bond elastomers to various substrates. In a preferred example of an embodiment of the present invention the substrates are metallic. The powder adhesives eliminate the environmental concerns caused by spray applying solvent-based adhesives, thereby allowing application of the adhesive without the need to capture and contain solvent vapor emissions. Further, powder adhesives may be electrostatic spray applied and any overspray can be captured, reclaimed, and reused thereby further eliminating waste and increasing transfer efficiency. 
         [0014]    In one embodiment of the present invention, the aforementioned issues relating to the need for a film former with a liquefaction temperature within a predetermined range was solved by identifying thermoplastic (high Tg) resins with liquefaction temperatures within certain narrow ranges. Additionally, low Tg polymers, like certain copolymers of dichlorobutadiene were synthesized that are semi-crystalline at room temperature, but which exhibit crystalline melting in the desired temperature range. 
         [0015]    Since the adhesive composition must be a powder at normal working temperature the lower limit of the liquefaction temperature should be above a normal operating temperature, commonly referred to as “room temperature”. Similarly, the upper limit of the liquefaction temperature will vary depending upon the heat stability of the constituents present in the adhesive composition. In one embodiment of the present invention, the adhesive composition is sintered on a substrate prior to elastomer molding, generally at a temperature of over 300° C. In this embodiment, the liquefaction temperature need only be less than the sintering temperature. 
         [0016]    In another embodiment of the present invention in which a crosslinker is employed, the liquefaction temperature of the film-former should be below the temperature at which the crosslinker reacts. Exceeding this temperature would cause the crosslinker to react and crosslink the adhesive film before it has contacted the elastomer resulting in weaker bonding. 
         [0017]    In a preferred embodiment of the present invention, the film former comprises a liquefaction temperature of at least 50° C. and more preferably at least 80° C. In another preferred embodiment of the present invention, the film former comprises a liquefaction temperature of no more than 300° C. and if a crosslinker is employed no more than 175° C. 
         [0018]    Additionally, the powder adhesive composition must form elastomer tearing bonds between the elastomer and the substrate. In the art, this is known as a “rubber tearing” bond and is measured by “rubber retention” which is defined as the percentage of the original bond area that is visibly covered by rubber after the rubber and substrate parts are pulled apart. For the purposes of the present invention, a successful powder adhesive will produce rubber tearing bonds with a rubber retention of at least 80% and preferably over 90% when tested to ASTM D 429 Method B. 
         [0019]    In a preferred embodiment of the present invention, the film former component comprises halogenated polyolefins. In a most preferred embodiment of the present invention, the film former comprises chlorinated and/or brominated polypropylene, polybutylene, or poly-butadiene type polyolefins such as poly(2,3-dichlorobutadiene), brominated poly(2,3-dichlorobutadiene), and poly(2,3-dichlorobutadiene) copolymers, hexachlorocyclopentadiene adducts of unsaturated polyolefins, chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated polyisoprene, and the like. 
         [0020]    The butadiene monomers useful for preparing the butadiene polymer can essentially be any monomer containing conjugated unsaturation. Typical monomers include 2,3-dichloro-1,3-butadiene; 1,3-butadiene; isoprene; 2,3-dimethylbutadiene; chloroprene; bromoprene; 2,3-dibromo-1,3-butadiene; 1,1,2-trichlorobutadiene; cyanoprene; hexachlorobutadiene; and combinations thereof. As described above, an especially preferred embodiment of the present invention is one wherein the butadiene polymer includes at least 60 weight percent, preferably at least 70 weight percent, 2,3-dichloro-1,3-butadiene monomer units. 
         [0021]    In a further embodiment of the present invention, the butadiene monomer can be copolymerized with other monomers to enhance bond strength and achieve a Tg or melting point within the necessary range. Such copolymerizable monomers include α-haloacrylonitriles such as α-bromoacrylonitrile and α-chloroacrylonitrile; α,β-unsaturated carboxylic acids such as acrylic, methacrylic, 2-ethylacrylic, 2-propylacrylic, 2-butylacrylic and itaconic acids; alkyl-2-haloacrylates such as ethyl-2-chloroacrylate and ethyl-2-bromoacrylate; α-bromovinylketone; vinylidene chloride; vinyl toluenes; vinylnaphthalenes; vinyl ethers, esters and ketones such as methyl vinyl ether, vinyl acetate and methyl vinyl ketone; esters amides, and nitriles of acrylic and methacrylic acids such as ethyl acrylate, methyl methacrylate, glycidyl acrylate, methacrylamide and acrylonitrile; and combinations of such monomers. 
         [0022]    The copolymerizable monomers, if utilized, are preferably those which provide functionality to enhance crosslinking between the film former and the elastomer. In a further preferred embodiment of the present invention, the copolymerizable monomer comprises α-haloacrylonitrile and/or α,β-unsaturated carboxylic acids. In an additional embodiment of the present invention, the copolymerizable monomers are generally employed in an amount of 0.1 to 15 weight percent, based on the weight of the total monomers utilized to form the butadiene polymer. 
         [0023]    In an additional embodiment of the present invention, the film former employs a base polymer which is post-chlorinated polypropylene (CPP). The base polymer comprises propylene repeating units. The film former includes derivatives of the post-chlorinated polypropylene. The base polymer weight average molecular weight is from 5,000 to 60,000, and preferably from 15,000 to 45,000. The chlorine content should be in the range of 10 to 60 weight percent, preferably 20-50 weight percent. As the base polymer comprising propylene repeating units, these include crystalline polypropylene, noncrystalline polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and propylene—C 4 -C 10 -α-olefin copolymer. The base polymer may actually be a blend of polypropylene homopolymer and a copolymer comprising propylene repeating units may also be used. As an example of a blend, 25 to 95 weight percent of a propylene homopolymer is combined with from 5 to 75 weight percent, preferably 10 to 60 weight percent of a random propylene copolymer containing repeating units based on 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene. 
         [0024]    Many suitable derivatives of chlorinated polypropylene useful herein are known. Such a representative derivative is a polymer comprising propylene repeating units which is modified by incorporating one or more ethylenic unsaturated monomers, e.g., acrylate or methacrylate monomers, macromonomers, vinyl-functional organosilanes, liquid terminal ethylenic polydiene polymers and/or other graft-functional materials such as maleic acid anhydride, or maleimides. In one such chlorinated polypropylene derivative, chlorinated polypropylene is derivatized with 0.1 to 10 weight “phr” (parts per hundred CPP) of maleic acid anhydride according to known methods. As a further alternative derivative, maleic acid anhydride and acryl- or methacryl-modified hydrogenated polybutadiene, are incorporated using peroxide under known conditions. In another chlorinated polypropylene derivative, chlorinated polypropylene is derivatized with 0.1 to 10 weight phr of epoxy by reacting the CPP with an epoxy group containing compound such as epichlorohydrin. 
         [0025]    In a further embodiment of the present invention, the powder adhesive further comprises a crosslinking or crossbridging agent to obtain acceptable bond strength and elastomer retention. The crosslinking agent may be either appended on the film former or added as a separate constituent to the adhesive composition. For example, if chlorinated polypropylene is employed as the film former, it alone may not produce commercially sufficient rubber tearing bonds in some applications, as illustrated in Example 11. However, as illustrated in Example 7, the addition of a crosslinker provides enhanced bonding of the adhesive formulation. 
         [0026]    In a further embodiment of the present invention, the crosslinking or crossbridging agents comprise, individually or in combination, di- or polynitrosoaromatics, bis- or polymaleimides, di- or polyisocyanates, epoxies, metal oxides, quinone dioximes and their adducts. 
         [0027]    The nitroso compound can be any aromatic hydrocarbon, such as benzenes, naphthalenes, anthracenes, biphenyls, and the like, containing at least two nitroso groups attached directly to non-adjacent ring carbon atoms. More particularly, such nitroso compounds are described as poly-C-nitroso aromatic compounds having from 1 to 3 aromatic nuclei, including fused aromatic nuclei, having from 2 to 6 nitroso groups attached directly to non-adjacent nuclear carbon atoms. The nuclear hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, halogen, and like groups. The presence of such substituents on the aromatic nuclei has little effect on the activity of the poly-C-nitroso compounds in the present invention. As far as is presently known, there is no limitation as to the character of the substituent, and such substituents can be organic or inorganic in nature. Thus, where reference is made to “DNB”, this collectively refers to poly-C-nitroso or di-C-nitroso aromatic compound, benzenes, or naphthalenes, and is understood to include both substituted and unsubstituted nitroso compounds as well as the monomeric form of the compound, unless otherwise specified. 
         [0028]    The metal oxides which are suitable for use in the present invention are zinc oxide and magnesium oxide. The metal oxides are well-known articles of commerce and need not be discussed here in detail. It is noted that other oxides including lead oxide, iron oxide and calcium oxide were tried in one-coat rubber-to-metal adhesives but failed to provide the required environment resistance. 
         [0029]    The effectiveness of the herein-described metal oxides, particularly with respect to providing environmental resistance for rubber-to-metal adhesive compositions is not fully understood. It is known that such metal oxides, as an amphoteric material, react with acids to form metal salts, thereby acting as an acid scavenger. Furthermore, such metal oxides are well known curing activators in the vulcanization of rubber. 
         [0030]    In one embodiment of the present invention, the powder adhesive is applied directly to a substrate. In an alternate embodiment of the present invention, the powder adhesive is applied to a primer coated substrate or a surface treated substrate such as zinc phosphatized steel. The primer may optionally comprise a conventional water-based or solvent-based primer. Typical conventional water-based primers include phenolic resin-type primers such as CHEMLOK® 802, CHEMLOK 805, CHEMLOK 8006, and CHEMLOK 8401 produced by Lord Corporation. Typical solvent-based primers include phenolic resin-type primers such as CHEMLOK 205 or CHEMLOK 207 produced by Lord Corporation. 
         [0031]    The powder adhesive compositions of the present invention have been found to be particularly useful for bonding a wide variety of elastomeric materials, including both vulcanized and vulcanizable elastomeric materials, to themselves or to other substrates, particularly to metal substrates. Elastomers which can be bonded include without limitation natural rubber, polychloroprene rubber, styrene-butadiene rubber, nitrile rubber, ethylene/propylene copolymer rubber (EPM); ethylene/propylene/diene terpolymer rubber (EPDM); butyl rubber, polyurethane rubber, PAREL type elastomers, and the like. Other substrates which can be effectively bonded to themselves or to elastomers include fabrics such as fiberglass, polyamides, polyester, aramides, glass, ceramics and the like. Metals and their alloys to which the elastomers can be bonded include steel, stainless steel, lead, aluminum, copper, brass, bronze, Monel metals, nickel, zinc, and the like, including treated metals such as phosphatized steel, galvanized steel, and the like. 
         [0032]    The powder adhesive may be made by various processes including preparation of an aqueous or solvent-based composition, then spray drying, freeze drying, precipitation or otherwise evaporating the solvent or aqueous solution followed by grinding, melt processing and subsequent grinding. The grinding step may be performed at room temperature or at cryogenic temperatures to enhance the processability of the powder. 
         [0033]    In one embodiment of the present invention, the powder adhesive is ground to an average particle size of less than about 70 microns. In a more preferred embodiment of the present invention, the powder adhesive is ground to an average particle size of less than about 30 microns. Generally, if the particle size is too large, problems arise with fluidization during the spray application and regulation or control of the ultimate film thickness. However, depending upon the application, it may be possible to employ powder adhesives with particle sizes greater than the preferred ranged specified herein. 
         [0034]    Thus, there has been outlined, rather broadly, the more important features of the invention in order that the detailed description that follows may be better understood and in order that the present contribution to the art may be better appreciated. There are, obviously, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. In this respect, before explaining several embodiments of the invention in detail, it is to be understood that the invention is not limited in its application to the details and construction and to the arrangement of the components set forth in the following description. The invention is capable of other embodiments and of being practiced and carried out in various ways. 
         [0035]    It is also to be understood that the phraseology and terminology herein are for the purposes of description and should not be regarded as limiting in any respect. Those skilled in the art will appreciate the concepts upon which this disclosure is based and that it may readily be utilized as the basis for designating other structures, methods and systems for carrying out the several purposes of this development. It is important that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. 
       EXAMPLES 
       [0036]    The powder adhesives of the present invention will bond a variety of rubbers to a variety of substrates. Unless otherwise noted, bonding studies were conducted using a 55 durometer sulfur-cured, carbon black reinforced natural rubber compound, which is typically used as a compound for engine mounts and similar applications. Unless otherwise noted, the steel substrate employed was zinc phosphatized mild steel coupons. Studies include mainly primary bond strengths, along with comparisons to select commercially available solvent or aqueous adhesives. 
         [0037]    In these Examples, the following abbreviations and/or commercially available products were employed: 
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 CHEMLOK ® 205 primer 
                 solvent based phenolic primer available from 
               
               
                   
                 Lord Corporation, Cary, NC. 
               
               
                 CHEMLOK 8007 primer 
                 aqueous phenolic primer available from Lord 
               
               
                   
                 Corporation, Cary, NC. 
               
               
                 CHEMLOK 6254 adhesive 
                 adhesive covercoat containing a mixture of 
               
               
                   
                 chlorinated polymers and dinitrosobenzene in 
               
               
                   
                 a mixture of organic solvents available from 
               
               
                   
                 Lord Corporation, Cary, NC. 
               
               
                 MetalJacket ® 
                 an autodepositable metal treatment and 
               
               
                 1100/2110 
                 primer system based on phenolic resins 
               
               
                 metal treatment 
                 available from Lord Corporation, Cary, NC. 
               
               
                 P(DCD/α-BRAN) 
                 dichlorobutadiene/bromoacrylonitrile 
               
               
                   
                 copolymer 
               
               
                 CPP 
                 chlorinated polypropylene 
               
               
                 CPPma 
                 chlorinated polypropylene modified with 
               
               
                   
                 maleic anhydride 
               
               
                 CPPepoxy 
                 chlorinated polypropylene containing 5% 
               
               
                   
                 epoxy 
               
               
                   
               
             
          
         
       
     
       Example 1 
       [0038]    A 90/10 P(DCD/α-BRAN) adhesive system was spray applied to a film thickness of 25.4 μm over CHEMLOK 205 primer. The rubber was bonded at 171° C. and 13.8 MPa for 14 minutes. 
       Example 2 
       [0039]    Brominated-P(DCD) at about 7 weight percent bromine was applied to a film thickness of 50.8 μm over CHEMLOK 205 primer and bonded as in Ex. 1. 
       Comparative Example 3 
       [0040]    Natural rubber was bonded with commercially available solvent-based CHEMLOK 205/CHEMLOK 6254 and cured for 15 minutes at 160° C. at 13.8 MPa. 
       Example 4 
       [0041]    A 90/10 P(DCD/α-BRAN) adhesive system was applied to a film thickness of 25.4 μm over MetalJacket 1100/2110 metal treatment, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
       Example 5 
       [0042]    Brominated-P(DCD) at about 7 weight percent bromine was applied to a film thickness of 50.8 μm over MetalJacket 1100/2110 metal treatment and bonded as in Example 4. 
       Example 6 
       [0043]    CPPma formulated with 27.75 weight percent dinitrosobenzene, 8 weight percent phenylene bis-maleimide and 0.4 weight percent chlorinated polyisoprene as a wetting agent was applied over CHEMLOK 205 primer. The rubber was then bonded at 160° C. and 13.8 MPa for 14 minutes. 
       Example 7 
       [0044]    CPP formulated with 27.75 weight percent dinitrosobenzene, 8 weight percent phenylene bis-maleimide and 0.4 weight percent chlorinated polyisoprene as a wetting agent was: 
         [0045]    A) applied over CHEMLOK 205 primer, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
         [0046]    B) applied over zinc phosphatized steel, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
       Example 8 
       [0047]    CPPepoxy formulated with 27.75 weight percent dinitrosobenzene, 8 weight percent phenylene bis-maleimide and 0.4 weight percent chlorinated polyisoprene as a wetting agent was: 
         [0048]    A) applied over CHEMLOK 205 primer, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
         [0049]    B) applied over zinc phosphatized steel, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example # 
                 Peel Value 
                 Rubber Retention 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 1 
                 126 N/cm 
                 90% 
                 rubber 
               
               
                   
                 2 
                 109 N/cm 
                 95% 
                 rubber 
               
               
                   
                 Comparative 3 
                 107 N/cm 
                 100% 
                 rubber 
               
               
                   
                 4 
                 114 N/cm 
                 98% 
                 rubber 
               
               
                   
                 5 
                 131 N/cm 
                 98% 
                 rubber 
               
               
                   
                 6 
                 100 N/cm 
                 100% 
                 rubber 
               
               
                   
                 7a 
                 103 N/cm 
                 100% 
                 rubber 
               
               
                   
                 7b 
                  70 N/cm 
                 34% 
                 rubber 
               
               
                   
                 8a 
                 212 N/cm 
                 100% 
                 rubber 
               
               
                   
                 8b 
                 145 N/cm 
                 100% 
                 rubber 
               
               
                   
                   
               
             
          
         
       
     
       Comparative Examples 9 to 11 
       [0050]    Individually, CPPma, CPPepoxy, and CPP were cryogenically ground, electrostatically sprayed over both zinc phosphatized steel and over MetalJacket 1100/2110 primed steel, and baked for five minutes at 121° C. After cooling, these were compression molded with natural rubber at 160° C. and 13.8 MPa for 14 minutes. The bonded samples were tested after completely cooling to room temperature. The average results for three samples each are given in the following table: 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                 Over Zinc 
                 Zinc phos 
                 Over 
                 MetalJacket 
               
               
                   
                   
                 phosphate 
                 % rubber 
                 MetalJacket 
                 % rubber 
               
               
                 Coating 
                 EX # 
                 (N/cm) 
                 retention 
                 (N/cm) 
                 retention 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 CPPma 
                 9 
                 21 
                 0 
                 37 
                 0 
               
               
                 CPPepoxy 
                 10 
                 0 
                 0 
                 16 
                 0 
               
               
                 CPP 
                 11 
                 0 
                 0 
                 — 
                 — 
               
               
                   
               
             
          
         
       
     
       Example 12 
       [0051]    CPPma formulated with 32 weight percent brominated poly(2,3-dichlorobutadiene) at 20 weight percent bromine, 27.75 weight percent dinitrosobenzene, 8 weight percent phenylene bis-maleimide and 0.4 weight percent chlorinated polyisoprene as a wetting agent, applied over CHEMLOK 205 primer, then natural rubber was bonded at 160° C. and 13.8 MPa for 14 minutes. 
         [0000]    
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example # 
                 Peel Value 
                 Rubber Retention 
               
               
                   
                   
               
             
             
               
                   
                 12 
                 107 N/cm 
                 100% rubber 
               
               
                   
                   
               
             
          
         
       
     
       Comparative Example 13 
       [0052]    CPPepoxy formulated with 37.5 weight percent dinitrosobenzene. Formulation was deposited on the coupons from a solvent solution. After drying, the dried films were sintered 5 minutes at 120° C. just as the dried ground powders from the previous examples. Bonding was evaluated using natural rubber bonded at 160° C. and 13.8 MPa for 15 minutes. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Peel Value 
                 % rubber 
               
               
                   
                 Steel substrate 
                 (N/cm) 
                 retention 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Blasted bare steel 
                 240 
                 95 
               
               
                   
                 Zinc phosphatized 
                 177 
                 98 
               
               
                   
                 CHEMLOK 205 
                 93 
                 100 
               
               
                   
                 MetalJacket 1100/2110 
                 93 
                 100 
               
               
                   
                   
               
             
          
         
       
     
       Examples 14 and 15 
       [0053]    The following polymers were isolated by precipitation in methanol and dried. The materials were the ground to powder and applied to MetalJacket coated steel coupons as a powder. The powder coating was sintered for 5 minutes at 125° C. prior to bonding with natural rubber. While the first blend alone will bond rubber, the second formulation with the addition of a crosslinking agent improves the performance: 
         [0054]    14) 50:50 blend of post brominated DCD (5.6% bromine) and a copolymer of 2,3-dichlorobutadiene (DCD) with 10% α-bromoacrylonitrile (α-BRAN). 
         [0055]    15) 50:50 blend of post brominated DCD (5.6% bromine) and a copolymer of 2,3-dichlorobutadiene (DCD) with 10% α-bromoacrylonitrile (α-BRAN) formulated with 5% dinitrosobenzene crosslinker. 
         [0000]    
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example # 
                 Peel Value 
                 Rubber Retention 
               
               
                   
                   
               
             
             
               
                   
                 14 
                 114 N/cm 
                  95% rubber 
               
               
                   
                 15 
                 161 N/cm 
                 100% rubber 
               
               
                   
                   
               
             
          
         
       
     
       Example 16 
       [0056]    The following formulation was melt mixed in a Haake Rheocord lab mixer at 75° C. and was ground into powder using a cryogenic hammermill. The powder coating was sintered for 5 minutes at 125° C. prior to bonding. 
         [0057]    62 weight percent CPPepoxy, 
         [0058]    29 weight percent dinitrosobenzene. 
         [0059]    5 weight percent magnesium oxide, 
         [0060]    4 weight percent phenylene bismaleimide, 
         [0000]    This adhesive formulation was then applied to all of the following substrates: 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                   
               
               
                 Adhesive applied over the following substrates: 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                   
                   
                 Steel coated 
                   
               
               
                   
                 phosphatized 
                 blasted 
                 with CHEMLOK 
                 glass filled 
               
               
                   
                 steel 
                 steel 
                 205 primer 
                 Nylon 6-6 
               
               
                   
                   
               
             
          
           
               
                 55 durometer black-reinforced, sulfur-cured natural rubber: 
               
             
          
           
               
                 Break values 
                 135 N/cm 
                 172 N/cm 
                 159 N/cm 
                 81 N/cm 
               
               
                 Rubber reten- 
                 100 
                 100 
                 100 
                 100 
               
               
                 tion (%) 
               
             
          
           
               
                 69 series epoxy (by Tiger Drylac) on phosphatized steel 
               
             
          
           
               
                 Break values 
                 194 N/cm 
                   
                   
                   
               
               
                 Rubber reten- 
                 90 
               
               
                 tion (%) 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                 Comparative 
               
               
                   
                   
                   
                   
                 Example: 
               
               
                   
                 Steel with 
                 Steel with 
                 Bare 6061 
                 steel with 
               
               
                   
                 Ch 205 
                 Ch 8007 
                 aluminum 
                 Ch 205/6254 
               
               
                   
                   
               
             
          
           
               
                 70 durometer black-reinforced, peroxide-cured EPDM rubber: 
               
             
          
           
               
                 Break values 
                 144 N/cm 
                 145 N/cm 
                 145 N/cm 
                 156 N/cm 
               
               
                 Rubber reten- 
                 rubber break 
                 rubber break 
                 rubber break 
                 rubber break 
               
               
                 tion (%) 
               
             
          
           
               
                 50 durometer black-reinforced, sulfur-cured Nitrile rubber: 
               
             
          
           
               
                 Break values 
                 165 N/cm 
                 182 N/cm 
                 158 N/cm 
                 172 N/cm 
               
               
                 Rubber reten- 
                 rubber break 
                 rubber break 
                 rubber break 
                 rubber break 
               
               
                 tion (%) 
               
             
          
           
               
                 65 durometer black-reinforced, metal oxide-cured Chlorobutyl rubber: 
               
             
          
           
               
                 Break values 
                 102 N/cm 
                 126 N/cm 
                 105 N/cm 
                 124 N/cm 
               
               
                 Rubber reten- 
                 55 
                 60 
                 60 
                 50 
               
               
                 tion (%) 
               
             
          
           
               
                 40 durometer black-reinforced, metal 
               
               
                 oxide-cured G type Neoprene rubber: 
               
             
          
           
               
                 Break values 
                 130 N/cm 
                 105 N/cm 
                 116 N/cm 
                 109 N/cm 
               
               
                 Rubber reten- 
                 rubber break 
                 rubber break 
                 rubber break 
                 rubber break 
               
               
                 tion (%) 
               
               
                   
               
             
          
         
       
     
         [0061]    Although the present invention has been described with reference to particular embodiments, it should be recognized that these embodiments are merely illustrative of the principles of the present invention. Those of ordinary skill in the art will appreciate that the compositions, apparatus and methods of the present invention may be constructed and implemented in other ways and embodiments. Accordingly, the description herein should not be read as limiting the present invention, as other embodiments also fall within the scope of the present invention as defined by the appended claims.