Alkoxylations of High Melting Point Substrates in Ketone Solvents

Abstract

Substrate or starting compounds which have high melting points, for instance, having a melting point of 150° C. or higher and having at least one active hydrogen may be reacted with one or more alkylene oxide in a ketone solvent at reduced temperatures compared with conventional, molten methods to give an adduct product having reduced color. By at least partially alkoxylating the substrate, its potential for crystallization is disrupted and the partially alkoxylated substrate has a lower melting point than the original substrate permitting it to be more readily further alkoxylated at the reaction temperature. Suitable ketone solvents include, but are not necessarily limited to, methyl isobutyl ketone, diethyl ketone, methyl ethyl ketone, and mixtures thereof. The alkoxylation reaction may be conducted at a temperature in the range of about 30 to about 140° C. Suitable catalysts may include tertiary amines or caustic compounds such as NaOH and KOH.

1 . A method for producing an alkoxylated product comprising:
 mixing a compound selected from the group consisting of alkylene oxide and arylene oxide, with a substrate having a melting point of 150° C. or higher and having at least one active hydrogen atom with a catalyst in the presence of a ketone solvent to give a reaction mixture, where the substrate is selected from the group consisting of diols, polyols, phenols, polyphenols, primary amines, secondary amines, polyfunctional amines, compounds with both amino and hydroxyl group(s), carboxylic acids, compounds with both amino and carboxylic group(s), and mixtures thereof, where the catalyst is selected from the group consisting of:
 a tertiary amine catalyst, and 
 a caustic compound selected from the group consisting of potassium hydroxide and sodium hydroxide, 
   reacting the compound with the substrate in the reaction mixture at a reaction temperature in the range of about 30 to 140° C. to give an at least partially alkoxylated substrate sufficiently alkoxylated to lower its melting point below the reaction temperature; and   continuing to alkoxylate the at least partially alkoxylated substrate.   
     
     
         2 . The method of  claim 1  where the compound selected from the group consisting of alkylene oxide and arylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and mixtures thereof. 
     
     
         3 . The method of  claim 1  where the ketone solvent is selected from the group consisting of methyl isobutyl ketone, diethyl ketone, methyl ethyl ketone, acetone, and mixtures thereof. 
     
     
         4 . The method of  claim 1  where the reaction is conducted at a pressure in the range from about 5 psig (about 0.03 MPa) to about 100 psig (0.7 MPa). 
     
     
         5 . The method of  claim 1  where the catalyst is a tertiary amine catalyst and the method is practiced in the absence of a dehydration step. 
     
     
         6 . The method of  claim 6  where the method is practiced in the absence of a neutralization step. 
     
     
         7 . The method of  claim 1  where the catalyst is a caustic compound and the method further comprises:
 heating the reaction mixture to dehydrate it; and   neutralizing the reaction mixture.   
     
     
         8 . The method of  claim 1  where the substrate is bisphenol A. 
     
     
         9 . A method for producing an alkoxylated product comprising:
 mixing a substrate having a melting point of 150° C. or higher and having at least one active hydrogen atom with a ketone solvent and a caustic compound catalyst to give a mixture, where the substrate is selected from the group consisting of diols, polyols, phenols, polyphenols, primary amines, secondary amines, polyfunctional amines, compounds with both amino and hydroxyl group(s), carboxylic acids, compounds with both amino and carboxylic group(s), and mixtures thereof, where the catalyst is selected from the group consisting of potassium hydroxide and sodium hydroxide;   heating the mixture to dehydrate it;   adding a compound selected from the group consisting of alkylene oxide and arylene oxide, to the mixture to give a reaction mixture;   reacting the compound with the substrate in the reaction mixture at a temperature in the range of about 30 to 140° C. to give an at least partially alkoxylated substrate sufficiently alkoxylated to lower its melting point below the reaction temperature; and;   continuing to alkoxylate the at least partially alkoxylated substrate.   
     
     
         10 . The method of  claim 9  where the compound selected from the group consisting of alkylene oxide and arylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and styrene oxide and mixtures thereof. 
     
     
         11 . The method of  claim 9  where the ketone solvent is selected from the group consisting of methyl isobutyl ketone, diethyl ketone, methyl ethyl ketone, acetone, and mixtures thereof. 
     
     
         12 . The method of  claim 9  where the reaction is conducted at a pressure in the range from about 5 psig (about 0.03 MPa) to about 100 psig (0.7 MPa). 
     
     
         13 . The method of  claim 9  where the substrate is a bisphenol A. 
     
     
         14 . A method for producing an alkoxylated product comprising:
 mixing a substrate having a melting point of 150° C. or higher and having at least one active hydrogen atom with a ketone solvent and a tertiary amine catalyst to give a mixture, where the substrate is selected from the group consisting of diols, polyols, phenols, polyphenols, primary amines, secondary amines, polyfunctional amines, compounds with both amino and hydroxyl group(s), carboxylic acids, compounds with both amino and carboxylic group(s), and mixtures thereof;   adding a compound selected from the group consisting of alkylene oxide and arylene oxide, to the mixture to give a reaction mixture;   reacting the compound with the substrate in the reaction mixture at a temperature in the range of about 30 to 140° C. to give an at least partially alkoxylated substrate sufficiently alkoxylated to lower its melting point below the reaction temperature; and   continuing to alkoxylate the at least partially alkoxylated substrate.   
     
     
         15 . The method of  claim 14  where the compound selected from the group consisting of alkylene oxide and arylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and styrene oxide and mixtures thereof. 
     
     
         16 . The method of  claim 14  where the ketone solvent is selected from the group consisting of methyl isobutyl ketone, diethyl ketone, methyl ethyl ketone, acetone, and mixtures thereof. 
     
     
         17 . The method of  claim 14  where the reaction is conducted at a pressure in the range from about 5 psig (about 0.03 MPa) to about 100 psig (0.7 MPa). 
     
     
         18 . The method of  claim 14  where the method is practiced in the absence of a dehydration step. 
     
     
         19 . The method of  claim 14  where the method is practiced in the absence of a neutralization step. 
     
     
         20 . The method of  claim 14  where the catalyst is selected from the group consisting of triethylamine, tributylamine, methyl alkyl amines, dimethyl alkyl amines, and mixtures thereof. 
     
     
         21 . The method of  claim 14  where the substrate is a bisphenol A. 
     
     
         22 . A method for producing an alkoxylated product comprising:
 mixing a compound selected from the group consisting of alkylene oxide and arylene oxide, with a prepolymer having at least one active hydrogen atom with a catalyst in the presence of a ketone solvent to give a reaction mixture, where the prepolymer is made from a substrate having a melting point of 150° C. or higher and selected from the group consisting of diols, polyols, phenols, polyphenols, primary amines, secondary amines, polyfunctional amines, compounds with both amino and hydroxyl group(s), carboxylic acids, compounds with both amino and carboxylic group(s), and mixtures thereof, where the catalyst is selected from the group consisting of:
 a tertiary amine catalyst, and 
 a caustic compound selected from the group consisting of potassium hydroxide and sodium hydroxide; 
   reacting the compound with the prepolymer in the reaction mixture at a temperature in the range of about 30 to 140° C. and a pressure in the range of from about 5 to about 100 psig (about 0.03 to about 0.7 MPa) to give an at least partially alkoxylated substrate sufficiently alkoxylated to lower its melting point below the reaction temperature; and; and   continuing to alkoxylate the at least partially alkoxylated substrate.