Process for producing carbamoyloxy (meth) acrylates and new carbamoyloxy (meth) acrylates

Abstract

The invention relates to a process for producing carbamoyloxy(meth)acrylates which comprises transesterification of hydroxyalkyl carbamates with an (meth)acrylate of formula CH 2 ═CR 29 —COOR 30 wherein R 29 is hydrogen or methyl and R 30 represents an alkyl group comprising from 1 to 8 carbon atoms, in the presence of an organotitanate, an organozirconate catalyst or an organotin catalyst, the carbamoyloxy(meth)acrylates thereby obtained and their use in radiation curable compositions.

1 - 27 . (canceled) 
     
     
         28 . Carbamoyloxy(meth)acrylates obtainable by a process which comprises the transesterification of an hydroxyalkyl carbamate of formula (I), (II), (III), (IV), (V), (VI) or (VII) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein
 k≧2 
 n=0 to 2 
 m=0 to 2 
 n+m≧1 
 p=n or m, q=n or m, r=n or m, s=n or m, v=n or m, w=n or m 
 (p+q)=(r+s)=(v+w)=(n+m)
 each R 1 , each R 2 , each R 20  is, independently, chosen from the group of
 hydrogen, 
 halogen, 
 hydroxy, 
 alkyl, optionally substituted by hydroxy; halogen; aryl and/or aryl substituted by hydroxy, halogen or alkyl; and optionally containing from 1 to 8 ether bridges, 
 alkenyl, optionally substituted by hydroxy; halogen; aryl and/or aryl substituted by hydroxy, halogen or alkyl; and optionally containing from 1 to 8 ether bridges, 
 aryl, optionally substituted by hydroxy; halogen; alkyl; alkyl substituted by hydroxy, halogen and/or aryl; and/or alkyl containing from 1 to 8 ether bridges, 
 
 R 3  is an alkyl, optionally substituted by hydroxy, tertiary amine and/or aryl, and optionally containing from 1 to 20 ether bridges and/or from 1 to 3 tertiary amine bridges, 
 R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15  and R 16  are, independently, chosen from the group of
 hydrogen, and 
 alkyl, optionally substituted by hydroxy, tertiary amine and/or aryl, and optionally containing from 1 to 8 ether bridges and/or from 1 to 3 tertiary amine bridges, 
 with the proviso that, respectively, R 3  and R 4 , R 5  and R 6 , R 12  and/or R 13  and/or R 14 , R 15  and R 16  may be linked together in order to form a ring, 
 
 R 7 , R 8 , R 9 , R 10 , R 17  and R 18  are, independently, chosen from alkylene, alkenylene, arylene and aralkylene chains which may contain from 1 to 8 ether bridges and/or from 1 to 3 tertiary amine bridges, 
 R 11  is hydrogen or alkyl; 
 R 19 , R 21 , R 22 , R 23 , R 25 , R 26 , R 27  and R 28 , are, independently, chosen from alkylene, alkenylene, arylene and aralkylene chains which may contain from 1 to 20 ether bridges, from 1 to 4 tertiary amine bridges, from 1 to 4 —CO— bridges and/or from 1 to 4 —O—CO— bridges; 
 A is 
 
 
       
         
           
           
               
               
           
         
         
           wherein R 24  is hydrogen or alkyl; 
         
         with an (meth)acrylate of formula (VIII)
   CH 2 ═CR 29 —COOR 30   (VIII) 
 
         wherein R 29  is hydrogen or methyl, and R 30  represents an alkyl group comprising from 1 to 8 carbon atoms; in an equivalent ratio of (meth)acrylate to hydroxyalkyl carbamate higher than 3.5 and in the presence of an organotitanate, an organozirconate or an organotin catalyst. 
       
     
     
         29 . Carbamoyloxy(meth)acrylates of formula (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV) and (XXVI) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein 
         k, n, m, p, q, r, S, V, w, A, R 7 , R 8 , R 9 , R 10 , R 17 , R 18 , R 11 , R 19 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are as defined in claim  1 , 
         t≧3 
         R 37  is an alkyl substituted by a tertiary amine, and optionally containing from 1 to 20 ether bridges and/or from 1 to 3 tertiary amine bridges; or an alkyl containing from 1 to 20 ether bridges and/or from 1 to 3 tertiary amine bridges, optionally substituted by —O—CO—CR 29 ═CH 2 , tertiary amine and/or aryl; 
         each R 38 , each R 40  is, independently, such as defined for R 31  with the proviso that at least one R 38  and at least one R 40  is chosen from the group of
 halogen, 
 —O—CO—CR 29 ═CH 2 , 
 alkyl substituted by —O—CO—CR 29 ═CH 2 ; halogen; aryl and/or aryl substituted by —O—CO—CR 29 ═CH 2 , halogen or alkyl; and optionally containing from 1 to 8 ether bridges, 
 alkyl containing from 1 to 8 ether bridges, 
 alkenyl, optionally substituted by —O—CO—CR 29 ═CH 2 ; halogen; aryl and/or aryl substituted by —O—CO—CR 29 ═CH 2 , halogen or alkyl; and optionally containing from 1 to 8 ether bridges, 
 aryl, optionally substituted by —O—CO—CR 29 ═CH 2 ; halogen; alkyl; alkyl substituted by —O—CO—CR 29 ═CH 2 , halogen and/or aryl; and/or alkyl containing from 1 to 8 ether bridges, 
 
         R 39  is 2-methyl-1,5-pentamethylene; or R 39  is chosen from alkylene containing from 1 to 8 ether bridges and/or from 1 to 3 tertiary amine bridges; alkenylene, arylene and aralkylene chains each of which may contain from 1 to 8 ether bridges and/or from 1 to 3 tertiary amine bridges, or R 39  is chosen from alkylene when at least one of R 35  and R 36  is different from hydrogen, 
         each R 31 , each R 32 , each R 50  is, independently, chosen from the group of
 hydrogen, 
 halogen 
 —O—CO—CR 29 ═CH 2 , 
 alkyl, optionally substituted by —O—CO—CR 29 ═CH 2 ; halogen; aryl and/or aryl substituted by —O—CO—CR 29 ═CH 2 , halogen or alkyl; and optionally containing from 1 to 8 ether bridges 
 alkenyl, optionally substituted by —O—CO—CR 29 ═CH 2 ; halogen; aryl and/or aryl substituted by —O—CO—CR 29 ═CH 2 , halogen or alkyl; and optionally containing from 1 to 8 ether bridges 
 aryl, optionally substituted by —O—CO—CR 29 ═CH 2 ; halogen; alkyl; alkyl substituted by —O—CO—CR 29 ═CH 2 , halogen and/or aryl; and/or alkyl containing from 1 to 8 ether bridges 
 
         R 33  is an alkyl, optionally substituted by —O—CO—CR 29 ═CH 2 , tertiary amine and/or aryl, and optionally containing from 1 to 20 ether bridges and/or from 1 to 3 tertiary amine bridges, 
         R 34 , R 35 , R 36 , R 42 , R 43 , R 44 , R 45  and R 46  are, independently, chosen from the group of
 hydrogen, and 
 alkyl, optionally substituted by —O—CO—CR 29 ═CH 2 , tertiary amine and/or aryl, and optionally containing from 1 to 8 ether bridges and/or from 1 to 3 tertiary amine bridges, 
 
         with the proviso that, respectively, R 33  and R 34 , R 35  and R 36 , R 42  and/or R 43  and/or R 44 , R 45  and R 46  may be linked together in order to form a ring. 
       
     
     
         30 . Carbamoyloxy(meth)acrylates of formula (XVIII) according to  claim 29 , wherein R 34  is hydrogen and R 37  is alkyl comprising at least 3 carbon atoms, containing one or two ether bridges and substituted by —O—CO—CR 29 ═CH 2    
     
     
         31 . Carbamoyloxy(meth)acrylates of formula (XX) according to  claim 29 , wherein R 39  is 2-methyl-1,5-pentamethylene. 
     
     
         32 . Carbamoyloxy(meth)acrylates of formula (XXIV), (XXV) and (XXVI) according to  claim 29 , wherein n+m, p+q, r+s and v+w are equal to 1. 
     
     
         33 . Carbamoyl(meth)acrylates according to  claim 29  wherein each R 31 , each R 32  and each R 50  is hydrogen. 
     
     
         34 . Carbamoyl(meth)acrylates according to  claim 29  wherein R 34 , at least one of R 35  and R 36 , at least one of R 42 , R 43  and R 44 , at least one of R 45  and R 46  is different from hydrogen. 
     
     
         35 . A radiation curable composition comprising a carbamoyloxy(meth)acrylate according to  claim 28 .