Multi-functional phenolic resins

Abstract

Disclosed herein are compositions and methods of making phenolic compounds and phenolic resins. The resins include multifunctional epoxies, amino glycidyl derivatives, alkanoate derivatives, alkyl ether derivatives, and multi-functional amines prepared from hydroxymethyl derivatives of novolac resin.

What is claimed is: 
     
         1 . A method of preparing a compound of formula I, 
       
         
           
           
               
               
           
         
         wherein:
 a is an integer from 1 to 10; 
 R 1  is H, Z, —C(═O)—CH═CH 2 , —(CH 2 —CH 2 —O) n H, —(CH 2 —CH 2 —CH 2 —O) n H, or —(CH 2 —CH 2 —O) n —(CH 2 —CH(CH 3 )—O) n H, where each n is, independently, an integer from 1 to 18; 
 each R 2  is, independently, H, Z, —C(═O)—CH═CH 2 , —(CH 2 —CH 2 —O) p H, —(CH 2 —CH 2 —CH 2 —O) p H, or —(CH 2 —CH 2 —O) p —(CH 2 —CH(CH 3 )—O) p H, where each p is, independently, an integer from 1 to 18; 
 R 3  is H, Z, —C(═O)—CH═CH 2 , —(CH 2 CH 2 —CH 2 —O) q H, —(CH 2 —CH 2 —CH 2 —O) q H, or —(CH 2 —CH 2 —O) q —(CH 2 —CH(CH 3 )—O) q H, where each q is, independently, an integer from 1 to 18; 
 R 4  is —NH 2 , —O—Z, —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 NH 2 ) 2 , —N(CH 2 CH 2 OH) 2 , —CH 2 —O—Z, —CH 2 —OH, —CH 2 —NH 2 , —N(CH 3 ) 2 , —O-(alkylene)-CH 3 , —CH 2 —Y, —NCO, —O—C(═O)—(CH 2 ) r —CH 3 , —NH—Z, —N[CH 2 O—C(═O)—CH═CH 2 ] 2 , —NH—C(═O)CH═CH 2 , —CH 2 CH 2 —O—Z, —CH 2 CH 2 OH, —O—C(═O)—CH═CH 2 , —N(CH 2 —CH 2 —NH 2 ) 2 , —(CH 2 —CH 2 —O) r H, —(CH 2 —CH 2 —CH 2 —O) r H, —N[CH 2 —CH 2 —O—C(═O)—CH═CH 2 ] 2 , or —N[CH 2 —CH 2 —NH—C(═O)—CH═CH 2 ] 2 , where each r is, independently, an integer from 1 to 18; 
 R 5  is —OH, —NH 2 , —O—Z, —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 NH 2 ) 2 , —N(CH 2 CH 2 OH) 2 , —CH 2 —O—Z, —CH 2 —OH, —CH 2 —NH 2 , —N(CH 3 ) 2 , —O-(alkylene)-CH 3 , —CH 2 —Y, —NCO, —O—C(═O)—(CH 2 ) t —CH 3 , —NH—Z, —N[CH 2 O—C(═O)—CH═CH 2 ] 2 , —NH—C(═O)CH═CH 2 , —CH 2 CH 2 —O—Z, —CH 2 CH 2 OH, —O—C(═O)—CH═CH 2 , —N(CH 2 —CH 2 —NH 2 ) 2 , —(CH 2 —CH 2 —O) t H, —(CH 2 —CH 2 —CH 2 —O) t H, —N[CH 2 —CH 2 —O—C(═O)—CH═CH 2 ] 2 , or —N[CH 2 —CH 2 —NH—C(═O)—CH═CH 2 ] 2 , where each t is, independently, an integer from 1 to 18; 
 R 6  is —OH, —NH 2 , —O—Z, —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 NH 2 ) 2 , —N(CH 2 CH 2 OH) 2 , —CH 2 —O—Z, —CH 2 —OH, —CH 2 —NH 2 , —N(CH 3 ) 2 , —O-(alkylene)-CH 3 , —CH 2 —Y, —NCO, —O—C(═O)—(CH 2 ) v —CH 3 , —NH—Z, —N[CH 2 O—C(═O)—CH═CH 2 ] 2 , —NH—C(═O)CH═CH 2 , —CH 2 CH 2 —O—Z, —CH 2 CH 2 OH, —O—C(═O)—CH═CH 2 , —N(CH 2 —CH 2 —NH 2 ) 2 , —(CH 2 —CH 2 —O) v H, —(CH 2 —CH 2 —CH 2 —O) v H, —N[CH 2 —CH 2 —O—C(═O)—CH═CH 2 ] 2 , or —N[CH 2 —CH 2 —NH—C(═O)—CH═CH 2 ] 2 , where each v is, independently, an integer from 1 to 18; 
 each R 7  is, independently, —OH, —NH 2 , —O—Z, —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 NH 2 ) 2 , —N(CH 2 CH 2 OH) 2 , —CH 2 —O—Z, —CH 2 —NH 2 , —N(CH 3 ) 2 , —O-(alkylene)-CH 3 , —CH 2 —Y, —NCO, —O—C(═O)—(CH 2 ) w —CH 3 , —NH—Z, —N[CH 2 O—C(═O)—CH═CH 2 ] 2 , —NH—C(═O)CH═CH 2 , —CH 2 CH 2 —O—Z, —CH 2 CH 2 OH, —O—C(═O)—CH═CH 2 , —N(CH 2 —CH 2 —NH 2 ) 2 , —(CH 2 —CH 2 —O) w H, —(CH 2 —CH 2 —CH 2 —O) w H, —N[CH 2 —CH 2 —O—C(═O)—CH═CH 2 ] 2 , or —N[CH 2 —CH 2 —NH—C(═O)—CH═CH 2 ] 2 , where each w is, independently, an integer from 1 to 18; 
 R 8  is —OH, —NH 2 , —O—Z, —N(Z) 2 , —N(CH 2 —O—Z) 2 , —N(CH 2 OH) 2 , —N(CH 2 CH 2 —O—Z) 2 , —N(CH 2 NH 2 ) 2 , —N(CH 2 CH 2 OH) 2 , —CH 2 —O—Z, —CH 2 —OH, —CH 2 —NH 2 , —N(CH 3 ) 2 , —O-(alkylene)-CH 3 , —CH 2 —Y, —NCO, —O—C(═O)—(CH 2 ) x —CH 3 , —NH—Z, —N[CH 2 O—C(═O)—CH═CH 2 ] 2 , —NH—C(═O)CH═CH 2 , —CH 2 CH 2 —O—Z, —CH 2 CH 2 OH, —O—C(═O)—CH═CH 2 , —N(CH 2 —CH 2 —NH 2 ) 2 , —(CH 2 —CH 2 —O) x H, —(CH 2 —CH 2 —CH 2 —O) x H, —N[CH 2 —CH 2 —O—C(═O)—CH═CH 2 ] 2 , or —N[CH 2 —CH 2 —NH—C(═O)—CH═CH 2 ] 2 , where each x is, independently, an integer from 1 to 18; 
 Z is 
 
       
       
         
           
           
               
               
           
         
         
            and 
           Y is Cl, Br, F, or I, 
         
         the method comprising:
 contacting a novolac compound with a formaldehyde or a paraformaldehyde to form a hydroxymethyl compound; and 
 contacting the hydroxymethyl compound with an epihalohydrin, an acrylic compound, an alkanoyl halide, an alkyl halide, ammonia, phosgene, or a dialkyl amine to form the compound. 
 
       
     
     
         2 . The method of  claim 1 , wherein contacting the novolac compound with the formaldehyde or the paraformaldehyde comprises contacting about 1 mole of the novolac compound with about 3 moles to about 10 moles of the formaldehyde or the paraformaldehyde in presence of a basic catalyst. 
     
     
         3 . The method of  claim 2 , wherein contacting the novolac compound with the formaldehyde or the paraformaldehyde in presence of the basic catalyst comprises mixing the novolac compound, the formaldehyde or the paraformaldehyde, and the basic catalyst in a solution having a pH of about 8 to a pH of about 11. 
     
     
         4 . The method of  claim 2 , wherein contacting the novolac compound with the formaldehyde or the paraformaldehyde in presence of the basic catalyst comprises mixing the novolac compound, the formaldehyde or the paraformaldehyde, and the basic catalyst in a solution for about 2 hours to about 6 hours. 
     
     
         5 . The method of  claim 2 , wherein contacting the novolac compound with the formaldehyde or the paraformaldehyde in presence of the basic catalyst comprises heating the novolac compound, the formaldehyde or the paraformaldehyde, and the basic catalyst to a temperature of about 50 C to about 70 C. 
     
     
         6 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the dialkyl amine comprises contacting with a dialkyl amine comprising dimethyl amine, diethyl amine, dipropyl amine, dibutyl amine, or any combination thereof. 
     
     
         7 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the acrylic compound comprises contacting with an acrylic compound comprising acrylic anhydride, acrylic acid, acryloyl chloride, or any combination thereof. 
     
     
         8 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the alkyl halide comprises contacting with an alkyl halide comprising isooctyl chloride, decyl chloride, hexyl chloride, heptyl chloride, nonyl chloride, or any combination thereof. 
     
     
         9 . The method of  claim 1 , wherein contacting the hydroxymethyl compound with the alkanoyl halide comprises contacting with an alkanoyl halide comprising isooctanoyl chloride, decanoyl chloride, hexanoyl chloride, lauroyl chloride, nonanoyl chloride, palmitoyl chloride, or any combination thereof. 
     
     
         10 . The method of  claim 1 , wherein contacting the hydroxymethyl compound comprises contacting the hydroxymethyl compound with the epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl halide, the ammonia, the phosgene, or the dialkyl amine, in a molar ratio of about 1:3 to about 1:10. 
     
     
         11 . The method of  claim 10 , wherein contacting the hydroxymethyl compound further comprises contacting the hydroxymethyl compound with the epihalohydrin or the dialkyl amine in presence of a reaction catalyst. 
     
     
         12 . The method of  claim 11 , wherein the reaction catalyst is selected from the group consisting of MgClO 4 , LiCl, LiOH, SnF 2 , LiClO 4 , and any combination thereof. 
     
     
         13 . The method of  claim 11 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in presence of the reaction catalyst further comprises heating the hydroxymethyl compound, the epihalohydrin, and the reaction catalyst along with a phase transfer catalyst. 
     
     
         14 . The method of  claim 13 , wherein the phase transfer catalyst is selected from the group consisting of benzyltrimethylammonium bromide, cetyltrimethylammonium bromide, tetrabutylammonium hydroxide, tetrabutyl ammonium chloride, and any combination thereof. 
     
     
         15 . The method of  claim 11 , wherein contacting the hydroxymethyl compound with the epihalohydrin compound in presence of the reaction catalyst further comprises adding an organic solvent. 
     
     
         16 . The method of  claim 15 , 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, and any combination thereof. 
     
     
         17 . The method of  claim 10 , wherein contacting the hydroxymethyl compound further comprises contacting the hydroxymethyl compound with the acrylic compound in presence of an antioxidant and an inhibitor. 
     
     
         18 . The method of  claim 17 , wherein the inhibitor is a substituted or a non-substituted quinone, hydroquinone, butylated hydroxyl toluene, or any combination thereof. 
     
     
         19 . The method of  claim 17 , wherein the antioxidant is tert-butylhydroquinone, a substituted quinone, butylated hydroxyl toluene, or any combination thereof. 
     
     
         20 . The method of  claim 10 , wherein contacting the hydroxymethyl compound further comprises contacting the hydroxymethyl compound with the ammonia or the phosgene in an autoclave. 
     
     
         21 . The method of  claim 20 , wherein contacting the hydroxymethyl compound comprises contacting the hydroxymethyl compound and the ammonia or the phosgene under a pressure of about 1 atmospheric pressure to about 1.5 atmospheric pressure. 
     
     
         22 . The method of  claim 10 , wherein contacting the hydroxymethyl compound comprises contacting the hydroxymethyl compound with the epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl halide, the ammonia, the phosgene, or the dialkyl amine at a temperature of about 50 C to about 90 C. 
     
     
         23 . The method of  claim 10 , wherein contacting the hydroxymethyl compound contacting the hydroxymethyl compound with the epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl halide, the ammonia, the phosgene, or the dialkyl amine for about 2 hours to about 6 hours.