Patent Publication Number: US-4839412-A

Title: Ethylene copolymer compositions

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a continuation-in-part of application Ser. No. 935,708, filed Nov. 25, 1986, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     Ethylene polymers, i.e., homopolymers and copolymers, are easily molded or extruded into shaped articles. Additives are frequently used to improve the strength of the polymers. Efforts have also been made to improve the flame and smoke resistance of such polymers by adding various flame and smoke retardants. However, many such retardants have a negative effect on mechanical properties, such as strength properties, and it is desirable to discover combinations of strength-enhancing additives and flame and smoke retardants that provide a good balance between strength properties and flame and smoke retardancy. This invention is directed to such combinations. 
     SUMMARY OF THE INVENTION 
     In its broad aspect, the compositions of this invention comprise: 
     (a) 20-100 parts of an ethylene polymer matrix comprising at least one thermoplastic ethylene copolymer of ethylene and at least one comonomer selected from vinyl acetate, esters of methacrylic acid or esters of acrylic acid; 
     (b) 10-80 parts, preferably 10-40 parts, of a copolymer selected from the class consisting of (i) an ethylene/propylene/diene copolymer grafted with 0.1 to 5 weight % anhydride functionality or (ii) at least one polyolefin grafted with 0.1 to 5 weight % anhydride functionality, or (iii) a mixture of both; and 
     (c) 75-130 parts, preferably 90-110, per 100 parts of polymeric components present, of magnesium hydroxide or alumina trihydrate, or a mixture of both. 
     (d) 0-80 parts of polyethylene, preferably medium density or linear low density polyethylene; 
     provided that the combined parts of components (a) and (d) is at least 80 parts. 
     When polyethylene is present, the preferred amount of component (a) present will be 30-40 parts. 
     In another embodiment, 3-20 parts of at least one ionomeric copolymer of ethylene and at least one alpha,beta-ethylenically unsaturated carboxylic acid of 3-6 carbons, such as methacrylic or acrylic acid can be present with components (a)-(c) or with components (a)-(c) that contain polyethylene. 
     Still another optional feature in any of the foregoing embodiments is the additional presence of an ethylene/propylene or ethylene/propylene/diene copolymer in amounts of up to 50 parts. 
     In still other embodiments, any one or more of the following copolymers may be present: a copolymer of ethylene/methacrylic or acrylic acid, a copolymer of ethylene/vinyl acetate grafted with anhydride functionality, a copolymer of ethylene and acrylic or methacylic acid esters of saturated aliphic alcohols grafted with anhydride functionality. 
     To add flame retardancy, magnesium hydroxide or alumina trihydrate, or a mixture of the two, is added. 
     To reduce low temperature brittleness, an ethylene/propylene/diene copolymer grafted with anhydride functionality or at least one polyolefin grafted with anhydride functionality, or a mixture of both, is added. 
     In addition, it was also found that an ionomeric copolymer of ethylene and a lower alkyl (meth)acrylic acid neutralized with metallic cations also provides resistance to low temperature brittleness, and these polymers can be used also. 
     It was also discovered that if an ethylene/propylene rubbery copolymer or ethylene/propylene/diene copolymer is added, the elongation properties of the compositions are enhanced. 
     DESCRIPTION OF THE INVENTION 
     The foregoing compositions are useful as flame retardant articles, or as insulation or protective coatings around electrical wire or cable. 
     The thermoplastic ethylene copolymer matrix has been found to more readily accept the magnesium hydroxide or alumina hydrate because of its polarity, and improves extrudability of the compositions. The ethylene copolymers are preferably copolymers of ethylene and vinyl acetate, but numerous other monomers may be used in place of vinyl acetate. For example, copolymers of ethylene with acrylic, methacrylic or methacrylic acid esters of saturated aliphatic alcohols can be used. The copolymers of ethylene and esters of acrylic acid and methanol or ethanol advantageously have a comonomer content of 9-49 wt. %. 
     It has been found that, preferably, polyethylene should be a component, and that preferably use of a medium density (i.e., maximum density 0.940 (ASTM D-1248, Type II)) polyethylene or linear low density polyethylene (maximum density 0.925) and use of a narrow molecular weight range polyethylene produces better mechanical properties in a wire or cable coating. Such polyethylenes are preferred. 
     The grafted polymers of component b may be grafted with alpha,beta-ethylenically unsaturated carboxylic acids or anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and the like. Maleic anhydride is a preferred graft material for both the polyolefin polymers and the ethylene/propylene/diene (EPDM) copolymer. The amount of grafting, i.e., anhydride functionality, will be about 0.1 to 5 weight %. The grafted copolymers impart good resistance to low temperature (e.g., about -40° or below, such as down to -60° C.) brittleness. They also increase yield elongation, and yield and break tensile strength. The polyolefin polymers can be polyethylene or copolymers of ethylene and higher olefins (C 3  -C 6 ) such as propylene and/or butylene. Thus, they include both crystalline and elastomeric polymers, and can be employed with one another herein. 
     By the term &#34;anhydride functionality&#34; is meant the group ##STR1## The concentration of anhydride in the graft polymer may be measured by infrared spectroscopy of hot pressed films. 
     The graft copolymers may be prepared as described in Flexman, U.S. Pat. No. 4,026,067 or Caywood, U.S. Pat. No. 3,884,882 and U.S. Pat. No. 4,010,223. The diene component of the graft copolymer is nonconjugated and includes linear aliphatic dienes of at least six carbon atoms which have one terminal double bond and one internal double bond, and cyclic dienes wherein one or both of the carbon-to-carbon double bonds are part of a carbocyclic ring. Of the linear dienes, 1,4-hexadiene are especially preferred. 
     Classes of cyclic dienes useful for graft formation include alkylidene bicycloalkenes, alkenyl bicycloalkenes, bicycloalkadienes, and alkenyl cycloalkenes. 
     The magnesium hydroxide [Mg(OH) 2  ] and alumina trihydrate (Al 2  O 3 .3H 2  O) are used to impart smoke and flame retardation to the compositions. These materials may be surface treated to aid in compatibilizing them with the matrix polymer or polymers. 
     It has also been found that presence of an ethylenic ionomeric copolymer also aids in reducing brittleness at low temperatures. The ionomeric copolymer employed as a component of the blends of this invention is preferably a copolymer of ethylene and alpha,beta-ethylenically unsaturated carboxylic acids containing 3-6 carbon atoms. The alpha-olefin content of the copolymer is preferably at least 70 mole percent, based on copolymer. The carboxylic acid groups are randomly distributed over the copolymer molecules and can be 10-90%, preferably 40-80%, neutralized by metal cations distributed over the carboxylic acid groups of the copolymer. The metal cations can be derived from any metals, but preferably are Zn, Na, Mg or Ca. Illustrative of the alpha,beta-ethylenically unsaturated carboxylic acids useful in the preparation of said ionic copolymer are acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of itaconic acid, maleic acid, and fumaric acid. Other monomers can, of course, be incorporated in the copolymer. 
     Finally, it has been found that if an ethylene/propylene (E/P) copolymer or ethylene/propylene/diene (EPDM) copolymer is added, the composition will have better elongation properties. Examples of EPDM copolymers are those ungrafted copolymers described previously. 
     Desired additives such as antioxidants, neutralizers, ultraviolet absorbers, antistatic agents, pigments, lubricants, slip agents, viscosity modifiers or the like can be added to the composition of this invention. 
     The components of the compositions of this invention can be blended by any of the conventional blending methods such as a roll mill, a Banbury mixer, a monoaxial extruder, biaxial extruder or the like. The compositions can be formed by any of the conventional methods such as compression molding, extrusion coating, injection molding, calendering, or the like. 
    
    
     EXAMPLES 
     The Examples are shown in tabular form. The blends described in the tables were prepared by blending the indicated ingredients on a Banbury mixer or two-roll mill. Compounding on a two-mill roll was carried out on a 4&#34;×8&#34; (10.2 cm×20.3 cm) two-roll mill heated with 165° C. steam. All of the polymer components were added to the mill, melted and mixed. Flame retardants and other additives were then added. When incorporation was complete and a band formed on the mill, the component was cut and folded six times. After cigar rolling and rebanding six times, the compound was sheeted off the mill. Compression molding of these samples was carried out on a 8&#34;×8&#34; (20.3 cm×20.3 cm) stainless steel mold. The bottom plate containing two 3&#34;×6&#34;×0.075 (7.6 cm×15.2 cm×0.2 cm) cavities was 3/4&#34; (1.9 cm) thick; the solid top plate was 3/8&#34; (0.95 cm) thick. The mold was heated to 177° C. in a Pasedena Hydraulic Press. 7.6 cm×15.2  cm×0.23 cm sheets of compound were placed in the preheated mold, using 2 mil &#34;Kapton&#34; polyimide film sprayed with Freekote 33 mold release as a mold liner. The closed mold was placed in the press and heated for 10 minutes with the platens closed to touch pressure. The pressure was then increased to 30,000 pounds force on the 10.2 cm ram as read from the pressure gauge of the press for 1 minute. The pressure was momentarily released and then returned to 30,000 pounds (133 kN) force for 2 minutes. The closed mold was then removed from the heated press and placed in a water-cooled press. When the mold reached room temperature, the samples were removed from the mold. 
     When a Banbury mixer was used, the chamber was heated to 150°-160° F. (66°-71° C.) with the cooling water off. The polymers and then flame retardants were added. Mixing to 250° F.-275° F. (166°-177° C.) with the cooling water off was carried out, followed by sweeping. The cooling water was turned on after sweeping. 
     With the cooling water on, mixing was carried out until a temperature of 330°-350° F. was reached and then the contents were dumped from the chamber. The contents were cut and folded on a mill and sheeted for molding. The sheeted compositions were pressed between sheets of &#34;Mylar&#34; or aluminum foil. Mold temperatures of 177° C. (350° F.) were used. The contents were held at contact pressure for 10 minutes. The contents were held at full pressure for 1 minute; the pressure was momentarily released then quickly reestablished and held for an additional two minutes. The sheet was removed and cooled quickly on a cold bench top. 
     Each example and comparison in the Tables consists of 100 parts by weight matrix polymer. This matrix polymer consists of an ethylene copolymer, as indicated, at 20-100 parts, and polyethylene, 0-80 parts. Varying amounts of other ingredients were added, expressed as parts per 100 parts of the above resin ingredients. 
     Samples for testing were compression molded according to the procedure outlined above and tests performed according to the procedures outlined in the Table below. 
     Where blanks appear in the Table property data, the property value was not determined. 
     
         ______________________________________                                    
Table of Test Methods                                                     
Test               Procedure                                              
______________________________________                                    
Yield Strength     ASTM D-638, D-412                                      
Elongation at Yield                                                       
                   ASTM D-638, D-412                                      
Tensile Strength   ASTM D-638, D-412                                      
Elongation at Break                                                       
                   ASTM D-638, D-412                                      
Low Temp. Brittle- ASTM D-746                                             
ness (LTB)                                                                
Limiting Oxygen    ASTM D-862                                             
Index (LOI)*                                                              
______________________________________                                    
 *Measured to nearest 1%.                                                 
 
    
     
         ______________________________________                                    
TABLE OF COMPOSITION                                                      
______________________________________                                    
EVA 1       28 wt. % VA, MI 3                                             
EVA 2       18 wt. % VA, MI 0.7                                           
EVA 3       9.5 wt. % VA, MI 0.8                                          
EEA         15 wt. % ethyl acrylate, MI 0.5                               
E/nBA       30 wt. % n-butyl acrylate                                     
HDPE        high density polyethylene                                     
MDPE        medium density polyethylene (Type II,                         
            ASTM D-1248)                                                  
LLDPE       linear low density polyethylene (Type I,                      
            ASTM D-1248)                                                  
Graft Copolymer 1                                                         
            Graft of maleic anhydride (about                              
            1.7 wt. %) onto EPDM rubber, MI                               
            about 3                                                       
Graft Copolymer 2                                                         
            Graft of maleic anhydride (about                              
            0.4 wt. %) onto polyethylene, MI                              
            about 13                                                      
Graft Copolymer 3                                                         
            Graft of maleic anhydride (about                              
            1.0 wt. %) onto polyethylene, MI                              
            about 12                                                      
Ionomer 1   Copolymer of ethylene with 15 wt. %                           
            methacrylic acid, 58% neutralized with                        
            zinc, MI 0.7                                                  
Ionomer 2   Copolymer of ethylene with 10 wt. %                           
            isobutyl acrylate and 10 wt. %                                
            methacrylic acid, 74% neutralized with                        
            Zn, MI 1.0                                                    
EPDM 1      Terpolymer of ethylene with 30 wt. %                          
            propylene and 3.7% hexadiene, Mooney                          
            viscosity, about 44, ASTM D-16467                             
EPDM 2      Same as EPDM 1, except Mooney viscosity                       
            is about 60                                                   
Melamine Resin                                                            
            &#34;Cyrez&#34; 963 from American Cyanamid                            
            Company                                                       
Antioxidant &#34;Irganox&#34; 1010, which is from Ciba Geigy                      
______________________________________                                    
 EVA = ethylene/vinyl acetate copolymer                                   
 MI = melt index                                                          
 EEA = ethylene/ethyl acrylate copolymer                                  
 E/nBA = ethylene/nbutyl acrylate copolymer                               
 EPDM rubber = ethylene/propylene/1,4hexadiene copolymer                  
 
    
     Examples 1 and 2 and Comparative Examples C1 to C4, Table 1, show that when EVA, LLDPE, graft copolymer, and Mg(OH) 2  are present, the same exhibits superior LOI (at 125 parts Mg(OH) 2 ) to samples in which any of these components is missing. At higher Mg(OH) 2  levels, as shown in Examples 3 and 4, Table 2, better than expected LOI&#39;s are obtained even in the absence of the polyethylene. The letter L before the LOI value means &#34;less than&#34;. Other properties are good, as seen in the Table. 
     Examples 5-9, Table 3, show that EVA containing 28 wt. % VA is superior to EVA containing only 18% or 9.5% VA. The EVA of higher vinyl acetate content gives compositions with generally higher elongation at break, when compared with the corresponding examples at lower VA levels. The EVA&#39;s of lower VA content still give acceptable properties for purposes of this invention. 
     Examples 10-13, Table 4, show that the presence of some polyethylene based graft copolymer gives significantly improved elongation at break compared to samples which use only the graft copolymer based on ethylene/propylene/diene rubber, at the same total levels of graft copolymer. In these preferred cases, the properties are even further improved when the polyethylene is LLDPE rather than MDPE 
     Examples 14-17, Table 5, show the advantage of replacing part of the graft copolymer with ethylene/propylene/diene rubber. While Example 14 already shows an excellent balance of properties, replacing progressively more and more of the graft copolymer with EPDM rubber results in still improved elongation, while maintaining tensile strength, and with only slight deterioration of low temperature properties. However, when high levels of EPDM rubber are added, at the expense of graft copolymer Examples 18 and 19 and Comparative Example C5, low temperature properties are compromised. Example 20, however, shows that at 10 parts graft copolymer, adequate low temperature properties can be obtained, provided that the amount of EPDM rubber is limited to about 10 parts. 
     Examples 21-29, Table 6, further illustrate the invention with compositions of EVA or EEA, LLDPE or MDPE, graft copolymer, and magnesium hydroxide or alumina trihydrate flame retardant. All samples give an acceptable spectrum of properties. 
     Examples 30-40, Table 7, further illustrate the invention with compositions which also include EPDM rubber. 
     Examples 41-47, Table 8, and Examples 48-54, Table 9, are similar to the examples in Tables 7 and 6, respectively, except that a small amount of ionomeric copolymer is also present. Examples 52-54 show the effect of adding ionomeric copolymer in increasing amounts. It is apparent from these examples that the presence of the ionomeric copolymer tends to give improved low temperature properties and tensile strength. 
     Comparative Examples C6 through C9, in Table 10, show that when the graft copolymer is left out of the composition, the elongation properties are greatly reduced. If EPDM rubber is present Comparative Examples C8 and C9, the elongation may be improved somewhat, but the low temperature properties are not improved. 
     Comparative Examples C-10 to C-12, Table 11, and C-3 and C-4, Table 1, show that when the ethylene copolymer is absent, the balance of properties is not maximized. (In Examples C-10 to C-12, the amount of  copolymer plus polyethylene is less than 100 parts. The amounts of other ingredients have not been normalized.) 
     The Tables follow. 
     
                       TABLE 1                                                     
______________________________________                                    
        1,    C1,     2,      C2,  C3,   C4                               
______________________________________                                    
EVA #1    40              100   40                                        
LLDPE     60      100           60   100   100                            
Graft Copol 1                                                             
          30      30      30         40                                   
Graft Copol 2                                                             
          10      10      10                                              
EPDM 1                                     40                             
Mg(OH).sub.2                                                              
          125     125     125   89   125   125                            
Antioxidant                                                               
          1       1       1     0.7  1     1                              
Tensile Str,                                                              
          1780    1925    1835  1437 1812  1651                           
PSI                                                                       
Tensile Str,                                                              
          12.27   13.27   12.65 9.91 12.49 11.38                          
MPa                                                                       
% Retention**                                                             
          96      98      98    96   102   90                             
% Elong. at                                                               
          376     414     503   570  307   677                            
Break                                                                     
% Retention**                                                             
          98      89      92    48   88    101                            
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
          1       *       *     *    *     *                              
-60° C.                                                            
          5                                                               
Limiting O.sub.2                                                          
          31      24      24    26   25    24                             
Index                                                                     
______________________________________                                    
 *Values uncertain  machine was not working properly.                     
 **% Retention means retention of the property after aging the sample at  
 100° C. for 48 hours in a circulating air oven.                   
 
    
     
                       TABLE 2                                                     
______________________________________                                    
Example:            3,        4                                           
______________________________________                                    
EVA #1              100       100                                         
Graft Copolymer 1   30        30                                          
Graft Copolymer 2   10        10                                          
Mg(OH).sub.2        145       135                                         
Antioxidant         1         1                                           
Tensile Str, PSI    1589      1559                                        
Tensile Str, MPa    10.96     10.75                                       
% Retention         93        97                                          
% Elong. @ Break    439       422                                         
% Retention         80        87                                          
Brittleness:                                                              
Failures/10 @                                                             
-45° C.      1         2                                           
-60° C.      10        10                                          
Limiting O.sub.2 Index                                                    
                    32        29                                          
______________________________________                                    
 
    
     
                       TABLE 3                                                     
______________________________________                                    
         5,     6,      7*,      8,    9                                  
______________________________________                                    
EVA #1     40       40                                                    
EVA #2                      40     40                                     
EVA #3                                   40                               
MDPE       60               60           60                               
LLDPE               60             60                                     
Graft Co-  30       30      30     30    30                               
polymer 1                                                                 
Graft Co-  10       10      10     10    10                               
polymer 2                                                                 
Mg(OH).sub.2                                                              
           110      110     110    110   110                              
Antioxidant                                                               
           1        1       1      1                                      
Tensile Str,                                                              
           2123     2071    1973   2386  1834                             
PSI                                                                       
Tensile Str,                                                              
           14.64    14.28   13.60  16.45 12.65                            
MPa                                                                       
% Retention                                                               
           105      98      105    106   103                              
% Elong. @ 325      440     364    308   290                              
Break                                                                     
% Retention                                                               
           76       92      87     88    70                               
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
           1        0       0      0     0                                
-60° C.                                                            
           0        0       2      0     4                                
Limiting O.sub.2    27      26                                            
Index                                                                     
______________________________________                                    
 *Duplications of this Example resulted in Elongation to Break values of  
 347, 280, 387, 352, 425, 260. Other property values were in the range of 
 those of Example 6.                                                      
 
    
     
                       TABLE 4                                                     
______________________________________                                    
             10,   11,      12,     13                                    
______________________________________                                    
EVA #2         40      40       40    40                                  
MDPE           60      60                                                 
LLDPE                           60    60                                  
Graft Co-      30      40       30    40                                  
polymer 1                                                                 
Graft Co-      10               10                                        
polymer 2                                                                 
Mg(OH).sub.2   110     110      110   110                                 
Antioxidant    1       1        1     1                                   
Tensile Str,   2017    2223     2195  2120                                
PSI                                                                       
Tensile Str,   13.91   15.33    15.13 14.62                               
MPa                                                                       
% Retention    102     110      100   121                                 
% Elong. @ Break                                                          
               387     229      407   205                                 
% Retention    83      90       86    114                                 
Brittleness:                                                              
Failures/10 @                                                             
-45° C. 1       0        0     0                                   
-60° C. 4       1        0     0                                   
Limiting O.sub.2                                                          
               26               26                                        
Index                                                                     
______________________________________                                    
 
    
     
                       TABLE 5                                                     
______________________________________                                    
       14   15,    16     17   18,  C5   19,  20                          
______________________________________                                    
EVA #1   40     40     40   40   40   40   30                             
EVA #2                                          40                        
LLDPE    60     60     60   60   60   60   70                             
MDPE                                            60                        
Graft Co-                                                                 
         30     20     15   10             10   10                        
polymer 1                                                                 
Graft Co-                                                                 
         10     10     10   10   10                                       
polymer 2                                                                 
EPDM 1          10     15   20   30   40   20   10                        
Mg(OH).sub.2                                                              
         110    110    110  110  110  110  130  110                       
Antioxidant                                                               
         1      1      1    1    1    1    1    1                         
Tensile Str,                                                              
         1992   1992   1788 1977 2076 1853 1724 1715                      
PSI                                                                       
Tensile Str,                                                              
         13.73  13.73  12.33                                              
                            13.63                                         
                                 14.31     11.89                          
                                                11.83                     
MPa                                                                       
% Retention                                                               
         104    96     108  99   96   87   90                             
% Elong. @                                                                
         453    567    535  664  764  754  643  506                       
Break                                                                     
% Retention                                                               
         92     85     105  97   96   93   90                             
Brittleness:                                                              
Failures/                                                                 
10 @                                                                      
-45° C.                                                            
         1      0      0    3    8    10   9    6                         
-60° C.                                                            
         4      7      7    10   10   10   10   10                        
______________________________________                                    
 
    
     
                       TABLE 6                                                     
______________________________________                                    
Example:      21,      22,      23,    24                                 
______________________________________                                    
EVA #1        40       30       40     40                                 
EVA #2                                                                    
EEA                                                                       
LLDPE         60       70       60     60                                 
MDPE                                                                      
Graft Co-     30       30       30     30                                 
polymer 1                                                                 
Graft Co-     10                10                                        
polymer 2                                                                 
MoO.sub.3                                                                 
Melamine Resin                                                            
              5                                                           
Mg(OH).sub.2  125      130      140    130                                
Antioxidant   1        1        1      1                                  
Tensile Str,  1848     1939     1805   1806                               
PSI                                                                       
Tensile Str,  12.74    13.37    12.45  12.45                              
MPa                                                                       
% Retention   99       97       95                                        
% Elong. @    495      437      354    372                                
Break                                                                     
% Retention   95       83       90                                        
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
              1        0        *      1                                  
-60° C.                                                            
              4        6        *      9                                  
Limiting O.sub.2                                                          
              30       L28      29     29                                 
Index                                                                     
______________________________________                                    
Example:     25,     26,     27    28,   29                               
______________________________________                                    
EVA #1               40                                                   
EVA #2                       40    40    40                               
EEA          60                                                           
MDPE                         60    60                                     
LLDPE        40      60                  60                               
Graft Co-    30      30      30    30    30                               
polymer 1                                                                 
Graft Co-    10      10            10    10                               
polymer 2                                                                 
MoO.sub.3                                10                               
Melamine Resin       5                                                    
Mg(OH).sub.2 110     110           55    124                              
Alumina                      110   55    20                               
Trihydrate                                                                
Antioxidant  1       1       1           1                                
Tensile Str, 1773    1872    1660  2143  2218                             
PSI                                                                       
Tensile Str, 12.22   12.91   11.45 14.78 15.30                            
MPa                                                                       
% Retention  95      104           113   106                              
% Elong. @   321     411     356   308   195                              
Break                                                                     
% Retention  72      82            89    89                               
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
             1       0       0     1     2                                
-60° C.                                                            
             1       0       2     0     5                                
Limiting O.sub.2                                                          
             L28     29                  28                               
Index                                                                     
______________________________________                                    
 *Values uncertain  machine was not working properly.                     
 
    
     
                                           TABLE 7                                 
__________________________________________________________________________
Example:                                                                  
        30,                                                               
           31 32,                                                         
                 33**                                                     
                    34,                                                   
                       35,                                                
                          36,                                             
                             37,                                          
                                38 39,                                    
                                      40                                  
__________________________________________________________________________
EVA #1  40    30 40 40 30 40 40 40 30 40                                  
EEA        40                                                             
LLDPE   60 60 70 60 60 70 60 60 60 70 60                                  
Graft   15 20 10 20 30 15 20 20 10 20 10                                  
Copol 1                                                                   
Graft   10 10 15 15 10 15 10 10 10 15 15                                  
Copol 2                                                                   
EPDM 1  15 10 20 15 10 20 10 10 20 15 20                                  
Mg(OH).sub.2                                                              
        135                                                               
           135                                                            
              145                                                         
                 150                                                      
                    150                                                   
                       150                                                
                          110                                             
                             154                                          
                                135                                       
                                   150                                    
                                      145                                 
Antioxidant                                                               
        1  1  1  1  1  1  1  1  1  1  1                                   
Tensile Str,                                                              
        1834                                                              
           1780                                                           
              1800                                                        
                 1772                                                     
                    1762                                                  
                       1511                                               
                          1979                                            
                             1403                                         
                                1700                                      
                                   1646                                   
                                      1658                                
PSI                                                                       
Tensile Str,                                                              
        12.65                                                             
           12.27                                                          
              12.41                                                       
                 12.22                                                    
                    12.15                                                 
                       10.42                                              
                          13.65                                           
                             9.67                                         
                                11.72                                     
                                   11.35                                  
                                      11.43                               
MPa                                                                       
% Retention                                                               
        93 90 93    94    104                                             
                             112                                          
                                95 94                                     
% Elong. @                                                                
        552                                                               
           435                                                            
              599                                                         
                 482                                                      
                    418                                                   
                       446                                                
                          550                                             
                             309                                          
                                599                                       
                                   349                                    
                                      549                                 
Break                                                                     
% Retention                                                               
        94 77 89    85    97 123                                          
                                91 103                                    
Brittleness:                                                              
Failures/10 @                                                             
-45&#39; C. 1  2  8  2  *  *  0  10 5  1  7                                   
-60&#39; C. 10 8  9  10       4  10 10 8  10                                  
Limiting O.sub.2                                                          
        30 L28                                                            
              29 29 30 31 L28                                             
                             L28                                          
                                L28                                       
                                   L28                                    
                                      L28                                 
Index                                                                     
__________________________________________________________________________
 *Brittleness Brittleness not accurately recorded due to machine          
 malfunction.                                                             
 **When When graft copolymer 2 is replaced with an ethylene/methacrylic   
 acid copolymer of MI 3, good results are obtained.                       
 
    
     
                       TABLE 8                                                     
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Example:   41,    42,    43,  44   45,  46,  47                           
______________________________________                                    
EVA #1     40     40     40   40   50   40   30                           
LLDPE      60     60     60   60   50   60   70                           
Graft Co-  10     10     20   20   15   15   35                           
polymer 1                                                                 
Graft Co-  10     10     10   10        10                                
polymer 2                                                                 
Graft Co-                          10                                     
polymer 3                                                                 
Ionomer 1  3             3    3    3    3    5                            
Ionomer 2         3                                                       
EPDM 1     20     20     10   10   15   15   10                           
Melamine Resin                                                            
MoO.sub.3  4      4           4    4    4    4                            
Mg(OH).sub.2                                                              
           135    135    135  135  135  135  100                          
Antioxidant                                                               
           1      1      1    1    1    1    0.2                          
Carbon Black                                 2                            
Tensile Str,                                                              
           1624   1496   1844 1635 1424 1589 2400                         
PSI                                                                       
Tensile Str,                                                              
           11.20  10.31  12.71                                            
                              11.27                                       
                                   9.82 10.96                             
                                             16.55                        
MPa                                                                       
% Retention                                                               
           100    103    90   99                                          
% Elong. @ 502    527    503  375  434  502  392                          
Break                                                                     
% Retention                                                               
           106    79     87   99                                          
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
           3             1    2              0                            
-60° C.                                                            
           10            7    10             1                            
Limiting O.sub.2                                                          
           31     30     29   30   29   29                                
Index                                                                     
______________________________________                                    
 
    
     
                       TABLE 9                                                     
______________________________________                                    
Example:   48,    49,    50   51   52,  53,  54                           
______________________________________                                    
EVA #1     40                 40                                          
EVA #2            40     40        40   40   40                           
MDPE                     60        60   60   60                           
LLDPE      60     60          60                                          
Graft Co-  20     30     30   30   20   20   20                           
polymer 1                                                                 
Graft Co-         10     10        20   20   20                           
polymer 2                                                                 
Ionomer 1  5      5           3                                           
Ionomer 2                5              3    10                           
MoO.sub.3                     4                                           
Mg(OH).sub.2                                                              
           110    152    110  145  110  110  110                          
Antioxidant                                                               
           1      1.4    1    1    1                                      
Carbon Black                                                              
           2      2.8                                                     
Tensile Str,                                                              
           2560   2700   1870 2088 1908 2149 2175                         
PSI                                                                       
Tensile Str,                                                              
           17.65  18.62  12.89                                            
                              14.40                                       
                                   13.16                                  
                                        14.82                             
                                             15.00                        
MPa                                                                       
% Retention                        106  99   101                          
% Elong. @ 223    199    395  193  287  415  337                          
Break                                                                     
% Retention                        90   59   77                           
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                                                            
           0      0      1    0    2    0    1                            
-60° C.                                                            
           0      0      8    3    7    0    1                            
LOI                           32                                          
______________________________________                                    
 
    
     
                       TABLE 10                                                    
______________________________________                                    
Example:       C6,      C7,     C8,    C9                                 
______________________________________                                    
EVA #2                          40     33                                 
EVA #3         40                                                         
EEA                                                                       
E/nBA                   40                                                
MDPE           60       60      60                                        
LLDPE                                  67                                 
EPDM 2                          20     11                                 
Mg(OH).sub.2   110      110     110    110                                
Antioxidant    1        1       1      1                                  
Carbon Black   2        2       2                                         
Tensile Str,   2440     1600    1520   1510                               
PSI                                                                       
Tensile Str,   16.82    11.03   10.48  10.41                              
MPa                                                                       
% Retention                                                               
% Elong. @     6        8       514    72                                 
Break                                                                     
% Retention                                                               
Brittleness:                                                              
Failures/10 @                                                             
-45° C.                  10     10                                 
-60° C.                  10                                        
Limiting O.sub.2 Index                                                    
______________________________________                                    
 
    
     
                       TABLE 11                                                    
______________________________________                                    
Example:       C10,      C11,      C12                                    
______________________________________                                    
MDPE           60        50                                               
HDPE                               60                                     
Graft Copol 1  10        10                                               
EPDM 1                             40                                     
EPDM 2         30        40                                               
Mg(OH).sub.2   110       110       110                                    
Antioxidant    1         1         1                                      
Carbon Black   2         2         2                                      
Tensile Str,   1480      1210      1500                                   
PSI                                                                       
Tensile Str,   10.20     8.34      10.34                                  
MPa                                                                       
% Elong. @     199       394       8                                      
Break                                                                     
Brittleness:                                                              
Failures/10 @  10        10                                               
-45° C.                                                            
______________________________________                                    
 
    
     
                       TABLE 12                                                    
______________________________________                                    
Example:        55,       56,      57                                     
______________________________________                                    
EVA #1          40        40       40                                     
LLDPE           60        60       60                                     
Graft Co-       20        20       20                                     
Polymer 1                                                                 
Graft Copolymer of                                                        
                15        --       --                                     
Maleic Anhydride                                                          
(1.1 wt %) on EVA                                                         
(18 wt % VA) MI 2.6                                                       
Graft Copolymer of                                                        
                --        15       --                                     
Maleic Anhydride                                                          
(0.9 wt %) on EVA                                                         
(9 wt % EVA) MI 0.8                                                       
E/MAA (9%), MI 3                                                          
                --        --       15                                     
Antioxidant     1         1        1                                      
Carbon Black    --        --       3.4                                    
Mg(OH).sub.2    135       150      150                                    
Tensile Str. PSI                                                          
                1688.0    1750.0   1846.0                                 
Tensile Str. MPa                                                          
                11.6      12.1     12.7                                   
% Elong. @ Break                                                          
                405.0     475.0    233.0                                  
Brittleness:                                                              
Failures/10 @ -45 C.               0.0                                    
Failures/10 @ -60 C.               0.0                                    
Limiting O.sub.2 Index                                                    
                29.0      30.0     27.0                                   
______________________________________