Epoxy resin containing a combination of high and low molecular weight polyoxyalkylene polyamine curing agents
BACKGROUND OF THE INVENTION 
     This application is related to abandoned application Ser. No. 952,017 filed Oct. 16, 1978. 
     1. Field of the Invention 
     This invention relates to curable epoxy resins having increased adhesive strength; and more particularly to epoxy resins cured with a combination of certain high and low molecular weight polyoxyalkylene polyamines. 
     2. Related Publications 
     The adhesion and other properties of epoxy resins have been enhanced by the addition of certain additives. In the abandoned application mentioned above, U.S. Pat. Nos. 3,645,969 and 3,306,809 were cited as prior art. These references contain epoxy resin formulations containing polyoxyalkylene polyamines in various combinations. It is believed that the particular combination claimed herein is different from and not obvious in view of the materials claimed in these patents. 
     Applicant is the inventor or co-inventor on the following applications concerning epoxy resin compositions in which the adhesion or other properties of epoxy resins were enhanced by addition of certain materials. Of particular interest are those disclosed in U.S. Pat. Nos. 4,115,360; 4,141,885; 4,115,361; 4,146,700 and 4,169,177. 
     Additional patents concerning epoxy resins with enhanced properties wherein Applicant, Harold George Waddill, is an inventor or co-inventor are U.S. Pat. Nos. 4,002,598; 4,011,281; 4,110,309; 4,110,310; 4,110,313; 4,113,697; 4,116,938; 4,139,524; 4,146,701; 4,147,857; 4,178,426; 4,178,427; 4,187,367 and 4,219,638. 
     H. G. Waddill, National SAMPE Tech. Conf. Series, Vol. 11, 282-294 (1979) discusses the adhesive improving additive bis(carbamoyl) derivative of a polyoxyalkylene polyamine. 
     SUMMARY OF THE INVENTION 
     An epoxy resin composition having superior adhesion properties and being the cured reaction product of a curable admixture which comprises a vicinal polyepoxide having an epoxide equivalency of greater than 1.8 and a curing amount of a combination of polyamines comprising about 15 wt.% or less of a polyoxyalkylene polyamine having an amine functionality greater than 2 and a molecular weight of about 5,000 or more and about 85 wt.% or more of a polyoxyalkylene polyamine of functionality 2 or greater and a molecular weight of about 200-450. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     According to the instant inventive concept, blends of a polyepoxide; a combination of about 85 wt.% or more, preferably 90 wt.% or more, of certain polyoxyalkylene polyamines having a molecular weight of less than about 450 and 15 wt.% or less, preferably 10 wt.% or less, of a polyoxyalkylene polyamine of greater than two primary amine functionality and a molecular weight of about 5,000 and above and, optionally, an accelerator and other standard ingredients are thoroughly admixed and cured in accordance with conventional methods to provide cured epoxy resins having unexpectedly superior adhesive strength. 
     The amine terminated polyether resins (polyoxyalkylene polyamines) useful in this invention are polyether resins made from an appropriate initiator to which lower alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof are added with the resulting hydroxyl terminated polyol then being aminated. When two or more oxides are used, they may be present as random mixtures or as blocks of one or the other polyether. In the amination step it is highly desirable that the terminal hydroxyl groups in the polyol be essentially all secondary hydroxyl groups for ease of amination. Normally, the amination step does not completely replace all of the hydroxyl groups. However, the majority of hydroxyl groups are replaced by amine groups. Therefore, the amine terminated polyether resins useful in this invention have greater than 50% of their active hydrogens in the form of amine hydrogens. If ethylene oxide is used it is desirable to cap the hydroxyl terminated polyol with a small amount of higher alkylene oxide to ensure that the terminal hydroxyl groups are essentially all secondary hydroxyl groups. The polyols so prepared are then reductively aminated as outlined, for example, in U.S. Pat. No. 3,654,370 and other prior art techniques. 
     According to one embodiment, a curable epoxy resin containing a glycidyl ether of 4,4&#39;-isopropylidene bisphenol and a curing amount of a combination of polyamines comprising about 15 wt.% or less of a polyoxyalkylene polyamine, an amine functionality greater than 2 and a molecular weight of about 5,000 or more and about 85 wt.% or more of a polyoxyalkylene polyamine of functionality 2 or greater and a molecular weight of about 200-450. 
     Preferably, the high molecular weight polyoxyalkylene polyamines have the structure ##STR1## wherein Y is hydrogen, a methyl radical or an ethyl radical, Z is a hydrocarbon radical of 3-5 carbon atoms, n is a number sufficient to impart a molecular weight of about 5,000 or more to the molecule and r is a number greater than 2. 
     Especially preferred is a high molecular weight polyoxyalkylene polyamine having the general structure: ##STR2## wherein x+y+z are numbers having a total such that the molecular weight of said polyoxyalkylene polyamine is about 5,000 or more. 
     Preferably, the low molecular weight polyoxyalkylene polyamines have the structure ##STR3## wherein Y is hydrogen, a methyl radical or an ethyl radical, Z is a hydrocarbon radical of 2-5 carbon atoms, n is a number sufficient to impart a molecular weight of about 200-450 to the molecular and r is a number 2 or greater. 
     Especially preferred are low molecular weight polyoxyalkylene polyamines of the general structure 
     
         H.sub.2 NCH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.w NH.sub.2 
    
     wherein w is a finite number such that the molecular weight of said polyoxyalkylene polyamine is from about 200 to about 300 or the general structure ##STR4## wherein x+y+z are finite numbers having a total such that the molecular weight of said polyoxyalkylene polyamine is about 400. 
     Generally, the amine cured vicinal polyepoxide containing compositions are organic materials having an average of at least 1.8 reactive 1,2-epoxy groups per molecule. These polyepoxide materials can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may be substituted if desired with other substituents besides the epoxy groups; e.g., hydroxyl groups, ether radicals, aromatic halogen atoms and the like. 
     Preferred polyepoxides are those of glycidyl ethers prepared by epoxidizing the corresponding allyl ethers or reacting, by known procedures, a molar excess of epichlorohydrin and an aromatic polyhydroxy compound; i.e., isopropylidene bisphenol, novolak, resorcinol, etc. The epoxy derivatives of methylene or isopropylidene bisphenols are especially preferred. 
     A widely used class of polyepoxides which are useful according to the instant invention includes the resinous epoxy polyethers obtained by reacting an epihalohydrin, such as epichlorohydrin, and the like, with either a polyhydric phenol or a polyhydric alcohol. An illustration, but by no means exhaustive, listing of suitable dihydric phenols includes 4,4&#39;-isopropylidene bisphenol, 2,4&#39;-dihydroxydiphenylethylmethane, 3,3&#39;-dihydroxydiphenyldiethylmethane, 3,4&#39;dihydroxydiphenylmethylpropylmethane, 2,3&#39;-dihydroxydiphenylethylphenylmethane, 4,4&#39;-dihydroxydiphenylpropylphenylmethane, 4,4&#39;-dihydroxydiphenylbutylphenylmethane, 2,2&#39;-dihydroxydiphenylditolylmethane, 4,4&#39;-dihydroxydiphenyltolylmethylmethane and the like. Other polyhydric phenols which may also be co-reacted with an epihalohydrin to provide these epoxy polyethers are such compounds as resorcinol, hydroquinone, substituted hydroquinones; e.g., methylhydroquinone, and the like. 
     Among the polyhydric alcohols which can be co-reacted with an epihalohydrin to provide these resinous epoxy polyethers are such compounds as ethylene glycol, propylene glycols, butylene glycols, pentane diols, bis(4-hydroxycyclohexyl)dimethylmethane, 4,4-dimethylolbenzene, glycerol, 1,2,6-hexanetriol, trimethylolpropane, manniatol, sorbitol, erythritol, pentaerythritol, their dimers, trimers and higher polymers; e.g., polyethylene glycols, polypropylene glycols, triglycerol, dipentaerythritol and the like, polyallyl alcohol, polyhydric thioethers, such as 2,2&#39;-, 3,3&#39;-tetrahydroxydipropylsulfide and the like, mercapto alcohols such as monothioglycerol, dithioglycerol, and the like, polyhydric alcohol partial esters, such as monostearin, pentaerythritol monoacetate, and the like, and halogenated polyhydric alcohols such as the monochlorohydrins of glycerol, sorbitol, pentaerythritol and the like. 
     Another class of polymeric polyepoxides which can be amine cured and are in accordance with the instant invention includes the epoxy novolak resins obtained by reacting, preferably in the presence of a basic catalyst; e.g., sodium or potassium hydroxide, an epihalohydrin, such as epichlorohydrin, with the resinous condensate of an aldehyde; e.g., formaldehyde, and either a monohydric phenol; e.g., phenol itself, or a polyhydric phenol. Further details concerning the nature and preparation of these epoxy novolak resins can be obtained in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Co., New York, 1967. 
     Other polyepoxides known to those skilled in the art may be useful in this invention. 
     Optionally, the epoxy resin formulations of the instant invention can include an &#34;accelerator&#34; to speed the amine cure of the epoxy resin, especially at ambient temperatures. In several applications, such acceleration is beneficial, especially when an epoxy resin is used as an adhesive in flammable environment, thus making elevated temperature cure inconvenient or even hazardous. Lee, H. and Neville, K., Handbook of Epoxy Resins, pp. 7-14 describes the use of certain amine-containing compounds as epoxy curing agent-accelerators. 
     Many accelerators are known in the art which can be utilized in accordance with the instant invention. Examples include salts of phenols, salicyclic acids, amine salts of fatty acids, such as those disclosed in U.S. Pat. No. 2,681,901, and tertiary amines such as those disclosed in U.S. Pat. No. 2,839,480. Preferred accelerators in accordance with the instant invention are disclosed in U.S. Pat. Nos. 3,875,072 and 4,195,153. 
     It will further be realized that various conveniently employed additives can be admixed with the polyepoxide containing composition of the instant invention prior to final cure. For example, in certain instances it may be desired to add minor amounts of other polyalkyleneamine co-catalysts as herein described, or hardeners along with various other accelerators and curing agent systems well known in the art. 
     Additionally, conventional pigments, dyes, fillers, flame retarding agents and the like which are compatible; natural or synthetic resins can be added. 
     Furthermore, although not preferred, known solvents for polyepoxide materials such as toluene, benzene, xylene, dioxane, ethylene glycol monomethyl ether and the like can be used. The polyepoxide resins containing the additives of the instant invention can be used in any of the above applications for which polyepoxides are customarily used. One outstanding feature of the instant composition resides in the fact that they are opaque upon curing and give a smooth, white lustrous surface which may be of particular benefit for certain molding and casting operations. The compositions of the instant invention can be used as impregnants, surface coatings, encapsulating compositions, laminants and, particularly and most importantly, as adhesive for bonding metallic elements or structures permanently together. 
    
    
     The following examples illustrate the nature of the instant invention but are not intended to be limitative thereof. 
     EXAMPLE 1 
     A polyoxyalkylene polyamine above a certain molecular size is necessary in order to develop enhanced adhesive properties when used in combination with a polyoxyalkylene polyamine of less than about 450. Those polyglycol amines of molecular weight less than 4,000 apparently are soluble in epoxy systems containing the low molecular weight polyoxyalkylene polyamine and, therefore, do not phase separate. Phase separation is necessary, apparently, for enhancement of adhesion properties. This may be shown as follows: 
     
         ______________________________________                                    
Formulation    A      B      C    D    E    F                             
______________________________________                                    
Epoxy resin.sup.1                                                         
               100     100    100 100  100  100                           
JEFFAMINE ® D-230                                                     
                32    31.2   30.9 30.5 29.9 29.1                          
JEFFAMINE D-2000                                                          
               --     1.5    3.5  7.6  12.8 19.4                          
Accelerator 399                                                           
                10     10     10  10   10   10                            
Adhesive Properties,                                                      
Cured 7 days, at 25° C.                                            
Tensile shear strength, psi                                               
               900    1100   1300 1200 1800 2600                          
T-peel strength, pli                                                      
               2.2    2.8    2.0  1.2  1.9  2.8                           
Appearance     Clear; no phase separation                                 
______________________________________                                    
Formulation     G      H         I    J                                   
______________________________________                                    
Epoxy resin      100   100        100  100                                
JEFFAMINE D-230 31.2   31.0      30.5 29.9                                
JEFFAMINE T-3000                                                          
                1.6    3.4       7.6  12.8                                
Accelerator 399  10     10        10   10                                 
Adhesive Properties,                                                      
Cured 7 days at 25° C.                                             
Tensile shear strength, psi                                               
                1100   900       1350 1600                                
T-peel strength, pli                                                      
                2.7    3.1       2.5   3.2                                
Appearance      Clear; no phase separation                                
______________________________________                                    
Formulation    K      L      M       N                                    
______________________________________                                    
Epoxy resin     100    100    100     100                                 
JEFFAMINE D-230                                                           
               31.2   31.1   30.9    30.5                                 
JEFFAMINE D-4000                                                          
               1.7    3.5    7.7     13.1                                 
Accelerator 399                                                           
                10     10     10      10                                  
Adhesive Properties,                                                      
Cured, 7 days at 25° C.                                            
Tensile shear strength, psi                                               
               1000   1100   1700    3200                                 
T-peel strength, pli                                                      
               2.7    1.9    3.3      6.6                                 
Appearance     Clear, no Partial   Dense                                  
               phase     phase     whitening;                             
               separation                                                 
                         separation                                       
                                   phase                                  
                         cloudiness                                       
                                   separation                             
______________________________________                                    
Formulation    O         P      Q    R    S                               
______________________________________                                    
Epoxy resin     100       100    100  100  100                            
JEFFAMINE D-230                                                           
               31.3      31.2   30.9 30.6 30.3                            
JEFFAMINE T-5000                                                          
               1.6       3.4    7.8  13.2 20.1                            
Accelerator 399                                                           
                10        10     10   10   10                             
Adhesive Properties,                                                      
Cured 7 days at 25° C.                                             
Tensile shear strength, psi                                               
               1400      2100   3500 3400 3300                            
T-peel strength, pli                                                      
               0.9       2.3    3.4   9.6 13.9                            
Appearance     Partial   Dense whitening;                                 
               phase     phase separation                                 
               separation                                                 
               cloudiness                                                 
______________________________________                                    
Formulation     T      U         V    W                                   
______________________________________                                    
Epoxy resin      100    100       100  100                                
JEFFAMINE D-230 31.3   31.2      31.0 30.8                                
Amin. THANOL ®  G-6500                                                
                1.6    3.5       7.8  13.2                                
Adhesive Properties,                                                      
Cured 7 days at 25° C.                                             
Tensile shear strength, psi                                               
                1200   2250      2500 2850                                
T-peel strength, pli                                                      
                1.1    2.0       6.2   8.0                                
Appearance      Dense whitening; phase separation                         
______________________________________                                    
 .sup.1 A diglycidyl ether of Bisphenol A of EEW ˜ 185. This resin i
 used in all formulations in this application.                            
 
    
     EXAMPLE 2 
     
         __________________________________________________________________________
Curing with JEFFAMINE ® D-230 at 2 Hrs at 80° C.               
and Then 3 Hrs at 125° C.                                          
Formulations                                                              
           A  B  C  D  E  F  G  H  J                                      
__________________________________________________________________________
EPON 828   100                                                            
              100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100                                             
                             100                                          
                                100                                       
                                   100                                    
JEFFAMINE D-230                                                           
           32.0                                                           
              31.2                                                        
                 30.9                                                     
                    30.5                                                  
                       29.9                                               
                          32.0                                            
                             31.1                                         
                                30.9                                      
                                   30.6                                   
JEFFAMINE D-2000                                                          
           -- 1.5                                                         
                 3.5                                                      
                    7.6                                                   
                       12.8                                               
wt. %      0.0                                                            
              1.1                                                         
                 2.6                                                      
                    5.5                                                   
                       9.0                                                
JEFFAMINE T-5000          -- 3.5                                          
                                7.8                                       
                                   13.2                                   
wt. %                     -- 2.6                                          
                                5.6                                       
                                   9.2                                    
__________________________________________________________________________
 Curing with JEFFAMINE D-230 at an Elevated Temperature                   
             T-Peel Strength (pli) at Concentration                       
             Level* (wt. %) of Additive                                   
Additive     0.0  1.1                                                     
                    2.6 5.5                                               
                          5.6  9.0                                        
                                 9.2                                      
__________________________________________________________________________
JEFFAMINE D-2000                                                          
             1.5  2.6                                                     
                    2.2 2.4                                               
                          --   2.4                                        
                                 --                                       
JEFFAMINE T-5000                                                          
             1.5  --                                                      
                    5.8 --                                                
                          10.3 --                                         
                                 14.1                                     
__________________________________________________________________________
             Tensile Shear Strength, psi, at Concen-                      
             tration Level (wt. %) of Additive                            
Additive     0.0 1.1                                                      
                    2.6 5.5                                               
                            5.6                                           
                               9.0                                        
                                  9.2                                     
__________________________________________________________________________
JEFFAMINE D-2000                                                          
             3850                                                         
                 4150                                                     
                    4200                                                  
                        3700                                              
                           --  4400                                       
                                  --                                      
JEFFAMINE T-5000                                                          
             3850                                                         
                 -- 4500   4300                                           
                               -- 4000                                    
__________________________________________________________________________
 *Wt. % is based on total system.                                         
 
    
     JEFFAMINE T-5000 is considerably more effective in enhancement of adhesion properties when added in small amounts to epoxy system cured with JEFFAMINE D-230 than is JEFFAMINE D-2000. 
     EXAMPLE 3 
     
         __________________________________________________________________________
Formulation   A  B  C  D  E  F   G  H  J  K  L  M                         
__________________________________________________________________________
EPON ® 828                                                            
              100                                                         
                 100                                                      
                    100                                                   
                       100                                                
                          100                                             
                             100 100                                      
                                    100                                   
                                       100                                
                                          100                             
                                             100                          
                                                100                       
JEFFAMINE D-230                                                           
              32.0                                                        
                 31.2                                                     
                    31.0                                                  
                       30.5                                               
                          29.9                                            
                             29.1                                         
                                 32.0                                     
                                    31.2                                  
                                       31.0                               
                                          30.5                            
                                             29.9                         
                                                32.0                      
JEFFAMINE D-2000                                                          
              -- 1.6                                                      
                    3.5                                                   
                       7.8                                                
                          13.1                                            
                             19.9                                         
                 1.6%                                                     
                    2.4%                                                  
                       5.2%                                               
                          8.5%                                            
                             12.5%                                        
JEFFAMINE T-3000                 -- 1.6                                   
                                       3.5                                
                                          7.8                             
                                             13.1                         
                                    1.1%                                  
                                       2.4%                               
                                          5.2%                            
                                             8.5%                         
JEFFAMINE T-5000                                --                        
Amin. THANOL ® G-6500                                                 
Accelerator 399                                                           
              10 10 10 10 10 10  10 10 10 10 10 10                        
__________________________________________________________________________
Formulation   N   P  Q  R  S   T  U  V   W  X  Y                          
__________________________________________________________________________
EPON ® 828                                                            
              100 100                                                     
                     100                                                  
                        100                                               
                           100 100                                        
                                  100                                     
                                     100 100                              
                                            100                           
                                               100                        
JEFFAMINE D-230                                                           
              31.3                                                        
                  31.2                                                    
                     30.9                                                 
                        30.6                                              
                           30.1                                           
                               32.0                                       
                                  31.3                                    
                                     31.2                                 
                                         31.0                             
                                            30.8                          
                                               30.5                       
JEFFAMINE D-2000                                                          
JEFFAMINE T-3000                                                          
JEFFAMINE T-5000                                                          
              1.6 3.4                                                     
                     7.8                                                  
                        13.2                                              
                           20.1                                           
              1.1%                                                        
                  2.4%                                                    
                     5.2%                                                 
                        8.5%                                              
                           12.5%                                          
Amin. THANOL ® G-6500      -- 1.6                                     
                                     3.4 7.7                              
                                            13.1                          
                                               20.0                       
                                  1.1%                                    
                                     2.4%                                 
                                         5.2%                             
                                            8.5%                          
                                               12.5%                      
Accelerator 399                                                           
              10  10 10 10 10  10 10 10  10 10 10                         
__________________________________________________________________________
             Rheometric Impact Properties on Curing                       
             With JEFFAMINE D-230: Ambient                                
             Temperature With Accelerator                                 
                        Total Energy (E) in Lbs at Concentration          
                        Level (wt. %) of Additive                         
             Additive   0 1.1                                             
                            2.4                                           
                              5.2                                         
                                8.5                                       
                                  12.5                                    
__________________________________________________________________________
             JEFFAMINE D-2000                                             
                        4 1 2 2 53                                        
                                  143                                     
             JEFFAMINE T-3000                                             
                        4 5 6 3 85                                        
                                  --                                      
             JEFFAMINE T-5000                                             
                        4 4 8 4 22                                        
                                  130                                     
             Amine G-6500                                                 
                        4 9 2 9 6 16                                      
__________________________________________________________________________
 
    
     Results were somewhat erratic but indicate improved impact properties with low concentrations of higher molecular weight polyoxyalkylene polyamines. 
     Examples 4 through 7 demonstrate the applicability of the invention to other low molecular weight polyoxyalkylene polyamines. 
     EXAMPLE 4 
     
         ______________________________________                                    
Formulation                                                               
          70A    70B      70C    70D    70E                               
______________________________________                                    
EPON ® 828                                                            
          100    100      100    100    100                               
JEFFA-    42.7   42.5     42.0   41.6   40.8                              
MINE ® T-403                                                          
JEFFA-    --     1.4 (1%) 4.4 (3%)                                        
                                 7.5 (5%)                                 
                                        12.2 (8%)                         
MINE D-2000                                                               
Adhesive                                                                  
Properties.sup.1                                                          
Tensile Shear                                                             
          3800   3700     3750   4200   4300                              
strength                                                                  
T-peel strength,                                                          
          2.2    2.3      2.4    2.2    2.7                               
pli                                                                       
______________________________________                                    
 .sup.1 Cured 1 hour at 125° C.                                    
 
    
     EXAMPLE 5 
     
         ______________________________________                                    
Formulation                                                               
           70A    66C       66D     47C                                   
______________________________________                                    
EPON 828   100    100       100     100                                   
JEFFAMINE  42.7   42.4      41.9    41.4                                  
T-403                                                                     
JEFFAMINE  --     4.7 (3.2%)                                              
                            10.5 (6.9%)                                   
                                    17.7 (11.1%)                          
T-5000                                                                    
Adhesive                                                                  
Properties                                                                
Tensile shear                                                             
           3800   4200      4200    3600                                  
strength, psi                                                             
T-peel     2.2    11.2      6.1     11.4                                  
strength, pli                                                             
______________________________________                                    
 
    
     EXAMPLE 6 
     
         ______________________________________                                    
Formulation                                                               
           68A    69A       48A     48B                                   
______________________________________                                    
EPON 828   100    100       100     100                                   
JEFFA-     56.8   56.2      55.4    54.4                                  
MINE D-400                                                                
JEFFA-     --     6.2 (3.8%)                                              
                            13.9 (8.2%)                                   
                                    23.4 (13.2%)                          
MINE T-5000                                                               
Adhesive                                                                  
Properties.sup.1                                                          
Tensile shear                                                             
           3000   3700      2600    2300                                  
strength, psi                                                             
T-peel     3.4    3.2       14.8    14.7                                  
strength, pli                                                             
______________________________________                                    
 .sup.1 Cured 1 hour at 125° C.                                    
 
    
     EXAMPLE 7 
     
         ______________________________________                                    
Formulation                                                               
          68A    68B      68C    68D    68E                               
______________________________________                                    
EPON 828  100    100      100    100    100                               
JEFFA-    56.8   56.4     55.8   55.1   54.0                              
MINE D-400                                                                
JEFFA-    --     1.6 (1%) 4.8 (3%)                                        
                                 8.1 (5%)                                 
                                        13.4 (8%)                         
MINE D-2000                                                               
Adhesive                                                                  
Properties.sup.1                                                          
Tensile shear                                                             
          4000   4050     3900   2900   2600                              
strength, psi                                                             
T-peel strength,                                                          
          3.4    2.9      3.2    3.6    4.5                               
pli                                                                       
______________________________________                                    
 .sup.1 Cured 1 hour at 125° C.                                    
 
    
     
         ______________________________________                                    
GLOSSARY                                                                  
______________________________________                                    
Accelerator 399                                                           
               a mixture of aminoethylpiperazine                          
               (5%), piperazine (25%) and tri-                            
               ethanolamine (70%). A product of                           
               Texaco Chemical Co.                                        
JEFFAMINE ® D-2000                                                    
               a polyoxyalkylene diamine of about                         
               2000 molecular weight. A product                           
               of Texaco Chemical Co.                                     
JEFFAMINE T-3000                                                          
               a polyoxyalkylene triamine of about                        
               3000 molecular weight. A product                           
               of Texaco Chemical Co.                                     
JEFFAMINE D-4000                                                          
               a polyoxyalkylene diamine of about                         
               4000 molecular weight. A product                           
               of Texaco Chemical Co.                                     
JEFFAMINE T-5000                                                          
               a polyoxyalkylene triamine of about                        
               5000 molecular weight. A product of                        
               Texaco Chemical Co.                                        
Aminated G-6500                                                           
               a polyoxyalkylene triamine of about                        
               6500 molecular weight. A product                           
               of Texaco Chemical Co.                                     
JEFFAMINE D-230                                                           
               a polyoxyalkylene diamine of about                         
               230 molecular weight. A product                            
               of Texaco Chemical Co.                                     
JEFFAMINE D-400                                                           
               a polyoxyalkylene diamine of about                         
               400 molecular weight. A product                            
               of Texaco Chemical Co.                                     
JEFFAMINE T-403                                                           
               a polyoxyalkylene triamine of about                        
               400 molecular weight. A product                            
               of Texaco Chemical Co.                                     
EPON ® 828 Liquid epoxy resin - a diglycidyl                          
               ether of Bisphenol A of EEW ˜ 185. - EEW is epoxy    
               equivalent weight.                                         
______________________________________