Methods and Systems for Making Thiol Compounds from Terminal Olefinic Compounds

Abstract

The application discloses thiol ester molecules and α-hydroxy thiol ester molecules having a thiol group located on one of the final two carbon atoms in a carbon chain or a terminal or α-hydroxyl groups, respectively. The disclosed thiol ester molecules and or α-hydroxyl thiol ester molecules es may be made from unsaturated ester molecules having one or more terminal alkene groups. The disclosed techniques also provide methods for making unsaturated ester molecules having one or more terminal alkene groups by the metathesis of unsaturated esters having one or more internal carbon-carbon double bonds (e.g. natural source oils). The thiol ester molecules or α-hydroxy thiol ester molecule may be used in reactions with isocyanate monomers, epoxide monomer, or material having multiple alkene groups to make sealants, coatings, adhesives, and other products.

1 . A thiol ester composition comprising thiol ester molecules, the thiol ester molecules having ester linkages comprising:
 a) a residue of a polyol; and   b) carboxylic acid residues having;
 i) at least 4 carbon atoms; and 
 ii) a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom; and 
   wherein the average ratio of carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom to hydroxyl groups of the polyol of the residue of the polyol is greater than 0.70:1.   
     
     
         2 . The thiol ester composition of  claim 1 , wherein the carboxylic acid residues are substantially devoid of hydroxyl groups. 
     
     
         3 . The thiol ester composition of  claim 2 , wherein the polyol of the residue of polyol was a diol, triol, or a tetraol. 
     
     
         4 . The thiol ester composition of  claim 2 , wherein the polyol of the residue of polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof. 
     
     
         5 . The thiol ester composition of  claim 2 , wherein the polyol of the residue of the polyol was glycerol. 
     
     
         6 . The thiol ester composition of  claim 2 , wherein the carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom have from 10 to 11 carbon atoms. 
     
     
         7 . The thiol ester composition of  claim 2 , wherein the carboxylic acid residues having the thiol group located on the terminal carbon atom or the carbon atom adjacent to the terminal carbon atom have only 10 carbon atoms. 
     
     
         8 . The thiol ester composition of  claim 2 , wherein the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %. 
     
     
         9 . The thiol ester composition of  claim 2 , wherein an average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1. 
     
     
         10 . The thiol ester composition of  claim 2 , wherein the polyol of the residue of the polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof, the carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom have from 10 to 111 carbon atoms, an average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1, and wherein the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %. 
     
     
         11 . The thiol ester composition of  claim 1 , wherein the carboxylic acid residue having the thiol group located on the terminal carbon atom or the carbon atom adjacent to the terminal carbon atom is a carboxylic acid residue having a terminal α-hydroxy thiol group. 
     
     
         12 . The thiol ester composition of  claim 11 , wherein the polyol of the residue of polyol was a diol, triol, or a tetraol. 
     
     
         13 . The thiol ester composition of  claim 11 , wherein the polyol of the residue of polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof. 
     
     
         14 . The thiol ester composition of  claim 11 , wherein the polyol of the residue of the polyol was glycerol. 
     
     
         15 . The thiol ester composition of  claim 11 , wherein the having a terminal α-hydroxy thiol group have from 10 to 11 carbon atoms. 
     
     
         16 . The thiol ester composition of  claim 11 , wherein the carboxylic acid residues having the thiol group located on the terminal carbon atom or the carbon atom adjacent to the terminal carbon atom have only 10 carbon atoms. 
     
     
         17 . The thiol ester composition of  claim 11 , wherein the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight percent. 
     
     
         18 . The thiol ester composition of  claim 11 , wherein the polyol of the residue of polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof, the carboxylic acid residues having a terminal α-hydroxy thiol group have from 10 to 11 carbon atoms, and the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %. 
     
     
         19 . A method of producing the composition of  claim 2 , the method comprising:
 a) contacting ethylene and natural source oil with a metathesis catalyst composition;   b) forming unsaturated ester molecules having terminal carbon-carbon double bonds at metathesis conditions capable of forming the unsaturated ester molecules having terminal carbon-carbon double bonds;   c) contacting the unsaturated ester molecules having terminal carbon-carbon double bonds and hydrogen sulfide; and   d) forming the thiol ester composition comprising thiol ester molecules having the thiol group located on the terminal carbon atom at conditions capable of forming thiol ester molecules having the thiol group located on the terminal carbon.   
     
     
         20 . The method of  claim 19 , wherein the metathesis catalyst composition comprises ruthenium carbene metathesis catalyst or a molybdenum carbene metathesis catalyst. 
     
     
         21 . The method of  claim 19 , wherein the metathesis catalyst comprises dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium. 
     
     
         22 . The method of  claim 19 , wherein the metathesis conditions include a ethylene partial pressure ranging from 50 to 3000 psig and a temperature ranging from 5° C. to 100° C. 
     
     
         23 . The method of  claim 19 , wherein the natural source oil comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, or a walnut oil, or any combination thereof. 
     
     
         24 . The method of  claim 19 , wherein the natural source oil is soybean oil, corn oil, canola oil, or castor bean oil. 
     
     
         25 . The method of  claim 19 , wherein the natural source oil is soybean oil. 
     
     
         26 . A method of producing the thiol ester composition of  claim 11 , the method comprising:
 a) contacting ethylene and natural source oil with a metathesis catalyst composition;   b) forming unsaturated esters molecules having terminal carbon-carbon double bonds at metathesis conditions capable of forming the unsaturated ester molecules having terminal carbon-carbon double bonds;   c) contacting the unsaturated ester molecules having terminal carbon-carbon double bonds and an oxygen containing compound;   d) forming epoxide ester molecules having terminal epoxide groups at conditions capable of forming epoxide ester molecules having terminal epoxide groups;   e) contacting the epoxide ester composition and hydrogen sulfide; and   f) forming the thiol ester composition comprising thiol ester molecules at conditions capable of forming thiol ester molecules, the thiol ester molecules having ester linkages comprising:
 i) a residue of a polyol; and 
 ii) carboxylic acid residues having a terminal α-hydroxy thiol group. 
   
     
     
         27 . The method of  claim 26 , wherein the metathesis catalyst composition comprises ruthenium carbene metathesis catalyst or a molybdenum carbene metathesis catalyst. 
     
     
         28 . The method of  claim 26 , wherein the metathesis catalyst comprises dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium. 
     
     
         29 . The method of  claim 26 , wherein the metathesis conditions include a ethylene partial pressure ranging from 50 to 3000 psig and a temperature ranging from 5° C. to 100° C. 
     
     
         30 . The method of  claim 26 , wherein the natural source oil comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, or a walnut oil, or any combination thereof. 
     
     
         31 . The method of  claim 26 , wherein the natural source oil is soybean oil, corn oil, canola oil, or castor bean oil. 
     
     
         32 . The method of  claim 26 , wherein the natural source oil is soybean oil.