Curable liquid polysulfide polymer based sealants
BACKGROUND OF THE INVENTION 
     The use of curable liquid polysulfide polymer based sealant compositions because of their durability and imperviousness to various agents which are known to affect other caulking compounds has long been practiced. For all their desirable properties, however, it has long been desired to improve the ability of these sealants to adhere more firmly to certain substrates such as glass in the presence of moisture and ultra-violet light. Improved adherence would allow more extensive use of these compounds in the fabrication of insulating glass units permitting the use of &#34;formed in place&#34; instead of &#34;preformed&#34; gaskets. The present invention relates to additives which supply greater adhesion to glass to the polysulfide polymer based caulks in which they are employed, to composltions formulated employing these additives, to processes for their preparation and use, and the articles of manufacture formed thereby. 
     SUMMARY OF THE INVENTION 
     The invention provides a curable liquid polysulfide polymer based sealant which comprises: 
     A. a curable liquid polysulfide polymer; 
     B. a polybutyl polymer, a polybutene polymer, or a mixture thereof as an adhesive additive; and 
     C. an oil absorbent filler. 
     The tangible embodiments of this composition aspect of the invention possess the inherent applied use characteristics of being useable as sealant compositions having greater adhesion to glass after exposure to moisture and ultra-violet light. In addition those embodiments in which the polybutyl or polybutene polymer is not incorporated as a water based latex show improved water vapor transmission characteristics. 
     The invention further provides a process for the enhancement of adhesiveness to glass in the presence of moisture and ultra-violet light of a curable liquid polysulfide polymer based sealant composition which comprises the admixture with the uncured sealant, in an amount effective to insure adequate bonding of the cured sealant to a substrate, of a polybutyl polymer, a polybutene polymer or a mixture thereof; and an oil absorbent filler. 
     The invention further provides a cured rubbery like polymer, prepared by admixing a curable liquid polysulfide polymer, a curing amount of an oxidative curing agent, a polybutyl polymer, a polybutene polymer latex, or a mixture thereof in an amount effective to insure adequate bonding of said cured rubber like polymer to a substrate, and an oil absorbent filler. 
     The tangible embodiments of this aspect of the invention possess the inherent applied use characteristics of being sealants improved adhesiveness to glass. 
     The invention further provides an improved article of manufacture requiring a sealant on at least one surface thereof; wherein the improvement comprises said sealant being a curable liquid polysulfide polymer based sealant composition, containing as an adhesive additive, a polybutyl polymer latex, a polybutene polymer latex, or a mixture thereof, and an oil absorbent filler. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The liquid polysulfide polymer based sealant compositions of the invention may be readily prepared. The admixture of the liquid polysulfide polymer and the polybutyl polymer, polybutene polymer or a mixture thereof, and the oil absorbent filler is readily accomplished by standard techniques. Other optional ingredients such as plasticizers or U.V. stabilizers and the like may be incorporated at the same time. The sealants may be packaged as two-part sealants, that is, the polysulfide-polybutyl or polybutene containing portion of the sealant will make up one package, and an oxidative curing agent may be separately packaged and the two mixed just prior to use. If a water emulsion of the adhesive additive is employed to formulate the sealant, a one package format may be employed. The oxidative curing agent may then be incorporated at the time as the rest of the formulation is mixed and packaged. 
     The polysulfide liquid polymers suitable for use in the present invention are the standard polysulfide polymers of commerce ranging in molecular weight from about 500 to 7500, those about 1000 to about 4000 particularly those of 4000 molecular weight are specially preferred. These polysulfide polymers are described in U.S. Pat. No. 2,466,963 and they may be represented by the formula HS--(RSS) n  --RSH where R is a hydrocarbon, oxahydrocarbon or thiahydrocarbon radical such as the ethyl formal radical (--CH 2  --CH 2  --O--CH 2  --O--CH 2  --CH 2  --) n , the butyl formal radical (--CH 2  --CH 2  --CH 2  --CH 2  --O--CH 2  --O--CH 2  --CH 2  --CH 2  --CH 2  --) n , the ethylether diradical (--CH 2  --CH 2  --O--CH 2  --CH 2  --) n  and the butylether diradical (--CH 2  --CH 2  --CH 2  --CH 2  --O--CH 2  --CH 2  --CH 2  --CH 2  --) n  and n will vary from about 4 to about 23. If desired, in addition to these thio terminated liquid polythio polymers some polysulfide polymers wherein the terminal thio groups have been inverted by treatment with heat and acid to hydroxyl terminals may be admixed. 
     The polybutyl and polybutene polymers suitable for use in the invention are any of the solid latices or liquid butyl or butene polymers which are commonly available. They may either be fully cured or have a minor fraction of sites available for further curing. The proportion of sites available for further curing may range from about 1% to about 10% preferably about 4%. The polymers may either be liquids, solids dispersed in the form of a latex or liquids dispersed in a solvent as an emulsion. Particularly suitable are such products as Polyvis 2000 SH manufactured by Cosden Oil and Chemical Company, a liquid 100% solid non-curing polybutene, Butyl LM 430 manufactured by Exxon-Enjay Chemical Company a 3 to 1 emulsion in toluene of a 4% curing site butyl liquid polymer, and Exxon BP 100 Butyl latex, a non-curing 63% solid emulsion in water. They may conveniently be incorporated in qualities ranging from about 1 to 200 parts more preferably 10 to 100 parts per 100 parts of polysulfide liquid polymer in the formulation. 
     The oil absorbent filler, used in the present invention to provide capatibility between the polysulfide polymer and the polybutyl or polybutene polymer, may be selected from among any non-acidic oil absorbent material commonly employed as fillers in compositions of this general type. Typical materials suitable for this purpose are: calcium carbonate, magnesium oxide, kaolin, other non-acidic clays, titanium dioxide and carbon black. A particular filler is not especially critical as long as one is employed, and will typically be selected by one skilled in the art to impart the particular combination of stiffness, workability, lack of slump in the uncured state, as well as hardness and curing time desired for the particular application. In addition other additives assisting in the control of the above as well as other properties may be incorporated. Typical of such additives are plasticizers such as chlorinated paraffins, sag control agents derived from castor oil derivatives, phthalate ester plasticizers which also serve to control fogging, pH control agents such as tridimethylaminophenol, and adhesion enhancers such as γ -glycidoxypropyltrimethoxysilane. Conventional curing agents may be incorporated directly into the sealant formulation when it is formulated with a water based butyl or butene latex to form a one package sealant. Typical of these sealants are MnO 2  and PbO 2  or mixtures thereof. If a polymer containing unsaturated curing sites is incorporated in the sealant a curing agent for this polymer may be incorporated also. Curing agents such as paraquinonedioxime and PbO 2 , or t-butyl perbenzoate and PbO 2  are convenient. The curing agent may also be packaged separately to form a two part sealant. Typically curing agents suitable for the one part sealant may also be employed for the two part sealant. 
     The one part sealants, or the two part sealants after mixing, may be applied to the desired substrate by conventional means commonly by extrusion from a caulking gun. The substrates to which they may be applied may be singly or in combination comprised of siliceous materials such as glass, metals, or concrete and the like. 
     The following examples further illustrate the best mode contemplated by the inventor for the practice of his invention. 
     EXAMPLE 1 
     A sealant formulation containing the following ingredients is prepared: 
     
         ______________________________________                                    
                          Parts by                                        
Ingredients               Weight                                          
______________________________________                                    
Liquid bis-dichloroethyl formal based poly-                               
sulfide polymer, average M.W. 4000 average                                
cross-linking 0.5%        100                                             
Butyl latex (fully cured 63% solids emulsion                              
in water)                 159                                             
CaCO.sub.3                200                                             
Low oil absorbtion TiO.sub.2                                              
                           10                                             
Alkyl aryl polyether alcohol (Rohm &amp; Haas Triton                          
X-100)                    0.5                                             
20% MnO.sub.2 in 51% chlorinated paraffin plasticizer                     
(ICI Cerechlor 51L)        20                                             
Total                     489.5                                           
Liquid polysulfide polymer/butyl polymer                                  
(solids/solids)           100/100                                         
Total % solids             88.1                                           
______________________________________                                    
 
    
     This mixture remains as a stable one package sealant until such time as it is applied to a substrate and the water permitted to evaporate. The following physical properties are possessed by this formulation: 
     Initial 
     Consistency; Medium ease of extrusion, good wet adhesion, no sag in horizontal position. 
     
         ______________________________________                                    
Hardness: Shore A Duro (1 day)                                            
                         15.20                                            
(Ultimate)             30                                                 
Tensile (psi/elongation (%)(est.)                                         
(1 day)                 80/1400                                           
(ultimate)             125/1500                                           
Time to tack free surface (minutes)                                       
                       15                                                 
______________________________________                                    
 
    
     After Heat Aging 1 week at 158° F 
     Consistency: Between medium and firm, medium to moderate resistance to extrusion, adequate wet adhesion. 
     
         ______________________________________                                    
Hardness: Shore A Duro (1 day)                                            
                       15-20                                              
(ultimate)             30-32                                              
Tensile (psi)/elongation (%) (est.)                                       
(1 day)                 80/1600                                           
(ultimate)              90/1400                                           
______________________________________                                    
 
    
     This formulation shows good adherence to glass upon cure, improved adhesion to concrete after immersion, a low modulus but high ultimate tensile strength. Because of the water in the formulation there is some shrinkage on drying, but less than in acrylic, vinyl, and butyl latex or solvent containing sealants. Evaporation of water apparently leaves the cured sealant microporous so that it is somewhat permeable to water vapor. Characteristic of butyl containing caulks the surface retains some residual tack on drying. 
     EXAMPLE 2 
     Two part sealant formulations containing the following ingredients are prepared: 
     
         __________________________________________________________________________
                         Parts by Weight                                  
                         1     2     3     Control                        
__________________________________________________________________________
Liquid bis-dichloroethylformal based polysulfide                          
polymer, average M.W. 4000, average cross-                                
linking 0.5%             100   100   100   100                            
Calcium carbonate        45    45    45    45                             
Titanium dioxide         15    15    15    15                             
Stearic Acid             0.5   0.5   0.5   0.3                            
Castor oil derivative sag control agent                                   
(Baker Thixcin GR)       10    10    10    10                             
γ-glycidoxy propyl-trimethoxy silane (Union                         
Carbide Silane A-187)    3     3     3     3                              
Saturated polybutene (100% solids, viscous liquid)                        
(Cosden polyvis 200 SH)  20    35    50    --                             
Part A Total             198.5 213.5 228.5 191                            
MnO.sub.2 --D Grade       10                                              
Phthalate plasticizer                                                     
(Monsanto, Santicizer S-278                                               
                         10                                               
Carbon black              0.6                                             
Part B Total             20.6                                             
__________________________________________________________________________
 
    
     Upon mixing Part A and Part B the sealants exhibited the following properties: 
     
         ______________________________________                                    
              1     2        3      Control                               
______________________________________                                    
Work Life (Min.)                                                          
               120      90       420  255                                 
Tensile (Instron) (psi)                                                   
               90       85       50   150                                 
Modulus (psi):100%                                                        
               75       66       38   123                                 
:200%          --       --       --   --                                  
Elongation (ultimate) (%)                                                 
               170      165      170  160                                 
Durometer (Shore A)                                                       
:1 day         32       26        8    35                                 
:1 week        36       30       20    40                                 
:Ultimate      38       35       22    48                                 
Adhesion to glass:                                                        
:1 week (room temp.)                                                      
               cohesive cohesive CF*  cohesive                            
:plus 1 week exposure                                                     
H.sub.2 O and U.V. light                                                  
               cohesive cohesive CF   --                                  
Moisture vapor transmis-                                                  
sion (g./m.sup.2 /24 hrs.)                                                
               9.1      5.4      3.5   8-12                               
______________________________________                                    
 *very heavy film, almost cohesive                                        
 
    
     Upon cure the sealants containing polybutene polymer retained tack similar to that of the sealant of Example 1. 
     EXAMPLE 3 
     Sealant compositions prepared in the same proportions as Example 2 but incorporating 0.6 parts by weight stearic acid in Part B when mixed gave identical properties to the sealant of Example 2 except that on testing for adhesion to glass the following results were found. 
     
         ______________________________________                                    
           Sealant                                                        
Adhesion to Glass                                                         
              1       2        3      Control                             
______________________________________                                    
1 week at    cohesive cohesive cohesive.sup.1                             
                                      cohesive                            
room temperature               film                                       
plus 102 hours                                                            
             cohesive cohesive cohesive                                   
                                      cohesive                            
exposure to water and          film   (Short)                             
U.V. light                                                                
plus 225 hours                                                            
             cohesive cohesive cohesive                                   
                                      cohesive                            
exposure to water and                                                     
             (Short)  film     film   (Short)                             
U.V. light                                                                
Moisture vapor                                                            
             6.5      4.3      3.4    11.5                                
transmission                                                              
(g./m.sup.2 /24 hours)                                                    
______________________________________                                    
 .sup.1 Very heavy film (almost cohesive)                                 
 
    
     EXAMPLE 4 
     Sealant compositions are prepared containing the following ingredients: 
     
         ______________________________________                                    
                   Parts by Weight                                        
                    1   2      3      4                                   
______________________________________                                    
Liquid polysulfide polymer as in                                          
                     100    100    100  100                               
Examples 1 and 2                                                          
Calcium carbonate    45     45     45   45                                
Titanium dioxide     15     15     15   15                                
Castor oil derivative                                                     
                     10     10     10   10                                
(Baker Thixcin GR)                                                        
4% unsaturated butyl liquid polymer in                                    
                     27     23     33   23                                
toluene (3:1) (Exxon, Enjay Chemical,                                     
LM 430)                                                                   
Saturated polybutene liquid polymer                                       
                      5     18     25   18                                
as in Example 2                                                           
γ-glycidoxypropyl-trimethoxy silane                                 
                      3      3      3   1.5                               
Liquid polysulfide polymer average                                        
                     --     --     --   1.5                               
MW 1000, 2% cross link inverted to OH                                     
terminals                                                                 
MnO.sub.2 /phthalate plasticizer/carbon                                   
                     21     21     21   21                                
black/(Monsanto S-278) stearic acid                                       
(10/10/0.6/0.6)                                                           
p-quinone dioxime    0.9    0.8    1.2  0.8                               
______________________________________                                    
 
    
     These formulations exhibited the following properties: 
     
         ______________________________________                                    
            1     2        3        4                                     
______________________________________                                    
Work Life (minutes)                                                       
              55      55       75     75                                  
Tensile (Instron) (psi)                                                   
             151      126      100    131                                 
Modulus (psi) : 100%                                                      
             100      80       60     71                                  
: 200%       146      112      88     105                                 
Elongation (ultimate)                                                     
             220      260      270    290                                 
Durometer (Shore A)                                                       
: 1 day       30      22       20     30                                  
: 1 week      40      35       33     35                                  
Adhesion to Glass                                                         
1 week room  cohesive cohesive cohesive.sup.1                             
                                      cohesive                            
temperature                    film                                       
+ 104 hours exposure                                                      
             cohesive cohesive cohesive                                   
                                      cohesive                            
H.sub.2 O + U.V.               film                                       
+ 250 hours exposure                                                      
             cohesive cohesive cohesive                                   
                                      cohesive                            
H.sub.2 O + U.V.               film                                       
Moisture vapor                                                            
             6.9      4.9      4.1    5.4                                 
transmission                                                              
(g./m.sup.2 /24 hours)                                                    
Surface Tack: 1 day                                                       
             none     none     slight none                                
: 1 week     none     none     slight none                                
______________________________________                                    
 .sup.1 Viscous film, virtually cohesive.                                 
 
    
     EXAMPLE 5 
     Sealant compositions are prepared containing the following ingredients: 
     
         __________________________________________________________________________
                        1   2    3    4    5    6    7    8               
__________________________________________________________________________
Liquid polysulfide polymer                                                
                       100  100  100  100  100  100  100  100             
as in Example 1                                                           
Calcium carbonate      45   45   45   45   45   45   45   45              
Titanium dioxide       15   15   15   15   15   15   15   15              
Stearic Acid           0.3  0.3  0.3  0.3  0.3  0.3  0.3  0.3             
Castor oil derivative  10   10   10   10   10   10   10   10              
(Baker Thixcin GR)                                                        
Butyl liquid polymer unsaturation                                         
                       35   35   35   35   35   35   40   40              
(4%) in toluene (3:1) (Enjay                                              
Chemical Butyl LM 430)                                                    
γ-glycidoxypropyl-tri-                                              
                       --    3   --   1.5  --    3    3   1.5             
methoxy-silane                                                            
Liquid polysulfide polymer                                                
                       --   --   1.5  1.5  --   1.5  --   1.5             
inverted to OH terminals                                                  
as in Example 4                                                           
Epichlorohydrin resin (Shell                                              
                       --   --   --   --    3   --   --   --              
Epon)/inverted polysulfide                                                
resin as above (1/0.5)                                                    
MnO.sub.2 /phthalate plasticizer                                          
(Monsanto santicizer S-278)/                                              
carbon black (10/10/0.6)                                                  
                       21   21   21   21   21   21   21   21              
p-quinone dioxime       2    2    2    2    2    2    2    2              
Tridimethylaminomethylphenol                                              
                       --   --   --   --   0.2  --   --   --              
__________________________________________________________________________
 
    
     The consistency of all formulation ranged from moderate to moderately firm. All were acceptable. None of the above formulations possessed any surface tack after 1 week. In addition, they possessed the following properties: 
     
         __________________________________________________________________________
                      1    2    3    4    5    6    7    8                
Work Life (min.)      35   50   45   50    5   60   50   50               
Tensile (psi/Elongation(%)                                                
:1 week               --   110/380                                        
                                --   --   --   --    87/470               
                                                          90/380          
:1 week (EST)         200/300                                             
                           200/500                                        
                                180/900                                   
                                     180/690                              
                                          180/790                         
                                               180/600                    
                                                    180/600               
                                                         150/610          
Durometer (Shore A)                                                       
:1 day                22   12   20   12   18   10    8   12               
:1 week               38   32   30   30   30   25   30   23               
:3 weeks              45   43   45   41   40   36   37   30               
Adhesion to Concrete (Qualitative Beads)                                  
:1 wk RT              Coh  Coh  Coh  Coh  Coh  Coh  Coh  Coh              
: above + 1 wk H.sub.2 O                                                  
                      NA   Coh  Coh/ Adh  Coh/ Adh  Coh  Adh/             
immersion                  Film Adh       Adh            Coh              
Adhesion to Glass (Qualitative Beads)                                     
:1 week at RT         NA   Coh  Coh/ Coh  Coh  Coh  Coh  Coh              
                                Adh                                       
:+ 108 hours exposure to                  v.thin                          
H.sub.2 O and U.V.    Adh       Adh  Coh  Coh  Coh  Coh  Coh              
                                     Film Film           Film             
                                          v.thin                          
:+ 200 hours exposure to                                                  
                      Adh       Adh  Coh  Coh  Coh  Coh  Coh              
H.sub.2 O and U.V.                   Film Film           Film             
__________________________________________________________________________
 
    
     EXAMPLE 6 
     Sealant compositions are prepared from the following ingredients: 
     
         ______________________________________                                    
                          1   2                                           
______________________________________                                    
Liquid polysulfide polymer as in Ex. 1                                    
                           100    100                                     
Calcium carbonate          45     45                                      
Titanium dioxide           15     15                                      
Castor oil derivative (Baker Thixcin GR)                                  
                           10     10                                      
Phthalate plasticizer (Monsanto santicizer S-278)                         
                           25     --                                      
(3:1) (Exxon Butyl LM 430) --     33                                      
γ-glycidoxypropyl-trimethoxy silane                                 
                            2      2                                      
Inverted polysulfide polymer as in Ex. 4                                  
                            1      1                                      
p-quinone dioxime          --      2                                      
2,4-dihydroxy benzophenone  2      2                                      
naphthyl triazole           2      2                                      
MnO.sub.2 /santicizer 278/carbon black/stearic acid                       
                           16     16                                      
(10/10/0.6/0.6)                                                           
PbO.sub.2 /poly-α-methyl styrene plasticizer                        
                            4      4                                      
(Dow V-276) (7.5/7.5)                                                     
______________________________________                                    
 
    
     These compositions have the properties shown: 
     
         ______________________________________                                    
                         1   2                                            
______________________________________                                    
Durometer, Shore A                                                        
:1 day                     10    42                                       
:1 week                    30    42                                       
Moisture vapor transmission (Gms/Day/Meter.sup.2)                         
                          8.0    5.2                                      
Tensile (psi)             161    152                                      
Elongation (%)            310    400                                      
Modulus 100%               91    65                                       
200%                      127    93                                       
Adhesion:Beads on Glass:                                                  
:Wet UV: (After 1 wk cure RT)                                             
                          Coh    Coh                                      
1 week                    NA     Coh                                      
2 weeks                   --     Coh                                      
3 weeks                   --     Coh                                      
4 weeks                   --     Coh                                      
6 weeks                   --     Coh                                      
8 weeks                   --     Coh                                      
:Water vapor, UV after 1 week cure (RT)                                   
                          Coh    Coh                                      
108 hours                 Coh-   Coh                                      
                          Film                                            
200 hours                 Coh-   Coh                                      
                          Film                                            
400 hours                 Adh    Coh-                                     
                                 Film                                     
______________________________________                                    
 
    
     EXAMPLE 7 
     Sealant formulations containing the ingredients shown are prepared: 
     
         ______________________________________                                    
                1    2      3      4    5                                 
Liquid polysulfide polymer as in                                          
                  100    100    100  200  200                             
Example 1                                                                 
Saturated polybutene (viscous                                             
                  300    300    200  200  100                             
liquid polymer) (Cosden polyvis                                           
200 SH                                                                    
Butyl liquid polymer in                                                   
                  100    100    200  100  200                             
toluene (3/1) (4% uncured)                                                
Enjay Butyl LM 430)                                                       
Calcium carbonate 200    300    300  300  300                             
p-quinone dioxime 3.5    3.5     7    7    7                              
Toluene           --      50     50   50   50                             
PbO.sub.2 /poly-α-methyl styrene                                    
plasticizer (Dow V-276) (7.5/7.5)                                         
                   15    --     --   --   --                              
MnO.sub.2 /phthalate plasticizer                                          
                  --      21     21   21   21                             
(Monsanto santicizer S-278)/                                              
carbon black (10/10/0.6)                                                  
______________________________________                                    
 
    
     The formulations possessed the following properties: 
     All formulations had a moderate consistency with good gunnability to a well formed easily curable bead. 
     
         ______________________________________                                    
          1    2        3        4     5                                  
______________________________________                                    
Tensile (psi)/                                                            
Elong. (%)                                                                
:1 day      0/50   20/200-  10/200 20/90 20/100                           
                   650                                                    
:1 week    0/200   25/320   100/225                                       
                                   40/90 90/200                           
Durometer                                                                 
(Shore A)                                                                 
:1 day     5       5        10     17    20                               
:1 week    3       10       23     30    36                               
Surface Tack                                                              
:1 day     v.      tacky    sl.    sl.   sl.                              
           tacky            tack   tack  tack                             
:1 week    v.      tacky    v.sl.  dry   dry                              
           tacky            tack                                          
______________________________________