Methods of Mercaptanizing Unsaturated Compounds and Compositions Produced Therefrom

Abstract

The present invention discloses polythiol compositions containing polythiol molecules having both thiol groups and intermolecular sulfide groups. Processes for producing such polythiol compositions also are described.

We claim: 
     
         1 . A polythiol composition comprising polythiol molecules having the structures: 
       
         
           
           
               
               
           
         
       
     
     
         2 . The composition of  claim 1 , further comprising a polythiol molecule having the structure: 
       
         
           
           
               
               
           
         
       
     
     
         3 . The composition of  claim 1 , wherein polythiol molecules having at least three SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 1000:1;   an average of from 0.1 mole % to 33 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   an average of from 67 mole % to 99 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   a mercaptan equivalent weight in a range from 118 to 190 g/eq; or   any combination thereof.   
     
     
         4 . The composition of  claim 1 , wherein polythiol molecules having at least three SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 3:1 to 50:1;   an average of from 2 mole % to 20 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   an average of from 75 mole % to 98 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   a mercaptan equivalent weight in a range from 120 to 140 g/eq; or   any combination thereof.   
     
     
         5 . An article of manufacture comprising the polythiol composition of  claim 1 . 
     
     
         6 . The article of  claim 5 , wherein the article is a coating, a paint, or an adhesive. 
     
     
         7 . The composition of  claim 1 , wherein the composition is produced by a process comprising:
 1) contacting:
 a) 1,3,5-triallylisocyanurate; 
 b) H 2 S; and 
 c) a phosphite compound; and 
   2) forming the polythiol composition;   
       wherein a molar ratio of H 2 S to carbon-carbon double bonds of 1,3,5-triallylisocyanurate is in a range from 5:1 to 500:1. 
     
     
         8 . The composition of  claim 7 , wherein the phosphite compound comprises a compound having the formula:
   P(OR 1 ) 3 ;   
       wherein each R 1  is independently a C 1 -C 10  hydrocarbyl group. 
     
     
         9 . The composition of  claim 7 , wherein:
 the molar ratio of H 2 S to carbon-carbon double bonds of 1,3,5-triallylisocyanurate is in a range from 15:1 to 150:1; and   a molar ratio of the phosphite compound to carbon-carbon double bonds of the unsaturated compound is in a range from 0.0005:1 to 0.10:1.   
     
     
         10 . The composition of  claim 7 , wherein the polythiol composition is formed in the presence of ultraviolet light. 
     
     
         11 . The composition of  claim 7 , wherein the polythiol composition is formed in the presence of ultraviolet light and a photoinitiator, wherein the photoinitiator is present at an amount in a range from 0.05 to 5 wt. %, based on the weight of 1,3,5-triallylisocyanurate. 
     
     
         12 . The composition of  claim 7 , wherein the polythiol composition is formed in the presence of a hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ether solvent, or any combination thereof. 
     
     
         13 . The composition of  claim 7 , wherein the process further comprises a step of removing at least a portion of the H 2 S, of the phosphite compound, of 1,3,5-triallylisocyanurate, of compounds having two or less sulfur atoms, or combinations thereof, from the polythiol composition. 
     
     
         14 . The composition of  claim 13 , wherein the H 2 S, the phosphite compound, 1,3,5-triallylisocyanurate, the compounds having two or less sulfur atoms, or combinations thereof, are removed by wiped film evaporation, distillation, short path distillation, or a combination thereof. 
     
     
         15 . A polythiol composition comprising polythiol molecules having the structures: 
       
         
           
           
               
               
           
         
       
     
     
         16 . The composition of  claim 15 , further comprising: 
       
         
           
           
               
               
           
         
       
     
     
         17 . The composition of  claim 15 , wherein polythiol molecules having at least three SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 1000:1;   an average of from 0.1 mole % to 33 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   an average of from 67 mole % to 99 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   a mercaptan equivalent weight in a range from 120 to 190 g/eq; or   any combination thereof.   
     
     
         18 . The composition of  claim 15 , wherein polythiol molecules having at least three SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 3:1 to 50:1;   an average of from 2 mole % to 20 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   an average of from 75 mole % to 98 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;   a mercaptan equivalent weight in a range from 122 to 140 g/eq; or   any combination thereof.   
     
     
         19 . An article of manufacture comprising the polythiol composition of  claim 15 . 
     
     
         20 . The composition of  claim 15 , wherein the composition is produced by a process comprising:
 1) contacting:
 a) pentaerythritol triallyl ether; 
 b) H 2 S; and 
 c) a phosphite compound; and 
   2) forming the polythiol composition;   
       wherein a molar ratio of H 2 S to carbon-carbon double bonds of pentaerythritol triallyl ether is in a range from 5:1 to 500:1. 
     
     
         21 . A polythiol composition comprising polythiol molecules having the formulas: 
       
         
           
           
               
               
           
         
         wherein R is a C 1 -C 18  hydrocarbyl group. 
       
     
     
         22 . The composition of  claim 21 , further comprising polythiol molecules having the formula: 
       
         
           
           
               
               
           
         
         wherein R is a C 1 -C 18  hydrocarbyl group. 
       
     
     
         23 . The composition of  claim 21 , wherein R is an ethyl group. 
     
     
         24 . The composition of  claim 23 , wherein polythiol molecules having at least two SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 1:1.5 to 1000:1;   an average of from 0.1 mole % to 60 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least two SH groups;   an average of from 40 mole % to 99 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least two SH groups;   a mercaptan equivalent weight in a range from 142 to 350 g/eq; or   any combination thereof.   
     
     
         25 . The composition of  claim 23 , wherein polythiol molecules having at least two SH groups have:
 an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 50:1;   an average of from 5 mole % to 30 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least two SH groups;   an average of from 70 mole % to 97 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least two SH groups;   a mercaptan equivalent weight in a range from 145 to 165 g/eq; or   any combination thereof.   
     
     
         26 . An article of manufacture comprising the polythiol composition of  claim 23 . 
     
     
         27 . The composition of  claim 21 , wherein the composition is produced by a process comprising:
 1) contacting a compound having the formula:   
       
         
           
           
               
               
           
         
          wherein R is a C 1 -C 18  hydrocarbyl group;
 b) H 2 S; and 
 c) a phosphite compound; and 
 
         2) forming the polythiol composition; 
       
       wherein a molar ratio of H 2 S to carbon-carbon double bonds of the compound having formula (IV) is in a range from 5:1 to 500:1.