Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same

Abstract

Compounds and methods of preparing compounds of the formula: RZ—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—A  (I) wherein n is an integer from 1 to 15, m is either 0 or 1; R a , R b , R c , and R d are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; Z is —O— or —NG—, wherein G is H, C 1 -C 12 alkyl or the radical R; wherein R is wherein R 1 is hydrogen, C 1 -C 18 alkyl, O, OH, CH 2 CN, C 1 -C 18 alkoxy, C 1 -C 18 hydroxyalkoxy, C 5 -C 12 cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy, C 3 -C 6 alkenyl, C 1 -C 18 alkynyl, C 7 -C 9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C 1 -C 4 alkyls, or an aliphatic C 1 -C 8 acyl; R 2 is hydrogen, C 1 -C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C 1 -C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 cycloalkyl; and A is either ZR or a hydrocarbyl group, which are useful for stabilizing polymer compositions against photo- and thermal degradation

What is claimed is:  
     
         1 . A compound having the formula (I):  
       RZ—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—A  (I)  
       wherein n is an integer from 1 to 15, m is either 0 or 1; R a , R b , R c , and R d  are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; Z is —O— or —NG—, wherein G is H, C 1 -C 12  alkyl or the radical R; wherein R is  
       
         
           
           
               
               
           
         
       
       wherein R 1  is hydrogen, C 1 -C 18  alkyl, O, OH, CH 2 CN, C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 12  cycloalkoxy, C 5 -C 12  hydroxycycloalkoxy, C 3 -C 6  alkenyl, C 1 -C 18  alkynyl, C 7 -C 9  phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C 1 -C 4  alkyls, or an aliphatic C 1 -C 8  acyl; R 2  is hydrogen, C 1 -C 8  alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6  are each a hydrogen, C 1 -C 8  alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10  cycloalkyl; and A is either ZR or a hydrocarbyl group.  
     
     
         2 . The compound of  claim 1 , wherein R 1  is a H, C 1 -C 4  alkyl, O, OH; C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 1-2  cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy; R 2  is H, or C 1 -C 4  alkyl; R 3 , R 4 , R 5 , and R 6  are each H or C 1 -C 4  alkyl; R a , R b , R c , and R d , are each a hydrogen, aromatic, or C 1 -C 4  alkyl; and n is from 4 to 11.  
     
     
         3 . The compound of  claim 1 , wherein R 1  is H or CH 3 ; R 3 , R 4 , R 5 , and R are each CH 3 ; R 2  is hydrogen; R a , R b , R c  and R d  are each a hydrogen; Z is —O—; m is 0 or 1; and n is and integer from 4 to 10.  
     
     
         4 . The compound of  claim 3  wherein A is ZR.  
     
     
         5 . The compound of  claim 4  wherein n is 4.  
     
     
         6 . A method of forming the compound of  claim 1  comprising: 
 combining one or more multi-functional carbonyl compounds of general structure:  
 DO—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—B  
 wherein n is an integer from 1 to 15, m is either 0 or 1; R a , R b , R c , and R d , are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and wherein one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; D is a hydrocarbyl group; and B is either OD or D; with one or more 1-substituted piperidin-4-ol or 4-aminopiperidines of general structure  
                     
 wherein Z is OH or NHG, wherein G is as defined in  claim 1;  R 1  is hydrogen, C 1 -C 18  alkyl, O, OH, CH 2 CN, C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 12  cycloalkoxy, C 5 -C 12  hydroxycycloalkoxy, C 3 -C 6  alkenyl, C 1 -C 18  alkynyl, C 7 -C 9  phenylalkyl, unsubstituted or 2 substituted on the phenyl with 1, 2 or 3 C 1 -C 4  alkyls, or an aliphatic C 1 -C 8  acyl; R 2  represents hydrogen, C 1 -C 8  alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6  are each a hydrogen, C 1 -C 8  alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10  cycloalkyl, to form a reaction mixture;  
 reacting the reaction mixture for a sufficient time to form the compound of formula (1); and  
 recovering the compound of formula (I) from the reaction mixture.  
 
     
     
         7 . The method of  claim 6 , wherein the one or more multifunctional carbonyl compounds is present in an amount of about 0.025 to 2.5 M and the molar ratio of the one or more multi-functional carbonyl compounds to the one or more 1-substituted piperidin-4-ol or 4-aminopiperidines is from about 20:1 to 1:5.  
     
     
         8 . The method of  claim 6 , wherein the substituted 4-piperidin-4-ol is 1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinol and the multi-functional carbonyl compound is selected from the group consisting of methyl 6-(methoxycarbonylamino)hexanoate, butyl 6-(butoxycarbonylamino) undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl 6-(methoxycarbonylamino)undecanoate, methyl 6-(methoxycarbonylamino)undecanoate, and combinations thereof.  
     
     
         9 . The method of  claim 6 , wherein the reaction mixture further comprises a solvent.  
     
     
         10 . The method of  claim 6 , wherein the reaction mixture further comprises a catalyst.  
     
     
         11 . The method of  claim 10 , wherein the catalyst comprises methoxide.  
     
     
         12 . The method of  claim 10 , wherein the catalyst comprises a Lewis acid selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.  
     
     
         13 . The method of  claim 10 , wherein the catalyst is present in an amount of less than about 30 mole percent based on the molar quantity of the multi-functional carbonyl compound.  
     
     
         14 . A method of forming the compound of  claim 1  from a lactam in a single-step comprising: 
 combining one or more lactams of general structure  
                     
 wherein n is an integer from 1 to 15 and R a , R b , R c , and R d  are each a hydrogen or a hydrocarbyl group with one or more carbonyl compounds of general structure  
                     
 wherein m is either 0 or 1, D is a hydrocarbyl group and B is a hydrocarbyl group or OD and Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, and the substitution pattern on the phenylene group may be an ortho, meta, or para substitution pattern, and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or other functional group; and one or more 1-substituted piperidin-4-ol or 4-aminopiperidines of general structure  
                     
 wherein Z is OH or NHG, wherein G is as defined in  claim 1;  R 1  is hydrogen, C 1 -C 18  alkyl, O, OH, CH 2 CN, C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 12  cycloalkoxy, C 5 -C 12  hydroxycycloalkoxy, C 3 -C 6  alkenyl, C 1 -C 18  alkynyl, C 7 -C 9  phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C 1 -C 4  alkyls, or an aliphatic C 1 -C 8  acyl; R 2  represents hydrogen, C 1 -C 8  alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6  are each a hydrogen, C 1 -C 8  alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached, form a C 5 -C 10 cycloalkyl to provide a reaction mixture;  
 reacting the reaction mixture for a sufficient time to form the compound of formula (I); and  
 recovering the compound of formula (I) from the reaction mixture.  
 
     
     
         15 . The method of  claim 14  wherein the carbonyl compound is selected from the group consisting of a dialkyl carbonate, a dialkyl oxalate, a dialkyl diester, an alkyl ester, and mixtures thereof.  
     
     
         16 . The method of  claim 14 , wherein the reaction mixture further comprises a catalyst.  
     
     
         17 . The method of  claim 16 , wherein the catalyst comprises a Lewis acid selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.  
     
     
         18 . The method of  claim 14 , wherein the reaction mixture further comprises a solvent.  
     
     
         19 . The method of  claim 18 , wherein the concentration of lactam is from about 0.025 to 10 M; the ratio of lactam to carbonyl compound is from about 2:1 to 1:4; the ratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine is from about 1:1; to 1:6; and further comprising a catalyst in an amount of less than about 30 mole percent relative to the amount of carbonyl compound.  
     
     
         20 . The method of  claim 16 , wherein n is from 3 to 12 and the catalyst comprises a base catalyst or a Lewis acid.  
     
     
         21 . The method of  claim 14 , wherein the lactam comprises caprolactam.  
     
     
         22 . The method of  claim 14 , wherein the lactam comprises laurolactam.  
     
     
         23 . A method of forming a multi-functional carbonyl compound having the structure  
       DO—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—B  
       wherein n is an integer from about 1 to 15, m is either 0 or 1; R a , R b , R c , and R d  are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is an integer from about 0 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; D is a hydrocarbyl group; and B is either OD or D, comprising: 
 combining one or more lactams of general structure  
                     
 wherein n and R a , R b , R c , and R d  are as defined above with one or more carbonyl compounds of general structure  
                     
 wherein D, B, Y, and m are as defined above; and a Lewis acid catalyst, or a base catalyst to provide a reaction mixture;  
 reacting the reaction mixture for a sufficient time to produce the multi-functional carbonyl compound; and  
 recovering the multi-functional carbonyl compound from the reaction mixture, wherein the temperature of the reaction mixture when said base catalyst is used is less than about 20° C.  
 
     
     
         24 . The method of  claim 23 , wherein n is from about 3 to 12.  
     
     
         25 . The method of  claim 23 , wherein the Lewis acid catalyst is selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.  
     
     
         26 . The method of  claim 23 , wherein the reaction mixture further comprises a solvent.  
     
     
         27 . The method of  claim 23 , wherein the lactam comprises caprolactam.  
     
     
         28 . The method of  claim 23 , wherein the lactam comprises laurolactam.  
     
     
         29 . The method of  claim 23 , wherein the temperature of the reaction mixture when said base catalyst is used is less than 15° C.