Abstract:
An improved method of making an ethylene acrylate (AEM) elastomer or a polyacrylate (ACM) elastomer wherein an aqueous solution of hexamethylene diamine (HMDA) is employed as the curative agent rather than hexamethylene diamine carbamate (HMDAC). The HMDA reacts with the curative-site monomer derived from the monoalkyl ester of a 1,4-butene-dioic acid in the presence of water, producing (i.e., after press-curing and any secondary heat-curing) a crosslinked elastomer with properties essentially indistinguishable from that produced using HMDAC as the curative agent. Advantageously, the aqueous solution of HMDA can be blended directly into the compound or it can be deposited on an additive such as silica or carbon black prior to blending. Elastomers produced by the improved method according to the present invention are particularly useful in automotive applications requiring oil resistant compositions.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS  
       [0001]    Applicant claims the benefit of priority to provisional application No. 60/376,778 filed Apr. 29, 2002; herein incorporated by reference in its entirety. 
     
    
     
       BACKGROUND OF THE INVENTION  
         [0002]    1. Field of the Invention  
           [0003]    The present invention relates to a method of manufacturing cured (i.e., crosslinked) ethylene acrylate elastomer or polyacrylate elastomer. More specifically, the present invention relates to the use of an aqueous solution of hexamethylene diamine (HMDA) as a curative agent for ethylene/alkyl acrylate copolymer and poly(alkyl acrylate) copolymer containing a mono alkyl ester cure-site termonomer.  
           [0004]    2. Description of the Related Art  
           [0005]    It is generally known in the art to cure a terpolymer of ethylene, an alkyl acrylate, and a mono alkyl ester cure-site monomer with hexamethylene diamine carbamate (HMDAC) to produce vulcanized elastomer. The resulting ethylene acrylate elastomers exhibit a combination of mechanical toughness, low brittle point, low oil swell, and a high level of heat aging resistance that is particularly conducive to certain commercial automotive applications. For example, U.S. Pat. No. 3,904,588 describes and claims the curing of random copolymer derived from the polymerization of ethylene, an alkyl acrylate (e.g., methyl and ethyl acrylate) and a monoester of maleic acid (e.g., methyl, ethyl, and propyl 1,4-butene-dioic acid). This reference discloses and claims the use of 1.5 parts of HMDAC per 100 parts by weight of the terpolymer containing the mono ester cure-site monomer along with other ingredients being blended on a roll mill followed by a press-curing step for 30 minutes at 180° C. at a total pressure of about 40,000 psig. The reference teaches that hexamethylene diamine can be used as the vulcanizing agent but does not teach the use of an aqueous solution of HMDA.  
           [0006]    In a companion U.S. Pat. No. 3,883,472 filed on the same day, an elastomeric composition having good scorch resistance is taught involving an acrylic ester/butenedioic acid monoester dipolymer or an ethylene/acrylic ester/butenedioic acid monoester terpolymer which is crosslinked with a vulcanizing agent and at least one vulcanization accelerator. Hexamethylene diamine carbamate, tetramethylenepentamine (TEPA), and hexamethylene diamine are employed as the curing agent during vulcanization. However, there is again no disclosure of the use of an aqueous solution of HMDA. Similarly, it is also generally known that polyacrylate elastomers typically involving two or more alkyl acrylates (e.g., ethyl acrylate, butyl acrylate and 2-methoxyethyl acrylate) copolymerized with a small amount of butene dioic acid monoalkyl ester cure-site termonomer can be crosslinked during curing by the use of various diamines such as HMDA and HMDAC, see for example Japanese patent application JP 2000-44757.  
           [0007]    In U.S. Pat. No. 4,412,043 an elastomeric composition derived from an ethylene/methyl or ethyl (meth)acrylate copolymer having a third cure-site involving 4-(dialkylamino)-4-oxo-2-butenoic acid termonomer is taught by employing a diamine curing agent. Again HMDA is identified as an alternative to HMDAC but no disclosure of the use of an aqueous solution of HMDA is present.  
           [0008]    In U.S. Pat. No. 4,026,851, the use of an aqueous 88% hexamethylene diamine solution is employed as a curing agent for curing a polyacrylate, ethylene/acrylate copolymer or ethylene/acrylate/methacrylate terpolymer wherein no monoester cure-site monomer is present.  
           [0009]    The problem with the above methodology for curing is that HMDAC is a relatively expensive crosslinking agent and even though it is a minor constituent it represents a significant cost and HMDA is relatively corrosive and difficult to handle with a melt/freeze point of about 40° C. As such, an alternate methodology and low cost alternative crosslinking agent would be potentially advantageous.  
         BRIEF SUMMARY OF THE INVENTION  
         [0010]    In view of the above-mentioned problems, it has now been discovered that an aqueous solution of HMDA can advantageously be used as the curative agent to crosslink both ethylene acrylate (AEM) type elastomer and polyacrylate (ACM) type elastomer having small amounts of butene dioic acid monoalkyl ester cure-site monomer present. It has now been discovered that even in the presence of the water of solution the conventional press-curing and secondary heat-curing steps produce elastomer properties essentially indistinguishable from those resulting from the use of HMDAC as the curative agent. Conveniently, commercially available HMDA aqueous solution (typically at about 70/30 weight ratio) can be employed as a substitute for HMDAC to be blended directly with the gum rubber copolymer, or such a solution can be mixed with and/or deposited on an additional additive such as carbon black, silica, di-ortho-tolyl guanidine (DOTG) or the like prior to blending with the polymer.  
           [0011]    Thus the present invention provides in a process for making a crosslinked ethylene acrylate elastomer or a polyacrylate elastomer involving the steps of blending a curative agent with an ethylene/alkyl acrylate copolymer containing a monoalkyl ester of a 1,4-butene-dioic acid cure-site termonomer or with a polyacrylate copolymer containing a monoalkyl ester of a 1,4-butene-dioic acid cure-site termonomer and optionally other additives and then press-curing at elevated temperature and elevated pressure for sufficient time to crosslink the copolymer followed by an optional post-cure heating at ambient pressure to further cure the elastomer, the specific improvement comprising the step of blending an aqueous solution of hexamethylene diamine with the copolymer as the curative agent. The present invention further provides an improved process as described above wherein the aqueous solution of HMDA and water is converted to a dry liquid concentrate before it is added to the mixer. The dry liquid concentrate can be made from several different fillers including carbon black, fumed silica, precipitated silica or other mineral fillers. Preferably the additive to which the aqueous solution is added prior to blending with the copolymer is carbon black or silica.  
         DETAILED DESCRIPTION OF THE INVENTION  
         [0012]    In this disclosure, the term “copolymer” is used to refer to polymers containing two or more monomers. The use of the term terpolymer and/or termonomer means that the copolymer has at least three different comonomers. “Consisting essentially of” means that the recited components are essential, while smaller amounts of other components may be present to the extent that they do not detract from the operability of the present invention. The term “(meth)acrylic acid” refer to methacrylic acid and/or acrylic acid, inclusively. Likewise, the term “(meth) acrylate” means methacrylate and/or acrylate.  
           [0013]    Ethylene acrylate (AEM) elastomers and polyacrylate (ACM) elastomers having small amounts of a butene dioic acid monoalkyl ester cure-site monomer present are widely used in the automotive industry because of their excellent resistance to lubricating oils and greases, heat and compression set resistance, mechanical toughness and low brittle point. As such, they are well suited for gaskets and seals, various types of automotive hoses, spark plug boots, and similar engine compartment rubber components. Typically a blend of the uncrosslinked (i.e., unvulcanized gum rubber) copolymer and diamine curing agent along with various fillers and other additives is subjected to a press-curing step at sufficient time, temperature and pressure to achieve covalent chemical bonding and crosslinking. Commercially, the practiced curing agent for AEM elastomer production is hexamethylene diamine carbamate (HMDAC).  
           [0014]    The novel process according to the instant invention involves the use of an aqueous solution of hexamethylene diamine (HMDA) as the curing agent. It has now been discovered that an aqueous solution of HMDA can be employed either directly as a curative agent or employed to make a HMDA concentrate by depositions on an additive substrate.  
           [0015]    Contrary to what may be expected, commercially available aqueous blends of HMDA and water (typically at a 70/30 weight ratio) can be employed as a direct substitute for HMDAC with a net effect of adding only about 0.5 pph (parts per hundred) of water to the resulting elastomer, essentially without affecting the critical properties of the elastomer.  
           [0016]    The advantages and benefits of such an improved process for curing ethylene acrylate (AEM) and polyacrylate (ACM) elastomers are considered significant. An aqueous solution of HMDA represents a far more economical alternative relative to the use of HMDAC. Also, HMDA is preferably employed in an aqueous solution rather than as a solid because as a pure solid it is a corrosive material with a melt/freeze point of 40° C.  
           [0017]    The aqueous solution of HMDA employed in the improved process of the instant invention can generally be any such solution provided that sufficient HMDA is employed to achieve the desired crosslinking and the quantity of water does not influence the final properties of the elastomer. Preferably, a concentrated solution of HMDA is employed wherein the HMDA is the major component. Conveniently a commercially available solution of typically 70/30 weight ratio HMDA/H 2 O is employed.  
           [0018]    Optionally, the aqueous solution of HMDA can be mixed or deposited onto one or more fillers or additives thus forming a concentrate. This concentrate can then be conveniently employed as the curing agent source during the manufacture of the elastomer by blending the copolymer to be cured with the concentrate.  
           [0019]    For purposes of this invention the phrase “a monoalkyl ester of a 1,4-butene-dioic acid cure-site termonomer” refers to and includes any unsaturated dicarboxylic acid or derivative thereof that after polymerization results in contributing a succinic acid type moiety along the backbone of the terpolymer which can ultimately be monoesterified. As such, the monoalkyl esters of maleic acid and fumaric acid are preferred. The most preferred monomers are monomethyl maleic acid and monoethyl maleic acid. The above phrase also includes the homologs of maelic acid such as itaconic and mesaconic acid monoalkyl esters.  
           [0020]    For purposes of the present invention an amide modification of the cure-site monomer such as described in U.S. Pat. No. 4,412,043 (herein incorporated by reference) is to be considered equivalent to the monoalkyl ester of a 1,4-butene-dioic acid cure-site termonomer. As such vulcanizable elastomeric copolymers comprising an ethylene/methyl or ethyl (meth) acrylate/4-(dialkylamino)-4-oxo-2-butenoic acid copolymer and/or methyl or ethyl(meth) acrylate copolymer with 4-(dialkylamino)-4-oxo-2-butinoic acid termonomer and elastomeric compositions containing the same are felt to be amenable to the benefits associated with the process of the instant invention.  
           [0021]    Preparation of the copolymers or manufacture of AEM elastomer of the present invention will be conducted as disclosed by Greene et al. for the preparation of ethylene/acrylate/1,4-butenedioic acid ester terpolymer in U.S. Pat. Nos. 3,883,472 and 3,908,588 and cited references therein, all hereby incorporated herein by reference. In particular, the copolymerization can be carried out in a pressure reactor at temperatures ranging from 90° to 250° C., preferably 130° to 180° C., and pressures ranging from 1600 to 2200 atmospheres (160 to 220 MPa), preferably 1800 to 2100 atmospheres (182 to 210 MPa). The polymerization will be run as a continuous process wherein the total conversion of monomers to polymer is 5 to 18 weight percent, preferably 10 to 16 weight percent. Unreacted monomer may be recirculated. The melt index of the terpolymers of the present invention will range from 0.1 to 50 dg/min., preferably 0.5 to 20 dg/min. Similarly, the preparation of the copolymers for manufacture of ACM elastomer of the present invention will be conducted as disclosed by Greene in U.S. Pat. No. 4,026,851 and cited references therein (all hereby incorporated herein by reference), provided that the cure-site 1,4-butenedioic acid ester termonomer be present.  
           [0022]    The alkyl acrylates useful in their preparation typically are selected from methyl acrylate and ethyl acrylate when ethylene is a comonomer (i.e., AEM elastomer). In such cases the methyl acrylate is preferred and comprises from about 40 to 75 weight percent of the terpolymer, preferably from 50 to 70 weight percent. The monoalkyl ester of 1,4-butene-dioic acid function as the cure-site monomer and comprises from about 0.5 to 10.0 weight percent of the terpolymer. In the AEM type elastomer the ratio of comonomers can be selected to influence the final properties. Thus good low temperature properties are derived from the non-polar ethylene monomer, while the polar methyl acrylate monomer provides the oil and fluid resistance. Similarly the relative amount of cure-site monomer influences the degree of crosslinking and resulting rheological and mechanical properties. Similarly, in the case of the poly alkyl acrylate polymer system (i.e., ACM elastomer) the alkyl acrylates usually employed are methyl or ethyl acrylate, n-butyl acrylate and 2-methoxy ethyl acrylate along with 1,4-butene dioic acid ester cure-site monomer. Again, the respective relative amounts of each can be selected such as to influence the properties of the resulting elastomer as generally known in the art.  
           [0023]    The terpolymers of the present invention can also be compounded in non-black formulations and vulcanized in the presence of peroxide curing systems such as discussed by Greene in U.S. Pat. No. 3,904,588. In such systems, the polymers possess the added advantage of improved tensile properties.  
           [0024]    The vulcanizates of the present invention may also contain an antioxidant system based on a phosphorus ester antioxidant, a hindered phenolic antioxidant, an amine antioxidant, or a mixture of two or more of these compounds. The phosphorus ester compound can be, for example: tri(mixed mono- and dinonylphenyl) phosphite, tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphate, high molecular weight poly(phenolic phosphonates), and 6-(3,5-di-t-butyl-4-hydroxy)benzyl-6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide.  
           [0025]    The hindered phenolic compounds include, for example, the following: 4,4′-butylidenebis(6- t -butyl-m-cresol), 1,3,5-trimethyl-2,4,6-tris-(3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-dimethylamino- p -cresol, and 4,4′-thiobis-(3-methyl-6-t-butyl-phenol).  
           [0026]    Suitable amine antioxidants include, among others, the following: polymerized 2,2,4-trimethyl-1,2-dihydroquinoline; N-phenyl-N′-( p -toluenesulfonyl)-p-phenylenediamine; N,N′-di(β-naphthyl) p-phenylene diamine; low temperature reaction product of phenyl (β-naphthyl) amine and acetone; and 4,4′-bis(α, α-dimethylbenzyl)-diphenylamine.  
           [0027]    The proportion of the antioxidant compound in the vulcanizing composition is 0.1 to 5 parts per 100 parts of polymer, the preferred proportion being 0.5 to 2.5.  
           [0028]    The antioxidant improves the heat aging of the compositions. The antioxidant effect is usually quite low below the preferred range and impractically low below the broad range recited above. Above the higher limits, little additional improvement is observed, and there may be adverse effects on the state of cure.  
           [0029]    It is often desirable to add fillers to reduce cost and to improve mechanical properties. A typical vulcanized composition will usually contain about 10 to 40 volume percent of fillers, for example, carbon black, barium sulfate, magnesium silicate, or silica. Other conventional fillers can also be used. The preferred proportion of the fillers is 15 to 25 volume percent, and also depends on the reinforcing effect of the individual fillers. Below the lower limit, the improvement of tensile properties is quite low, while above the upper limit, the viscosity of the compound is too high and the hardness of the cured compound is too high. Also the percent elongation may be too low.  
           [0030]    The ingredients of the vulcanizable composition can be mixed in conventional equipment, such as a two-roll mill or a Banbury mixer. The vulcanizate may be formed and press-cured using conventional procedures at about 170° to 210° C. for about 3 to 60 minutes.  
           [0031]    The amount of aqueous HMDA solution used in this vulcanization process is about 0.06 to 0.30 mole of amino function per kilogram of polymer, preferably 0.12 to 0.22 mole per kilogram. Below the lower limit, the polymer tends to be undercured; while above the upper limit, the polymer tends to have impractical low elongation and poor heat aging resistance. It is to be noted that the aqueous HMDA, solution can include various branched isomers and homologs of HMDA, provided they too are water soluble. The vulcanization can also include various vulcanization accelerators belonging to the following classes:  
           [0032]    1. alkali metal salts of weak inorganic acids and alkali metal hydroxides;  
           [0033]    2. alkali metal salts of weak organic acids, alkali metal alcoholates and phenolates;  
           [0034]    3. quaternary ammonium and quaternary phosphonium hydroxides, alcoholates, phenolates, halides, and salts with weak acids;  
           [0035]    4. tertiary amines;  
           [0036]    5. guanidine, aryl- and alkylguanidines; and  
           [0037]    6. heterocyclic, tertiary amines.  
           [0038]    Examples of class (1) accelerators include sodium, potassium, and lithium hydroxides, phosphates, carbonates, bicarbonates, borates, hydrogen phosphates, and dihydrogen phosphates. The preferred accelerator is sodium hydroxide. The amount of a class (1) accelerator is 0.02 to 0.2 mole per kilogram of polymer; the preferred amount is 0.06 to 0.10 mole per kilogram.  
           [0039]    Representative class (2) accelerators are sodium methoxide, potassium stearate, sodium and potassium isopropoxides, potassium laurate, sodium or potassium phenoxides, benzoates, or salts of lower aliphatic acids, e.g., acetates, and formates. The preferred accelerator is potassium stearate. About 0.02 to 0.2 mole of the accelerator per kilogram of polymer is be used, the range of 0.06 to 0.10 mole per kilogram being preferred.  
           [0040]    Class (3) accelerators include, for example, tetrabutylammonium hydroxide, (C 8 H 17 -C 10 H 21 ) 3 (CH 3 )NCl (sold under the trade name, Aliquat 336, by General Mills, Chemical Div., Kankakee, Ill.), benzyltriphenylphosphonium chloride, tetrabutylammonium methoxide, and tetrabutylammonium stearate. The preferred compounds are tetrabutylammonium hydroxide and (C 8 H 17 -C 10 H 21 ) 3 (CH 3 )NCl. These accelerators are used at a level of 0.01 to 0.1 mole per kilogram of polymer, preferably 0.02 to 0.05 mole per kilogram of polymer.  
           [0041]    Tertiary amines representative of class (4) accelerators include triethylenediamine, N, N,N′,N′-tetramethyl-1,4-butanediamine, N,N,N′,N′-tetramethyl-2,6-diaminophenol, and N,N-dimethylaminoethanol. Triethylenediamine is the preferred accelerator in this class. About 0.01 to 0.1 mole of accelerator of this class per kilogram of polymer is used, the range of 0.02-0.05 mole per kilogram being preferred.  
           [0042]    Representative class (5) accelerators include tetramethylguanidine, tetraethylguanidine diphenylguanidine and di-ortho-tolyl guanidine. The level of application of class (5) accelerators is 0.01 to 0.12 mole per kilogram of polymer, preferably 0.02 to 0.09 mole per kilogram. The preffered accelerators are diphenylguanidine and di-ortho-tolyl guanidine  
           [0043]    Typical class (6) accelerators include imidazole, pyridine, quinoline, and N-phenylmorpholine. The preferred amine of this class is imidazole. Class (6) accelerators are used in amounts of 0.02 to 0.09 moles per kilogram of polymer.  
           [0044]    Two or more accelerators as defined herein may be used.  
           [0045]    The preferred accelerators are those of classes (4) and (5), above, because they have the minimum effect on compound scorch (premature curing at low temperature) and on the heat resistance of the vulcanizates.  
           [0046]    The following examples are presented to more fully demonstrate and further illustrate various aspects and features of the present invention. As such, the showings are intended to further illustrate the differences and advantages of the present invention but are not meant to be unduly limiting. 
       
    
    
     EXAMPLE 1  
       [0047]    For comparative evaluation a series of four different blends was prepared and tested. In each respective run a commercial grade of a random ethylene/methyl acrylate copolymer (41% by weight ethylene and 55% methyl acrylate) having 4 weight % methyl hydrogen maleate termonomer present as the cure-site monomer (sold under the tradename Vamac® by E. I. du Pont de Nemours and Company) was employed. Runs 1 and 3 employed 1.5 parts per weight HMDAC per 100 parts of the Vamac terpolymer as the curative agent. Runs 2 and 4 employed 1.55 parts by weight HMDA in the form of a 70/30 HMDA/water solution (pH≈12) as the curative agent. The 1.5 pph HMDAC and 1.55 pph of the 70/30 HMDA/H 2 O used the same molar amount of curative. Runs 1 and 2 also employed the standard level of 4 parts by weight per 100 parts of Vamac® of di-ortho-tolyl guanidine (DOTG) which is the accelerator for the cure while runs 3 and 4 did not use DOTG as the accelerator. Each run further included 60 parts by weight carbon black along with antioxidants and other additives. Details of the respective compositions and resulting data are presented in Table 1.  
         [0048]    The respective starting ingredients were blended on an 0° C. Banbury mixer using an upside down mix procedure and a dump temperature of 100° C. followed by further mixing on a two-roll mill at about 25° C. to achieve a homogeneous mixture. Vulcanized slabs of 75 mils (0.075 inch or 1.9 mm) inch thick were prepared by press-curing the blended mixtures for 5 minutes at 175° C. at a pressure of about 1,100 psig. The vulcanizates were then post-cured at 175° C. for four hours at ambient pressure.  
         [0049]    As seen in the data, the rheology of compounds 1 and 2 and the cured physicals for compounds 1 and 2 are essentially the same.  
         [0050]    Also the rheology of compounds 3 and 4 and the cured physicals for compounds 3 and 4 are essentially the same. DOTG makes significant improvements in the cure rate and the physical properties of the conventional HMDAC cure. The HMDA/H 2 O cure also benefits from using DOTG as an accelerator.  
                                                                     TABLE 1                           Properties of Compounds made with HMDA/H 2 O and also       with and without DOTG                Run Number                1   2   3   4                        Vamac   100   100   100   100       Carbon Black, N550   60   60   60   60       TP-759   10   10   10   10       StearicAcid   1.5   1.5   1.5   1.5       Vanfre VAM   1   1   1   1       Armeen 18D   0.5   0.5   0.5   0.5       Naugard 445   2   2   2   2       Diak #1   1.5       1.5       70 HMDA/30 H 2 O       1.55       1.55       DOTG   4   4   0   0       Total PPH   180.5   180.55   176.5   176.55       Rheology of Compounds       Mooney Viscosity       ML(1 + 4) @ 100° C.   36   36   43   43       Mooney Scorch - 121° C.       Minimum Viscosity - MU   13.2   13.1   15.5   15.4       t10 -- metricminutes   12.8   13.1   14.9   15.4       t18 -- metricminutes   18.8   19.7       MDR summary at 177, 1°       arc       ML, lbf-in   0.56   0.56   0.68   0.67       MH, Ibf-in   22.1   23.1   14   13.6       TS2, metric minutes   0.85   0.84   1.35   1.36       t50, m minutes   2.4   2.5   4.1   4.1       t90, m minutes   10.1   10.9   16.7   16.8       Physical properties       after cure       5 min in Press cure at       175° C.       4 Hours of Post cure at       175° C.       Hardness Shore A   65   64   67   66       Modulus at 100%   775   860   725   722       Elongation psi       Tensile Strength, psi   2322   2442   2343   2342       % Elongation   314   293   289   293       Compression set 168   23.5   22.3   44.9   48.2       hrs/150° C.       Age 1 week at 175 C. in air       Hardness Shore A   69   75   70   66       Modulus at 100%   893   975   694   636       elongation psi       Tensile strength psi   2371   2223   1882   1841       % Elongation   280   270   288   290       Change in Hardness, points   4   11   3   0       % change in 100% modulus   15.2%   13.4%   −4.3%   −11.9%        % change in tensile   2.1%   −9.0%   −193.7%   −21.4%       % change in elongation   −10.8%   −7.8%   −0.3%   −1.0%       Age 6 weeks at 150° C.       in air       Hardness Shore A   69   73   69   68       Modulus at 100%   884   936   802   740       elongation psi       Tensile strength psi   2168   2091   1937   1884       % Elongation   277   298   304   316       Change in Hardness, points   4   9   2   2       % change in 100% modulus   14.1%   8.8%   10.6%   2.5%       % change in tensile   −6.6%   −14.4%   −17.3%   −19.6%       % change in elongation   −11.8%   1.7%   5.2%   7.8%                  
 
       EXAMPLE 2  
       [0051]    In a manner analogous to that of Example 1, a series of six additional runs was performed and tested. Run 1 is the control. Runs 2 and 3 use a silica carrier for the HMDA/H 2 O solution. Runs 4 and 5 use carbon black as the carrier for the HMDA/H 2 O solution. Run 6 uses DOTG as the carrier.  
         [0052]    The concentrates were prepared by blending the HMDA/H 2 O solution with the dry silica, carbon black or DOTG. They were mixed in a beaker with a stirring rod. The silica compounds were still free flowing compounds after the addition of the HMDA/H 2 O and were very easy to add to the Banbury. The carbon black mixture used in run 4 (2 to 1 ratio of black to HMDA/H 2 O) was relatively easy to add to the Banbury. However, the carbon black mixture used in run 5 (1 to 1 ratio of black to HMDA/H 2 O was difficult to add to the mixture because it was a “pasty” consistency. The concentrate used in run 6 was a blend of 4 parts of DOTG and 1.55 parts of HMDA/H 2 O (standard cure level). This concentrate was also “pasty” and difficult to feed to the Banbury. The resulting data are presented in Table 2.  
                                             TABLE 2                           Properties of Compounds made with HMDA/H 2 0 Deposited       on Additive Before Blending With Polymer            Run Number   1   2   3   4   5   6               Vamac   100   100   100   100   100   100       Black, N550   60   56.85   58.45   56.85   58.45   60       TP-759   10   10   10   10   10   10       Stearic Acid   1.5   1.5   1.5   1.5   1.5   1.5       Vanfre VAM   1   1   1   1   1   1       Armeen 18D   0.5   0.5   0.5   0.5   0.5   0.5       Naugard 445   2   2   2   2   2   2       Diak #1   1.5       33 HMDA/H2O, 67 Silica (A)       4.7       50 HMDA/H2O, 50 Silica (B)           3.1       33 HMDA/H2O, 67 Black               4.7       (C)       50 HMDA/H2O, 50 Black                   3.1       (D)       27.9 HMDA/H2O, 72.1                       5.55       DOTG (E)       DOTG   4   4   4   4   4   0       Total PPH   180.5   180.55   180.55   180.55   180.55   180.55       Rheology of Compounds       Viscosity, ML (1 + 4) @ 100° C.   35.2   35.2   34.5   33.4   34.8   31.5       Mooney Scorch - 121° C.       Minimum Viscosity - MU   11.8   12.2   11.6   11.4   11.3   10.7       t3 -- metric minutes   7.7   7.7   7.8   7.9   7.9   7.7       t10 -- metric minutes   12.8   13.1   13.3   13.4   13.3   13.1       t18 -- metric minutes   18.8   20.3   20.3   19.8   20.2   18.8       MDR summary at 177, 1° arc       ML, lbf-in   0.52   0.54   0.52   0.51   0.54   0.51       MH, lbf-in   22.1   23.1   23.5   21.3   24.2   20.5       tS1, metric minutes   0.65   0.64   0.65   0.65   0.66   0.64       tS2, metric minutes   0.85   0.84   0.86   0.86   0.86   0.84       t10, m minutes   0.88   0.88   0.91   0.91   0.93   0.84       t50, m minutes   2.4   2.5   2.6   2.6   2.7   2.3       t90, m minutes   9.3   11.5   11.2   10.7   11   10.2       Slope, (0.9*MH-ML + 2)/(t90-   2.53   2.09   2.19   2.10   2.29   2.13       tS2)       Slope, (0.5*MH-ML + 2)/(t50-   13.8   13.4   13.0   11.9   12.6   13.7       tS2)       Physical properties after cure       5 min in Press cure at       175° C.       4 Hours of Post cure at       175° C.       Hardness, Shore A   67   66   67   69   68   67       Modulus at 100%   826   813   869   877   893   748       Elongation, psi       Tensile Strength, psi   2293   2323   2421   2397   2439   2385       % Elongation   294   286   281   276   279   319       Die C tear, pli   204   207   210   203   186   195       Compression set 168   20.3   21.1   19.1   17.4   20.9   20.4       hrs/150° C.                  
 
       EXAMPLE 3  
       [0053]    In a manner analogous to and using the same procedures of Example 1, a series of five additional blends using two different polyacrylate (ACM) type elastomers (i.e., AR-12 and AR-14, commercially available from Zeon Corporation, Japan) known to be cross-linkable with the HMDAC/DOTG cure system was prepared and tested. Run 1 was performed using HMDAC/DOTG curative system and runs 2 and 4 used HMDA/water plus DOTG curative system and run 5 HMDA/water deposited/dispersed on precipitated silica plus DOTG. Run 3 did not employ a diamine curative agent. The resulting data presented in Table 3 establish that the aqueous HMDA curative agent of the instant invention is operative for polyacrylate (ACM) type elastomers.  
                                         TABLE 3                           Properties of Compounds made with HMDA/H 2 0 and/or       HMDA/H 2 0 Deposited on Additive Before Blending With Polyacrylate       (ACM) Polymer            RUN NUMBER   1   2   3   4   5               AR 12   100   100           100       AR 14           100   100       Carbon Black, N550   55   55   55   55   55       Stearic Acid   1   1   1   1   1       Vanfre VAM   0.5   0.5   0.5   0.5   0.5       Armeen 18D   0.5   0.5   0.5   0.5   0.5       Naugard 445   2   2   2   2   2       Struktol WB 222   2   2   2   2   2       Diak #1   0.6       0.0       70 HMDA/30 H2O       0.62       0.62       Concentrate*                   0.96       DOTG   2   2   2   2   2       Total PHR   163.6   163.62   163.0   163.62   163.96       Rheology of Compounds       Mooney Viscosity       ML (1 + 4) @ 100° C.   46.6   45.5   38.7   46.2   46.3       Mooney Scorch - 121° C.       Initial Visc -- MU -- 1 min   27.8   27   24.5   26.2   26.5       preheat       Minimum Viscosity -- MU   22.8   21.7   18.2   23.2   21.7       t3 -- metric minutes   6.76   7.01       4.43   6.75       t10 -- metric minutes   9   9.43       6.07   9.23       t18 -- metric minutes   10.2   10.6       7.27   10.58       MDR summary at 177, 1° arc       30 minutes       ML, lbf-in   2.26   2.28   2.19   2.6   2.28       MH, lbf-in   15   15.4       13.4   15       tS1, metric minutes   0.48   0.46       0.53   0.47       tS2, metric minutes   0.64   0.62       0.83   0.63       t10, m minutes   0.52   0.51       0.55   0.51       t50, m minutes   1.72   1.7       2.91   1.68       t90, m minutes   8.32   8.62       14.4   8.54       Slope, (0.9*MH-(ML + 2))/   1.20   1.20       0.55   1.17       (t90-tS2)       Slope, (0.5*MH-(ML + 2))/   3.0   3.2       1.0   3.1       (t50-tS2)       Physical properties after cure       5 min in Press cure at 175° C.       4 Hours of Post cure at       175° C.       Hardness   61.5   59.9   34.5   61.3   59.6       Modulus at 100% Elongation   498   544   52   861   549       Tensile Strength, psi   1461   1516       1423   1395       % Elongation   232   219       138   209       Die C tear, pli   106   101   31   73   113       Compression set 168   12.8   12.4   90.7   21.5   14.6       hrs/150° C.                          
 
         [0054]    Having thus described and exemplified the invention with a certain degree of particularity, it should be appreciated that the following claims are not to be so limited but are to be afforded a scope commensurate with the wording of each element of the claim and equivalents thereof.