Phenolic epoxy compounds

Abstract

Disclosed herein are compositions and methods of making phenolic compounds, and resins comprising these phenolic compounds. The compounds include multifunctional epoxies, amino glycidyl derivatives, and multi-functional amines prepared from hydroxymethyl derivatives of phenols and bisphenols

What is claimed is: 
     
         1 . A method of preparing a compound of Formula I: 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  is H or Z; 
         R 2  is —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 NH 2 ) 2 , —O—Z, —CH 2 —O—Z, —CH 2 CH 2 —O—Z, —CH 2 OH, or —O—C—(CH 3 ) 3 ; 
         R 3  is —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 NH 2 ) 2 , —O—Z, —CH 2 —O—Z, —CH 2 CH 2 —O—Z, —CH 2 OH, or —O—C—(CH 3 ) 3 , 
         R 4  is —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 NH 2 ) 2 , —O—Z, —CH 2 —O—Z, —CH 2 CH 2 —O—Z, —CH 2 OH, or —O—C—(CH 3 ) 3 ; and 
         Z is 
       
       
         
           
           
               
               
           
         
         the method comprising: 
         contacting a phenolic compound with a formaldehyde or a paraformaldehyde to form a hydroxymethyl compound; and 
         contacting the hydroxymethyl compound with an epihalohydrin compound, a diethanolamine compound, or an ammonia to form the compound. 
       
     
     
         2 . The method of  claim 1 , wherein the phenolic compound is phenol, bisphenol A, bisphenol F, bisphenol S, bisphenol sulphone, bisphenol sulfoxide, bisphenol chloral, bisphenolvinylidene dichloride, or bisphenol methylenedifluoride. 
     
     
         3 . The method of  claim 1 , wherein the hydroxymethyl compound is trihydroxymethyl phenol, tetrahydroxymethyl bisphenol A, tetrahydroxymethyl bisphenol F, tetrahydroxymethyl bisphenol S, tetrahydroxymethyl bisphenol sulphone, tetrahydroxymethyl bisphenol sulfoxide, tetrahydroxymethyl bisphenol chloral, tetrahydroxymethyl bisphenolvinylidene dichloride, or tetrahydroxymethyl bisphenol methylenedifluoride. 
     
     
         4 . The method of  claim 1 , wherein contacting the phenolic compound with the formaldehyde or the paraformaldehyde comprises contacting about 1 mole of the phenolic compound with about 3 moles to about 5 moles of the formaldehyde or the paraformaldehyde in presence of a basic catalyst. 
     
     
         5 . The method of  claim 4 , wherein contacting the phenolic compound with the formaldehyde or the paraformaldehyde in the presence of the basic catalyst comprises mixing the phenolic compound, the formaldehyde or the paraformaldehyde, and the basic catalyst in a solution having a pH of about 8 to about 10. 
     
     
         6 . The method of  claim 4 , wherein contacting the phenolic compound with the formaldehyde or the paraformaldehyde in the presence of the basic catalyst comprises heating the phenolic compound, the formaldehyde or the paraformaldehyde, and the basic catalyst to a temperature of about 50° C. to about 70° C. 
     
     
         7 . The method of  claim 4 , wherein contacting the phenolic compound with the formaldehyde or the paraformaldehyde in the presence of the basic catalyst comprises heating the phenolic compound, the formaldehyde or the paraformaldehyde, and the basic catalyst for about 2 hours to about 6 hours. 
     
     
         8 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound comprises contacting about 1 mole of the hydroxymethyl compound with about 2 moles to about 10 moles of the epihalohydrin compound in presence of a reaction catalyst. 
     
     
         9 . The method of  claim 8 , wherein the reaction catalyst is selected from the group consisting of MgClO 4 , LiCl, LiOH, SnF 2 , LiClO 4 , or combination thereof. 
     
     
         10 . The method of  claim 8 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in the presence of the reaction catalyst comprises heating the hydroxymethyl compound, the epihalohydrin compound, and the reaction catalyst to a temperature of about 50° C. to about 90° C. 
     
     
         11 . The method of  claim 8 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in the presence of the reaction catalyst comprises heating the hydroxymethyl compound, the epihalohydrin compound, and the reaction catalyst for about 2 hours to about 6 hours. 
     
     
         12 . The method of  claim 8 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in the presence of the reaction catalyst comprises adding an organic solvent, wherein the organic solvent is selected from the group consisting of 1-butanol, a secondary butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-phenoxyethanol, 1,4-dioxane, 1,3-dioxane, diethoxyethane, acetonitrile, dimethyl sulfoxide, dimethyl formamide, or combination thereof. 
     
     
         13 . The method of  claim 8 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in the presence of the reaction catalyst comprises heating the hydroxymethyl compound, the epihalohydrin compound, and the reaction catalyst along with a phase transfer catalyst. 
     
     
         14 . The method of  claim 11 , wherein the phase transfer catalyst is selected from the group consisting of benzyltrimethylammonium bromide, cetyltrimethylammonium bromide, tetrabutylammonium hydroxide, tetrabutyl ammonium chloride, or combination thereof. 
     
     
         15 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the diethanolamine compound comprises contacting about 1 mole of the hydroxymethyl compound with about 2 moles to about 10 moles of the diethanolamine compound in presence of a reaction catalyst. 
     
     
         16 . The method of  claim 15 , wherein the reaction catalyst is selected from the group consisting of MgClO 4 , LiCl, LiOH, SnF 2 , LiClO 4 , or combination thereof. 
     
     
         17 . The method of  claim 15 , wherein contacting the hydroxymethyl compound with the diethanolamine compound in the presence of the reaction catalyst comprises heating the hydroxymethyl compound, the diethanolamine compound, and the reaction catalyst to a temperature of about 50° C. to about 70° C. 
     
     
         18 . The method of  claim 15 , wherein contacting the hydroxymethyl compound with the diethanolamine compound in the presence of the reaction catalyst comprises heating the hydroxymethyl compound, the diethanolamine compound, and the reaction catalyst for about 2 hours to about 6 hours. 
     
     
         19 . The method of  claim 15 , wherein contacting the hydroxymethyl compound with the diethanolamine compound in the presence of the reaction catalyst further comprises adding an organic solvent selected from the group consisting of acetone, methyl ethyl ketone, methanol, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane, dimethyl sulfoxide, dimethyl formamide, or combination thereof. 
     
     
         20 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the ammonia comprises contacting about 1 mole of the hydroxymethyl compound with about 1 mole to about 1.5 moles of the ammonia in an autoclave under a pressure of about 1 atmospheric pressure to about 1.5 atmospheric pressures, and heated to a temperature of about 50° C. to about 70° C.