Patent Publication Number: US-4097467-A

Title: Process for the preparation of a copolymerizable composition

Description:
BACKGROUND OF THE INVENTION 
     Process for the preparation of a copolymerizable composition. 
     The invention relates to a process for the preparation of a copolymerizable composition and to a process for the preparation of a peroxide composition to be used in the copolymerization of said copolymerizable composition. 
     By unsaturated polyester resins are to be understood solutions of unsaturated polyesters in reactive monomers and one or more polymerizable CH 2  ═ C &lt; groups such as styrene, vinyl toluene, methyl methacrylate, diallyl phthalate and divinyl benzene. 
     The ratio monomer to unsaturated polyester is generally 30 - 50 % by weight of monomer to 70 - 50 % by weight of polyester. 
     The unsaturated polyester is obtained by reaction of approximately equivalent amounts of a polyvalent alcohol such as ethylene glycol, propylene glycol, diethylene glycol and an unsaturated dibasic carboxyylic acid such as maleic acid, fumaric acid, itaconic acid in the presence, if desired, of a saturated acid such as phthalic acid, isophthalic acid, tetrachlorophthalic acid, malonic acid, adipinic acid, sebacinic acid, succinic acid and the like. 
     In order to improve the stability of the unsaturated polyester, inhibitors are incorporated in them in amounts ranging from 0.001 to 0.03 % by weight. The most commonly used inhibitors are hydroquinone, quinone and para tert. butyl catechol. 
     The above-described unsaturated polyester resins may be copolymerized at room temperature under the influence of organic peroxides yielding free radicals and in the presence of one or more accelerators for the peroxide used. 
     The British Patent Specification 954 600 describes the use of particular aldehyde peroxides as initiators in combination with a cobalt compound and a secondary amine in the copolymerization of unsaturated polyester resins at room temperature. 
     These aldehyde peroxides are obtained by condensation of an aldehyde with hydrogen peroxide under reaction conditions which are not specified. The impression is given, however, that the reaction must be so conducted that the condensation product preferably contains 1-hydroxy-1-alkylhydroperoxide and bis(1-hydroxy alkyl) peroxide. These peroxides may be regarded as aldehyde peroxides which contain respectively 1 active oxygen atom and 1/2 active oxygen atom per carbonyl group of the aldehyde used in the preparation of the peroxide. It is recommended that in practice the copolymerization of unsaturated polyester resins should be carried out using a combination of bis(1-hydroxy heptyl) peroxide and a cobalt accelerator. Unsaturated polyester resins in which such a combination is incorporated have a short gel time, which meets with practical drawbacks. 
     Description of the Invention 
     It has now been found that it is possible to obtain a copolymerizable composition which not only rapidly cures but also has a gel time acceptable in practice if in a copolymerizable unsaturated polyester resin which already contains a metal accelerator there is incorporated a peroxide composition which substantially consists of an alkyl aldehyde peroxide substituted or not with alkyl groups or aryl groups, which alkyl aldehyde peroxide contains not more than 20 C-atoms and has at least 11/2 active oxygen atoms per carbonyl group of the alkyl aldehyde used for the preparation of the peroxide composition. 
     The peroxide composition to be used according to the invention may be incorporated in the unsaturated polyester resin in amounts ranging from 0.1 to 10 % by weight, and preferably from 3 to 7 % by weight, calculated on the unsaturated polyester resin. It can be incorporated in it as such. For reasons of safety, however, it is incorporated in one or more softeners and/or phlegmatizing agents and/or solid carriers and/or low or high boiling solvents. The peroxide compositions not only permit being processed in the form of solutions but also in the form of pastes or putties. 
     As softeners, phlegmatizing agents or solvents can be used esters such as dialkyl phthalates with an alkyl group of 1 to 10 carbon atoms, and those having ring structures, ethyl acetate, butyl acetate, trialkyl phosphates or triaryl phosphates, hydrophilic solvents such as monohydric or polyhydric alcohols, diethylene or triethylene glycols, particularly ketones and hydroxy or alkoxy ketones such as diacetone alcohol, and hydrophobic solvents such as benzene, toluene, xylene or aliphatic hydrocarbons. 
     It is recommended that the peroxide composition according to the invention be incorporated in fillers such as clay, calcium carbonate or silica. It may be of advantage to add to the peroxide composition flame or fire retarding or suppressing agents, annd stabilizers such as mono or dipicolinic acid, pyrophosphates, aluminium compounds, (poly)ethylene glycol ethers, pyrrolidone, N-methyl pyrrolidone, polyvinyl pyrrolidone, aliphatic or hydroxyaliphatic amines, sequestering or masking agents such as nitrilotriacetic acid, ethylene diaminetetra-acetic acid or salts thereof. 
     As metal accelerators may be used salts of transition metals such as halides or acylates or cobalt, iron, manganese, vvanadium, copper, cerium, tin, silver and mercury, preferably however of cobalt, manganese and vanadium, in amounts of 0.001 - 0.5 % by weight, and preferably of 0.005 to 0.05 % by weight of metal, calculated on the unsaturated polyester resin. 
     The peroxide compositions according to the invention can be obtained by reacting alkyl aldehydes having not more than 20 C-atoms with hydrogen peroxide in a solvent in which both the starting aldehydes and the aldehyde peroxides formed therefrom are soluble in the presence of an acid catalyst, with the water being removed during the reaction. 
     The above-described procedure is a safe way of preparing the peroxide composition to be used according to the invention. Moreover, the presence of a colvent increases the reaction speed and consequently shortens the reaction time. 
     Finally, the presence of the solvent facilitates the removal of the acid catalyst upon completion of the reaction. 
     As examples of starting aldehydes may be mentioned: n-butyraldehyde, iso-butyraldehyde, dichlooracetaldehyde, phenylacetaldehyde, diethylacetaldehyde, 2,2-dimethyl-3-hydropropanal heptanal, 2-ethylhexanal, 3,3,5-trimethylhhexanal, dodecanal and stearylaldehyde. 
     The preparation is carried out at a temperature in the range of 10° to 50° C. and preferably at 20° to 40° C.. The hydrogen peroxide is added as a solution in water with a H 2  O 2  content of 30 - 85% by weight, and preferably of 50 - 70 % by weight. The starting aldehyde is used in such an amount that the molar ratio of carbonyl group to H 2  O 2  is between 1 : 15 and 1 : 4.0, and preferably between 1 : 1.6 and 1 : 2.5. 
     As acid catalyst is used a mineral acid such as sulphuric acid, phosphoric acid or nitric acid, a strongly acid ion exchanger or a strong organic acid such as benzene syphonic or toluene sulphonic acid, chloro-substituted acetic acid or formic acid. These catalysts are used in amounts ranging from 0.2 - 200 mg equivalents per mole aldehyde, and preferably in 2 to 50 mg equivalents. The water formed during the reaction is removed during the reaction by distillation and preferably under reduced pressure or azeotropically while using suitable solvents such as benzene, toluene, butyl acetate or other liquids, which, together with water, form an azeotrope. After the reaction the acid catalyst is removed by washing with an aqueous alkaline solution which contains alkali bicarbonate, alkali hydroxide or alkali carbonate by adding calcium oxide or magnesium oxide or calcium carbonate or magnesium carbonate followed by filtration or just by filtering through an ion exchanger. 
     It is preferred that after adding a suitable phlegmatizing agent such as dialkyl phthalates, trialkyl phosphates, alkylene glycols, alkylene glycol monoethers or diethers, diethylene glycols, diethylene glycol monoethers or diethers, alkylene glycol or dialkylene glycol monoether ester, high-boiling alcohols such as dodecanol, octyl alcohol or nonyl alcohol, cyclohexanol, diacetone alcohol, hexylene glycol, polyethylene glycol (M. &lt; 2000), hexamethylene gllycol, 1,4-butylene glycol, neopentyl glycol, 2-pyrrolidone or N-methyl-2-pyrrolidone, the low-boiling solvent used in the preparation is removed, preferably by distillation, provided that this solvent differs from the above-mentioned phlegmatizing agent. The object is to obtain a phlegmatized peroxide composition having an active acid content of 2 - 12 % by weight. 
     Description of the Preferred Embodiments 
     The invention is further described in the following examples. 
     Where in these examples mention is made of an unsaturated polyester resin a &#34;standard&#34; unsaturated polyester resin for general purposes is meant, which unsaturated resin is obtained by condensation of 1 mole of maleic anhydride, 1 mole of phthalic anhydride, 1.1 moles of ethylene glycol and 1.1 moles of propylene glycol to an acid number of about 35, followed by adding 35 parts by weight of styrene to 65 parts by weight of the condensate thus obtained. The resulting unsaturated polyester monomer mixture is subsequently stabilized by adding 0.012 parts by weight of hydroquinone. 
     By gel time is to be understood the time elapsed between adding a peroxide composition according to the invention and the aforedescribed unsaturated polyester resin to which an accelerator has been added. 
    
    
     EXAMPLE 1 
     To 50 g of diisobutyl phthalate were added 2.5 g of a strongly acid ion exchanger (Dower 50 W; 4 mg eq. acid per g substance) and 53.6 g of a 70% by weight-hydrogen peroxide solution (1.1 moles). The reaction flask was rinsed with nitrogen. Subsequently, 60.4 g of heptanal (purity 94.3%) (0.5 moles) were added over a period of 15 minutes. During adding and for 1 hour after stirring the temperature was kept at 20° C. by cooling. Next, the reaction flask was connected to a vacuum system and water was slowly destilled off from the reaction mixture at 20° C.. In 4 hours 31 g of water containing 6.8 g of H 2  O 2  were distilled off along with 1 g of aldehyde. 
     After the ion exchanger had been removed by filtration, 136 g of peroxide solution were obtained with a total AO content of 10.6%. After mixing with 100 ml of hexane at 0° C. the 7,10-dihydroperoxide-8,9-dioxahexadecane crystallized out and had a melting point of 61°- 62° C. : AO content 15.8 %; purity 97 % (D.L.C.). The infrared absorption spectrum showed a strong band at 3438 cm -1  , which is attributable to O -- -- H. 100 g of the above-mentioned peroxide solution with an AO content of 10.6 % were diluted with 71 g of diethylene glycol, resulting in a solution with an AO content of 6.2 %. Likewise, solutions were prepared of 1,1,6,6-tetrachloro-2,5-dihydroperoxide-3,4-dioxahexane starting from dichloroacetaldehyde, of 3,8-diethyl-4,7-dihydroperoxy-5,6-dioxadecane starting from diethylacetaldehyde and of 2,2,7,7-tetramethyl-3,6-dihydroperoxy-4,5-dioxa-1,8-octane diol starting from 2,3-dimethyl-3-hydroxypropanol. 
     EXAMPLE 2 
     To a solution of 0.3 g of p-toluene sulphonic acid in 60 ml of toluene were added 14.6 g of 70 % by weight - hydrogen peroxide solution (0.3 moles) and subsequently, with stirring while keeping the temperature at 20° C. by cooling, 27.6 g of dodecanal (0.15 moles). During adding a white precipitate was formed. 
     Next, the reaction vessel containing the reaction mixture was connected to a vacuum system and heated to 40° C., at which temperature water was slowly removed by an azeotropic distillation. After 30 minutes a clear solution was formed and in 31/2 hours 9 ml of water was obtained containing 13.6 % of active oxygen. The dry peroxide solution thus obtained had an AO content of 3.94 % and was cooled to -10° C.. After the precipitated crystalline product had been isolated by filtration and dried, 29.3 g of 12,15-dihydroperoxy-13,14-dioxa-hexacosane were obtained with a melting point of 56°- 58° C. and an AO content of 10.7% (calculated: 11.6 %). Purity 97 %. According to D.L.C. analysis no other peroxides were present. The infrared absorption spectrum showed a strong band at 3438 cm -1 , which is attributable to O -- O -- H. 89 g of the above-mentioned peroxide solution in toluene were washed until free of acid with an aqueous sodium bicarbonate solution. 12 g of dimethyl phthalate and 12 g of methoxyethoxyethanol (methyl oxitol) were added, after which the toluene was removed at reduced pressure. Of this peroxide a solution was left in a mixture of dimethyl phthalate and methyl oxitol with an AO content of 6.3 %. 
     EXAMPLE 3 
     To a mixture of 250 ml of n-butyl acetate, 2,8 g of p-toluene sulphonic acid 1 aq. and 53.5 g of a 70% by weight - hydrogen peroxide solution (1.1 moles) were added, with stirring, 36 g (0.5 moles) of isobutyraldehyde over a period of 15 minutes at 20° C. (cooling). After 1 hour at 20° C. the reaction flask was evacuated with slow azeotropic distillation at 35°0 C. 
     In 3 hours 25 ml of water containing about 5.6% hydrogen peroxide were removed from the reaction mixture. 
     The reaction mixture was cooled to 20° C. and the peroxide solution was susequently washed with a concentrated ammonium sulphate solution and with an 8% by weight sodium carbonate solution. To the resulting solution (about 290 g) were added 100 g of dimethyl phthalate and 40 g of hexylene glycol, which after removal of butyl acetate by distillation under reduced pressure yielded about 210 g of peroxide solution containing 8.0 % of active oxygen. By D.L.C. analysis it was shown that about 85% of the AO content was in the form of the dihydroperoxide 2,7-dimethyl-3,6-dihydroxyperoxy-4,5-dioxaoctane. In the same way solutions were prepared of 4,7-dihydroperoxy5,6-dioxadecane starting from n-butylaldehyde, of 1,6-diphenyl2,5dihydroperoxy-3,4-dioxahexane starting from phenylacetaldehyde, of 7,10-dihydroperoxy-8,9-dioxahexadecane starting from heptanal, of 5,10-diethyl-6,9-dihydroperoxy-7,8dioxatetradecane starting from 2-ethylhexannal, and of 2,4,4,11,11,13-hexamethyl-6,9-dihydroperoxy-7,8-dioxatetradecane starting from 3,3,5-trimethyl hexanal. 
     EXAMPLE 4 
     To 100 parts by weight of the afore-described &#34;standard&#34; unsaturated polyester resin were added 0.5 parts by weight of a solution of cobalt octoate in xylene, containing 1 % by weight of cobalt and 2.4 parts by weight of a peroxide composition which contained a bis(1-hydroperoxyalkyl) peroxide with 11/2 atoms of active oxygen per starting aldehyde. Of the mixture the gel time at 20° C. and the Persoz hardness were determined after 1, 2, 4 and 6 hours. 
     Corresponding measurements were carried out on a mixture containing the same accelerator and the same peroxide, although in different amounts. The same measurements were carried out on mixtures containing the same accelerator but different peroxide compositions according to the invention. The used peroxide compositions according to the invention and the mixtures prepared, and the gel times and the hardness values are shown in the following table. 
     For comparison the bis(1-hydroxyheptyl) peroxide with an active oxygen content of 6.1 % by weight (peroxide P) is included in the table. 
     
         ______________________________________                                    
Peroxide                                                                  
        derived from  Act. O-content in % by wt                           
______________________________________                                    
A       n-butylraldehyde                                                  
                      8.64                                                
B       iso-butylraldehyde                                                
                      6.43                                                
C       phenylacetaldehyde                                                
                      6.90                                                
D       heptanal      7.30                                                
E       dodecanal     10.70                                               
______________________________________                                    
 
    
     
                                           TABLE I                                 
__________________________________________________________________________
RESIN       100                                                           
               100                                                        
                  100                                                     
                     100                                                  
                        100                                               
                           100                                            
                              100                                         
                                 100                                      
                                    100                                   
                                       100                                
                                          100                             
                                             100                          
__________________________________________________________________________
Cobalt accelerator                                                        
            0.5                                                           
               1.0                                                        
                  0.5                                                     
                     1.0                                                  
                        0.5                                               
                           1.0                                            
                              0.5                                         
                                 1.0                                      
                                    0.5                                   
                                       1.0                                
                                          0.5                             
                                             1.0                          
  A         2.4                                                           
               1.2                                                        
                  -- -- -- -- -- -- -- -- -- --                           
  B         -- -- 3.3                                                     
                     1.6                                                  
                        -- -- -- -- -- -- -- --                           
  C         -- -- -- -- 3.0                                               
                           1.5                                            
                              -- -- -- -- -- --                           
  D         -- -- -- -- -- --  2.88                                       
                                  1.44                                    
                                    -- -- -- --                           
  E         -- -- -- -- -- -- -- -- 2.0                                   
                                       1.0                                
                                          -- --                           
  P         -- -- -- -- -- -- -- -- -- -- 3.4                             
                                             1.7                          
Gel time (min.) 20° C.                                             
             29                                                           
                33                                                        
                   41                                                     
                      55                                                  
                         28                                               
                            29                                            
                               32                                         
                                  49                                      
                                     14                                   
                                        18                                
                                          5  4                            
Persoz hardness                                                           
after 1 hour                                                              
             63                                                           
                31                                                        
                   41                                                     
                     --  56                                               
                            41                                            
                               40                                         
                                  39                                      
                                    118                                   
                                        37                                
                                          102                             
                                              78                          
after 2 hours                                                             
             91                                                           
                69                                                        
                  106                                                     
                      88                                                  
                         84                                               
                            71                                            
                               86                                         
                                  54                                      
                                    137                                   
                                        89                                
                                          125                             
                                             112                          
after 4 hours                                                             
            123                                                           
               114                                                        
                  140                                                     
                     128                                                  
                        112                                               
                           103                                            
                              115                                         
                                 112                                      
                                    156                                   
                                       123                                
                                          -- --                           
after 6 hours                                                             
            129                                                           
               127                                                        
                  152                                                     
                     141                                                  
                        132                                               
                           120                                            
                              132                                         
                                 128                                      
                                    162                                   
                                       143                                
                                          170                             
                                             152                          
__________________________________________________________________________
 
    
     EXAMPLE 5 
     To 100 parts by weight of the afore-described &#34;standard&#34; unsaturated polyester resin were added 0.5 parts by weight of the cobalt octoate solution described in Example 4 and 2.5 parts by weight of a peroxide composition according to the invention, which contained an alkyl aldehyde peroxide with 2 atoms of active oxygen per starting aldehyde. 
     Of the mixture the gel time at 20° C. and the Persoz hardness after 1, 2, 4 and 6 hours were determined. Corresponding measurements were carried out on a mixture which contained the same accelerator and the same peroxide, although in different quantities. The same measurements were carried out on mixtures containing the same accelerator but different peroxide compositions according to the invention. 
     The used peroxide compositions according to the invention and the prepared mixtures, the gel times and the hardness values are give in the following table. For comparison the bis(1-hydroxy-2-phenylethyl) peroxide with an active oxygen content of 5.84% by weight (peroxide Q) is included in the table 
     
         ______________________________________                                    
Peroxide                                                                  
        Derived from  Act. O-content in wt %                              
______________________________________                                    
F       n-butylaldehyde                                                   
                      8.26                                                
G       phenylacetaldehyde                                                
                      6.58                                                
H       heptanal      6.95                                                
J       isobutylraldehyde                                                 
                      5.60                                                
K       2-methylpentanol                                                  
                      10.78                                               
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                                           TABLE II                                
__________________________________________________________________________
RESIN       100                                                           
               100                                                        
                  100                                                     
                     100                                                  
                        100                                               
                           100                                            
                              100                                         
                                 100                                      
                                    100                                   
                                       100                                
                                          100                             
                                             100                          
__________________________________________________________________________
Cobalt accelerator                                                        
            0.5                                                           
               1.0                                                        
                  0.5                                                     
                     1.0                                                  
                        0.5                                               
                           1.0                                            
                              0.5                                         
                                 1.0                                      
                                    0.5                                   
                                       1.0                                
                                          0.5                             
                                             1.0                          
  F         2.5                                                           
                1.25                                                      
                  -- -- -- -- -- -- -- -- -- --                           
  G         -- -- 3.2                                                     
                     1.6                                                  
                        -- -- -- -- -- -- -- --                           
  H         -- -- -- -- -- -- -- -- -- -- -- --                           
  J         -- -- -- -- -- --  3.75                                       
                                  1.88                                    
                                    -- -- -- --                           
  K         -- -- -- -- -- -- -- --  1.95                                 
                                        0.97                              
                                          -- --                           
  Q         -- -- -- -- -- -- -- -- -- -- 3.6                             
                                             1.8                          
Gel time in min. 20° C.                                            
             18                                                           
                19                                                        
                   15                                                     
                      14                                                  
                         16                                               
                            16                                            
                               13                                         
                                  16                                      
                                     16                                   
                                        13                                
                                          7  4                            
Persoz hardness                                                           
after 1 hour                                                              
             62                                                           
                58                                                        
                   93                                                     
                      93                                                  
                         52                                               
                            58                                            
                               50                                         
                                  89                                      
                                     65                                   
                                       114                                
                                           92                             
                                              79                          
after 2 hours                                                             
             85                                                           
                82                                                        
                  115                                                     
                     112                                                  
                         73                                               
                            80                                            
                               69                                         
                                 109                                      
                                     83                                   
                                       128                                
                                          109                             
                                             101                          
after 4 hours                                                             
            115                                                           
               115                                                        
                  127                                                     
                     126                                                  
                        119                                               
                           113                                            
                              104                                         
                                 138                                      
                                    111                                   
                                       141                                
                                          137                             
                                             128                          
after 6 hours                                                             
            133                                                           
               131                                                        
                  148                                                     
                     150                                                  
                        127                                               
                           129                                            
                              124                                         
                                 152                                      
                                    122                                   
                                       168                                
                                          148                             
                                             143                          
__________________________________________________________________________
 
    
     EXAMPLE 6 
     To 100 parts by weight of the afore-described &#34;standard&#34; unsaturated polyester resin were added 0.5 parts by weight of the cobalt solution described in Example 4 and 1.33 parts by weight of a peroxide composition according to the invention, which in addition to an alkylaldehyde peroxide with 11/2 atoms of active oxygen contained an alkylaldehyde peroxide with 2 atoms of active oxygen per starting aldehyde. Of the mixture the gel time at 20° C. and the Persoz hardness after 1, 2, 4 and 6 hours were determined. 
     Corresponding measurements were carried out as described in Examples 4 and 5. The used peroxide compositions according to the invention and the prepared mixtures, the gel times and the hardness values are listed in the following table 
     
                       TABLE III                                                   
______________________________________                                    
                Act. O-content in wt %                                    
Peroxide                                                                  
        Derived from  total    11/2   2                                   
______________________________________                                    
L       heptanal      7.90     3.00   4.90                                
M       heptanal      5.50     2.90   2.60                                
N       diethylacetaldehyde                                               
                      9.40     5.00   4.40                                
O       2,2-dimethyl-3-                                                   
                      4.50     1.80   2.70                                
        hydroxy propanol                                                  
______________________________________                                    
 
    
     The cured unsaturated polyester/monomer mixture thus obtained can be used e.g. for the manufacture of casings for refrigerators, automobile parts, articles for the electronic industry, glass reinforced pipes, drains, tanks and the like. 
     
                                           TABLE III                               
__________________________________________________________________________
RESIN       100                                                           
               100                                                        
                  100                                                     
                     100                                                  
                        100                                               
                           100                                            
                              100                                         
                                 100                                      
                                    100                                   
                                       100                                
                                          100                             
                                             100                          
                                                100                       
                                                   100                    
__________________________________________________________________________
Cobalt accelerator                                                        
            0.5                                                           
               1.0                                                        
                  0.5                                                     
                     1.0                                                  
                        0.5                                               
                           1.0                                            
                              0.5                                         
                                 1.0                                      
                                    0.5                                   
                                       1.0                                
                                          0.5                             
                                             1.0                          
                                                0.5                       
                                                   1.0                    
  L          1.33                                                         
                2.66                                                      
                  -- -- -- -- -- -- -- -- -- -- -- --                     
  M         -- -- 1.9                                                     
                     3.8                                                  
                        -- -- -- -- -- -- -- -- -- --                     
  N         -- -- -- -- 1.1                                               
                           1.1                                            
                              2.2                                         
                                 -- -- -- -- -- -- --                     
  O         -- -- -- -- -- -- -- 2.3                                      
                                    2.3                                   
                                       4.7                                
                                          -- -- -- --                     
  P         -- -- -- -- -- -- -- -- -- -- 3.4                             
                                             1.7                          
                                                -- --                     
  Q         -- -- -- -- -- -- -- -- -- -- -- -- 3.6                       
                                                   1.8                    
Gel time in min. 20° C.                                            
             13                                                           
                18                                                        
                   20                                                     
                      12                                                  
                         14                                               
                            17                                            
                               14                                         
                                  18                                      
                                     15                                   
                                        15                                
                                          5  4  7  4                      
Persoz hardness                                                           
after 1 hour                                                              
             35                                                           
                56                                                        
                   35                                                     
                      46                                                  
                         49                                               
                            70                                            
                               76                                         
                                  40                                      
                                     60                                   
                                        54                                
                                          102                             
                                              78                          
                                                 92                       
                                                    79                    
after 2 hours                                                             
             52                                                           
                76                                                        
                   42                                                     
                      76                                                  
                         71                                               
                            93                                            
                               98                                         
                                  61                                      
                                     79                                   
                                        76                                
                                          125                             
                                             112                          
                                                108                       
                                                   101                    
after 4 hours                                                             
             81                                                           
               105                                                        
                   83                                                     
                     104                                                  
                         99                                               
                           125                                            
                              121                                         
                                  83                                      
                                    104                                   
                                        97                                
                                          -- -- 137                       
                                                   128                    
after 6 hours                                                             
            102                                                           
               122                                                        
                   99                                                     
                     127                                                  
                        118                                               
                           128                                            
                               96                                         
                                  96                                      
                                    113                                   
                                       110                                
                                          170                             
                                             132                          
                                                148                       
                                                   143                    
__________________________________________________________________________