Thermally stable high molecular weight acyl peroxycarbonic esters in vulcanization of silicone rubber
This is a division of application Ser. No. 696,463, filed June 16, 1976. 
    
    
     This invention relates to organic peroxide compositions and their use as polymerization initiators. More particularly, the invention relate to certain higher molecular weight acyl peroxycarbonic esters that exhibit improved thermal stability, together with increased polymerization initiation efficiencies and other improved properties. 
     U.S. Pat. No. 3,108,093 describes a number of peroxycarbonic esters including a group of acyl peroxycarbonic esters. The molecules disclosed therein are stated to have thermal stabilities which do not &#34;complicate the polymerization process they catalyze.&#34; The patentees, thus, recognize the potential problem of thermal stability in molecules of this type. 
     U.S. Pat. Nos. 3,585,232, 3,653,524 and 3,736,344 describe a group of acyl peroxycarbonic esters having lower molecular weights than described in said U.S. Pat. No. 3,108,093 and which have improved efficiencies in the polymerization of monomers. 
     The present invention provides a group of related acyl peroxycarbonic esters which demonstrate dramatically improved thermal stabilities as compared with analogous molecules described in U.S. Pat. No. 3,108,093. Further, in addition to being more thermally stable, they exhibit improvements in the polymerization of certain compounds, including ethylene, styrene, vinyl chloride, vinyl chloride and vinyl acetate comonomers, methyl methacrylate, ethylenically unsaturated polyester, and in the vulcanization of general purpose silicone rubber (silicone rubber that is cross-linkable through ethylenically unsaturated sites). Particularly outstanding improvements have been found in the polymerization of methyl methacrylate. Also, in the polymerization of ethylenically unsaturated polyester in the presence of tertiary amine promoters it has been found that the present initiators produce less yellowing in the polymeric end product. 
    
    
     These improvments are obtained in the present invention through the use of acyl peroxycarbonic esters of the formula: ##STR2## where R is selected from methyl and ethyl; and R&#39; is an alkyl group which together with R contains a total of 17 to about 25 carbon atoms. Preferably, R and R&#39; have a total of 17 to about 20 carbon atoms. 
     Apart from the employment of the novel compounds of this invention, the polymerization and vulcanization processes in which they are used is consistent with the teachings of the prior art, including quantities of reactants, temperatures, solvents, optional additives and the like. 
     The following example which is for the preparation of acetyl peroxystearyl carbonate illustrates the procedure utilized to prepare the various acyl peroxycarbonic esters listed in Table I. The other novel compounds of this invention were prepared by substitution of the appropriate chloroformate and peracid in the following example. 
     To 9.34 g. (0.0295 mole) of 24% peracetic acid in ethyl acetate and 25 ml acetone containing 1 drop of Triton X-100 surfactant is added simultaneously 8.94 g. (0.0268 mole) of stearyl chloroformate and 2.76 g. (0.0349 mole) of pyridine over a 17-minute period at -3° to -5° C. The addition funnel was rinsed with 7-8 ml of hexane. The reaction mixture is well stirred during these additions. After the reaction mixture is stirred an additional two hours at -5° C., the reaction mixture is filtered to remove the pyridinium hydrochloride. The filter cake and reactor were rinsed with ether. The cake was transferred to a separatory funnel and extracted with 50 ml CHCl 3  and then with 50 ml ether. These two extractions were combined with the initial filtrate in another separatory funnel. The organic layer was washed as follows: once with 100 ml saturated NaCl solution, pH 6-7; once with 100 ml cold 1% H 2  SO 4  solution, pH 2; once with 100 ml saturated NaCl solution, pH 2; once with 100 ml saturated NaHCO 3  solution, pH 8; once with 100 ml ice water, pH 8; and finally twice with 100 ml saturated NaCl solution, both pH&#39;s 7. The organic layer was filtered through a cake of anhydrous MgSO 4  and concentrated under vacuum on a 10° C. H 2  O bath. Product A.O. (active oxygen) analysis: Theory, 4.29; found 3.79, 88.45% pure; 81.1% yield. 
     
                                           TABLE I                                 
__________________________________________________________________________
 ##STR3##                                                                 
__________________________________________________________________________
                R + R&#39;                Ten Hour, Half-Life.sup.1)          
                                                  Synthesis Results       
Peroxide        (No. of C Atoms)                                          
                          % Purity                                        
                                m.p.° C                            
                                      Temp, ° C.                   
                                                  % Purity                
                                                       %                  
__________________________________________________________________________
                                                       Yield              
  Acetyl peroxycetyl                                                      
                17        96.3  44-45 55.1        94.12                   
                                                       87.7               
  carbonate (APCC)                                                        
  Acetyl peroxystearyl                                                    
                19        97.7  54-55 54.9        88.45                   
                                                       81.1               
  carbonate (APSC)                                                        
  Propionyl peroxycetyl                                                   
                18        96.0  30-31 51.5        88.72                   
                                                       85.0               
  carbonate (PPCC)                                                        
  Propionyl peroxystearyl                                                 
                20        96.0  39-40 52.3        87.87                   
                                                       84.4               
  carbonate (PPSC)                                                        
  Lauroyl peroxyoctyl                                                     
                19        98.7  4-6   51.4        87.58                   
                                                       88.7               
  carbonate (LPOC)                                                        
__________________________________________________________________________
 .sup.1) 0.2 M peroxide in benzene                                        
 
    
     The storage stability of the new molecules of this invention, including the improved thermal stability at 30° C is shown in the following Table II. The abbreviations of the molecule names are the same throughout and are defined in Table I. LPOC is included as typical of the prior art as disclosed in U.S. Pat. No. 3,108,093. 
     
                                           TABLE II                                
__________________________________________________________________________
Storage Stability of Various Acyl Peroxycarbonic Esters at 30° C   
Peroxide                                                                  
        APSC      APCC     PPSC     PPCC     LPOC                         
T A O.sup.1)                                                              
        4.29      4.64     4.14     4.46     4.29                         
Days Elapsed                                                              
        A.0..sup.2)                                                       
             % Purity                                                     
                  A.O.                                                    
                      % Purity                                            
                           A.O.                                           
                               % Purity                                   
                                    A.O.                                  
                                        % Purity                          
                                             A.O.                         
                                                 % Purity                 
__________________________________________________________________________
 0      4.19 97.67                                                        
                  4.55                                                    
                      98.06                                               
                           3.90                                           
                               94.20                                      
                                    4.36                                  
                                        97.76                             
                                             4.22                         
                                                 98.37                    
 1      --   --   --  --   --  --   --  --   3.57                         
                                                 83.22                    
 4      --   --   --  --   --  --   --  --   2.04                         
                                                 47.55                    
 6      --   --   --  --   --  --   --  --   1.52                         
                                                 35.43                    
 7      --   --   --  --   --  --   1.95                                  
                                        43.74                             
                                             --  --                       
 8      --   --   --  --   --  --   --  --   1.19                         
                                                 27.74                    
11      --   --   --  --   --  --   1.27                                  
                                        28.48                             
13      --   --   --  --   3.84                                           
                               92.75                                      
25      4.16 96.97                                                        
                  4.55                                                    
                      98.06                                               
                           --  --                                         
28      --   --   --  --   3.58                                           
                               86.47                                      
32      --   --   --  --   3.17                                           
                               76.57                                      
39      4.14 96.50                                                        
                  4.57                                                    
                      98.49                                               
                           --  --                                         
46      --   --   --  --   1.07                                           
                               25.85                                      
52      4.12 96.00                                                        
                  --  --                                                  
53      --   --   4.57                                                    
                      98.49                                               
80      4.07 94.86                                                        
                  --  --                                                  
81      --   --   4.52                                                    
                      97.41                                               
95      --   --   4.51                                                    
                      97.20                                               
97      4.10 95.57                                                        
                  --  --                                                  
__________________________________________________________________________
 .sup.1) Theoretical Active Oxygen                                        
 .sup.2) Active Oxygen                                                    
 
    
     In view of the extraordinary stability of APSC and APCC, these two molecules were further tested at an even higher temperature of 41°-42° C. for a period of time. The results of this additional test are shown in Table II-A below. 
     
                       TABLE II-A                                                  
______________________________________                                    
Storage Stability of Two Acyl Peroxycarbonic                              
Esters at 41-42° C.                                                
Peroxide     APSC          APCC                                           
TAO          4.29          4.64                                           
Days Elapsed A.O.    % Purity  A.O.  % Purity                             
______________________________________                                    
 0           4.22    98.37     4.60  99.14                                
 3           4.22    98.37     4.59  98.92                                
 9           4.22    98.37     4.47  96.34                                
15           4.20    97.90     2.57  55.39                                
17           --      --        1.03  22.20                                
20           4.25    99.07                                                
28           4.22    98.37                                                
35           4.15    96.74                                                
42           4.16    96.97                                                
______________________________________                                    
 
    
     The compounds of this invention are relatively safely handled peroxides as shown by OPPSD tests (standard safety tests of Society Of The Plastics Industry, Inc., Organic Peroxide Producers Safety Division) as set forth in Table III below. 
     
                                           TABLE III                               
__________________________________________________________________________
OPPSD Tests Made on Various Acyl Peroxycarbonic                           
Esters (99% Purity)                                                       
Peroxide          APSC   APCC   PPSC                                      
__________________________________________________________________________
  Rapid Heat                                                              
        Decomp. Temp,° C                                           
                  82      77    85                                        
        Force     Inter.sup.1)                                            
                          Inter Inter                                     
  PVT   Vent Diameter, mm                                                 
                  &lt;11/2   2     &lt;1                                        
        Hazard    Low-Inter                                               
                          Inter Low                                       
  Burning                                                                 
        Flame Height, cm                                                  
                  46      122   137                                       
        Hazard    Low     Inter-Max                                       
                                Inter-Max                                 
  Autoignition at 330-340° C                                       
                  None   None   None                                      
  SADT (Estimated) for 7#                                                 
                  55° C                                            
                         4° C                                      
                                43° C                              
  in 4 gal Fiberpak                                                       
__________________________________________________________________________
 .sup.1) Intermediate                                                     
 
    
     The utility and improved efficiencies of the present molecules in polymerization reactions is demonstrated by the following examples in connection with a series of different polymerizable and vulcanizable materials. 
     Polyester Resins 
     Data on the testing of these new acyl peroxycarbonic esters as initiators of ethylenically unsaturated polyester resins are found in Tables IV-VI. 
     In Table IV, results of testing a series of peroxides at equivalent A.O. in a Hot Block Gel Tester at 180° F. are shown. Four commercial peroxides are included for comparison purposes. Of the acyl peroxycarbonic esters tested, the acetyl derivatives gave higher peak temperatures than the other three, indicating a somewhat higher degree of cure. 
     The data in Tables V and VI demonstrate the improved utility of APSC over two commercial peroxides presently used because of their fire resistant properties. In Table V, Hot Block gel tests were done at 140°-200° F. using three peroxides. Results indicate that APSC &#34;kicks-off&#34; at a lower temperature than either 2,5-dimethyl-2,5-di(2-ethyl hexanoyl peroxy) hexane or benzoyl peroxide. In addition, lower concentrations of APSC can be used to achieve similar or superior results over the entire temperature range. 
     Table VI shows that APSC can also be used in room temperature curing of unsaturated polyesters using the same promoter systems as used with benzoyl peroxide (PBO). Several tertiary amines commonly used in the industry were screened. Results indicate that faster cure cycles are obtained with the APSC systems as compared to the BPO systems. In addition, smaller amounts of promoter can be used with APSC to match the performance of the equivalent BPO system. Tertiary amines are known to be poor promoters for outdoor applications with BPO because of the yellowing problem. However, with APSC, the color is much lighter even at equivalent amounts of any of these amines. 
     
                                           TABLE IV                                
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Hot Block Gel Tests With Polyester Resin Using Various Peroxides.sup.1)   
Resin: Hatco GR941 (Isophthalic)                                          
Block Temp: 180° F. (82° C.)                                
Concentration of each peroxide equal to AO equivalent of 3.50%            
                 Ten-Hour Half-Life Gel Time,                             
                                           Exotherm                       
                                                  Peak Temp,              
Peroxide         Temp, ° C                                         
                             % Wt Used                                    
                                    Min.   Time, Min.                     
                                                  ° F              
                                                      (° C)        
__________________________________________________________________________
  LPOC           51.4        0.82   2.87   3.97   260 (127)               
  PPCC           51.5        0.78   2.65   3.67   272 (133)               
  PPSC           52.3        0.85   2.72   3.79   272 (133)               
  APSC           54.9        0.82   3.35   4.60   293 (145)               
  APCC           55.1        0.75   3.36   4.58   289 (143)               
  t-Butyl peroxy pivalate                                                 
                 55          0.38   3.05   4.00   298 (148)               
  Decanoyl Peroxide                                                       
                 62          0.75   3.87   4.99   293 (145)               
  2,5-Dimethyl-2,5-di-                                                    
                 68          0.47   6.3    7.63   303 (151)               
  (2-ethyl hexanoyl peroxy)                                               
  hexane                                                                  
  Benzoyl peroxide                                                        
                 72          0.53   8.35   10.76  264 (129)               
__________________________________________________________________________
 .sup.1) 5 cc of a 50 g mixture charged to Hot Block                      
 .sup.2) 0.2 M. peroxide in benzene                                       
 
    
     
                                           TABLE V                                 
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Hot Block Gel Tests at 140-200° F Using Three Peroxides.sup.1)     
Resin: Hatco GR14017 (Isophthalic)                                        
                                     2,5-Dimethyl-2,5-                    
                                     di(2-ethyl hexanoyl                  
Block Temp.,                                                              
        Peroxide         APSC        Peroxy) hexane                       
                                                 Benzoyl Peroxide         
° F                                                                
        Conc,% wt. 0.5   0.75  1     0.5   1     1                        
__________________________________________________________________________
140     Gel Time, Min                                                     
                   --    --    20.56 --    --    --                       
        Exotherm Time, Min                                                
                   --    --    22.43 --    --    --                       
        Peak Temp, ° F                                             
                   --    --    262.5 --    --    --                       
150                --    12.91 8.94  --    19.91 --                       
                   --    14.10 10.33 --    21.35 --                       
                   --    276   287.5 --    292.5 --                       
160                7.47  6.01  4.46  13.94 8.34  23.84                    
                   8.86  7.04  5.31  15.34 9.47  25.26                    
                   291.8 303   304   293.5 313.5 287                      
170                4.32  3.31  2.97  7.35  4.69  10.06                    
                   5.31  4.09  3.60  8.50  5.52  11.25                    
                   303.2 310.8 313   317   315   311                      
180                3.0   2.29  1.86  5.25  3.41  8.01                     
                   3.66  2.97  2.43  5.97  3.85  8.84                     
                   308.0 314   317   318   314   322.5                    
200                0.86  0.53  0.40  1.34  0.74  2.33                     
                   1.46  1.19  0.94  1.89  1.22  2.89                     
                   315   317.3 318.5 324   328   326                      
__________________________________________________________________________
 .sup.1) 5 cc of a 50 g. mixture charged to Hot Block                     
 
    
     
                                           TABLE VI                                
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Room Temperature Gel Tests Using 1% wt.                                   
Acetyl Peroxy Stearyl Carbonate (APSC)                                    
or Benzoyl Peroxide (BPO) With Various Promoters.sup.1)                   
Temperature: 23-24.5° C.                                           
Resin: 50 g Hatco GR-941                                                  
               Conc,                                                      
                   Gel Time,                                              
                          Exotherm                                        
Peroxide  Protomer                                                        
               % Wt.                                                      
                   Min.   Time, Min.                                      
                                 Peak Temp, ° C                    
__________________________________________________________________________
  APSC (a)                                                                
          DMA.sup.2)                                                      
               0.15                                                       
                   8.3    15.0   166                                      
               0.30                                                       
                   4.15   10.0   169.5                                    
       (b)                                                                
          DEA.sup.3)                                                      
               0.30                                                       
                   22.8   31.5   166                                      
       (c)                                                                
          DMT.sup.4)                                                      
               0.15                                                       
                   4.35    9.5   168                                      
       (d)                                                                
          MPEA.sup.5)                                                     
               0.15                                                       
                   16.25  23.0   172.2                                    
  BPO  (a)                                                                
          DMA  0.30                                                       
                   9.8    17.0   161.5                                    
       (b)                                                                
          DEA  0.30                                                       
                   38.1   47.0   166.5                                    
       (c)                                                                
          MPEA 0.30                                                       
                   13.7   20.5   166.6                                    
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 .sup.1) 50g of mixture used in a 3oz. water cup                          
 .sup.2) Dimethyl aniline                                                 
 .sup.3) Diethyl aniline                                                  
 .sup.4) Dimethyl p-toluidine                                             
 .sup.5) Methyl phenyl ethanol amine                                      
 
    
     Polymerization of MMA 
     Bulk polymerization of methyl methacrylate was done at 70° C. using six peroxides at equal molar concentrations. Results are shown in Table VII. t-Butyl peroxy privalate was included in this test because it is a commercial peroxide with a comparable 10-hour half-life temperature to the acyl peroxycarbonic esters. Except for LPOC, all of the initiators cured the monomer in about the same length of time. However, APSC and APCC were somewhat faster than the others. 
     The data in Table VII was obtained in the following manner. 
     The approximate amount of 100 percent of pure initiator required for 30 grams of monomer mixture was weighed into a 2-ounce wide-mouth bottle to 0.1 milligram. The amount of inhibited monomer needed for the desired initiator concentration was calculated and weighed to 0.01 gram. The bottle was capped and shaken, and 25 grams of the mixture was then weighed into a 25 × 150 millimeter test tube. 
     A stainless steel temperature-recorded probe was centered in the test tube through three rubber stoppers with the probe protruding a distance of approximately 70 milimeters. Before each run, the end of the probe was coated with a 3 percent aqueous solution of polyvinyl alcohol as a moldrelease agent. 
     The probe was inserted while flushing the test tube with a stream of nitrogen and the sealed unit placed into a stirred constant-temperature bath (70°±0.2° C.) containing glycerine, to a depth of 110 millimeters. 
     
                                           TABLE VII                               
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Polymerization of Methyl Methacrylate at 70° C                     
With Various Acyl Peroxycarbonic Esters                                   
1.72 × 10.sup.-4 mole initiator/100g MMA in 25 mm tube              
                Exotherm Time,                                            
                         Peak Time,                                       
                                Time to Return                            
                                           Temp Rise,° C           
Peroxide  %Wt Used                                                        
                Min.     Min.   to Bath Temp, Min.                        
                                           (ΔT)                     
__________________________________________________________________________
  APSC    0.064 108      113    142        53                             
  APCC    0.059 112      117    143        57                             
  PPCC    0.066 138      168    223        25                             
  PPCC    0.062 132      158    200        28                             
  LPOC    0.064 very long       ˜360.sup.1)                         
                                           ≦ 5                     
                flat exotherm                                             
  t-Butyl peroxy                                                          
          0.03  135      143    180        51                             
  pivalate                                                                
__________________________________________________________________________
 .sup.1) Cured hard much slower than other runs shown.                    
 
    
     Initiators for the Suspension Polymerization of Vinyl Chloride and Vinyl Chloride/Vinyl Acetate. 
     Suspension polymerization was done at 60° C. in pop bottles for both homopolymer and copolymer. Again, t-butyl peroxypivalate was included in the testing because it is used commercially for this purpose. As can be seen from the date in Table VIII, the acyl peroxycarbonic esters are not as efficient as t-butyl peroxypivalate on an equal weight basis, but are superior to it on an equal molar basis. 
     The data in Table VIII was obtained in the following manner. 
     The suspension polymerizations were performed in 12 fluid ounce pop bottles using uninhibited monomer. Each bottle contained 188.0 g. of suspension solution and 75 g. of monomer (water/monomer ratio = 2.5/1). The amount of suspension agent per 100 g. monomer = 0.35 g. Methocel 90HG, 100 cps. For the copolymer runs, 75 g. of a mixture of 88% wt vinyl chloride and 12% wt vinyl acetate were used. 
     After the desired amounts of pure initiator were added to the pop bottles, they were capped, the contents almost melted, and the bottles placed in a rotating constant temperature bath at 60° C. for varying lengths of time. Duplicate bottles were pulled at each time interval. The bottles were frozen before venting-off excess monomer. The polymer was filtered, washed, and dried. 
     
                                           TABLE VIII                              
__________________________________________________________________________
Suspension Polymerization of Vinyl Chloride and                           
Vinyl Chloride-Vinyl Acetate in Pop Bottles at 60° C               
                   % Conversion                                           
Peroxide    % Wt. Used                                                    
                   Time, Hrs                                              
                          1.5   3.5   5                                   
__________________________________________________________________________
(A) Hompolymer                                                            
  APSC      0.055          9.9  32.5  53.3                                
             0.118.sup.1) 21.1  60.5  91.8                                
  APCC      0.055         10.4  34.7  58.1.sup.2)                         
             0.109.sup.1) 20.5  65.4  93.2                                
  t-Butyl peroxy                                                          
             0.055.sup.1) 15.0  53.4  84.4                                
  privalate (TBPP)                                                        
(B) Copolymer                                                             
  APSC      0.055         12.1   32.2.sup.2)                              
                                      52.6                                
             0.118.sup.1)  22.0.sup.2)                                    
                                64.0  89.7                                
  PPSC      0.055         12.2  --    52.9                                
             0.122.sup.1) 23.3  60.8  86.0                                
  TBPP       0.055.sup.1) 18.9  57.3  79.1                                
__________________________________________________________________________
 .sup.1) 3.16 × 10.sup.-4 mole/100 g VCM or VC-VA                   
 .sup.2) poor duplication                                                 
 
    
     Vulcanization of Silicone Rubber 
     Vulcanization of a general purpose silicone rubber was done in the Brabender Plasticorder at 110° C. using four initiators at equal molar concentrations. Results are shown in Table IX. 2,4-Dichloro benzoyl peroxide (2.4 DiCl BZP) was used in this work because it is the preferred commercial peroxide used for vulcanization of silicone rubber. Although the acyl peroxycarbonic esters are not as efficient as 2,4DiCl BZP, they do vulcanize this type of silicone rubber. APSC and APCC gave almost identical results, whereas PPSC was only about 25 percent as efficient as they were. 
     The data in Table IX was obtained in the following manner. 
     53 g. of milled rubber (Dow Corning Silastic 4506U) were added within 1 minute to the mixing head maintained at the desired temperature. The rubber was added in small pieces. Net torque is equal to the maximum torque minus the minimum torque just before crosslinking begins. The time to reach maximum torque is equal to the elapsed time from zero. 
     
                                           TABLE IX                                
__________________________________________________________________________
Vulcanization of Silicone Rubber in the Brabender Plasticorder            
with Various Acyl Peroxycarbonic Esters at 110° C                  
1.645×10.sup.-3 mole initiator / 100g Silicone Rubber; 30 RPM Rotor 
Speed                                                                     
Peroxide     phr 50% Paste                                                
                      Net Torque, Mg.                                     
                                Time to Reach Maximum Torque,             
__________________________________________________________________________
                                Min.                                      
  APSC       1.23     798       4.3                                       
  APCC       1.13     790       4.3                                       
  PPSC       1.27     208       5.4                                       
  2,4-Dichlorobenzoyl                                                     
             1.25     950       2.4                                       
  Peroxide                                                                
__________________________________________________________________________