Addition-fragmentation agents

Abstract

Addition-fragmentation agents of the formula are disclosed: wherein R 1 , R 2 and R 3 are each independently Z-Q-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least one of R 1 , R 2 and R 3 is Z m -Q-, Q is a linking group have a valence of m+1; Z is an ethylenically unsaturated polymerizable group, m is 1 to 6; each X 1 is independently —O— or —NR 4 —, where R 4 is H or C 1 -C 4 alkyl, and n is 0 or 1.

1 . An addition-fragmentation agent of the formula: 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  and R 3  are each independently Z m -Q-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least one of R 1 , R 2  and R 3  is Z m -Q-, 
         Q is a linking group have a valence of m+1; 
         Z is an ethylenically unsaturated polymerizable group, 
         m is 1 to 6; 
         each X 1  is independently —O— or —NR 4 —, where R 4  is H or C 1 -C 4  alkyl, and 
         n is 0 or 1. 
       
     
     
         2 . The addition-fragmentation agent of  claim 1  where Z comprises a vinyl, vinyloxy, (meth)acryloxy, (meth)acrylamido, styrenic and acetylenic functional groups. 
     
     
         3 . The crosslinking agent of  claim 1  where Z is selected from: 
       
         
           
           
               
               
           
         
         wherein R 4  is H or C 1 -C 4  alkyl 
       
     
     
         4 . The addition-fragmentation agent of  claim 1  wherein Q is selected from from —O—. —S—, —NR 4 —, —SO 2 —, —PO 2 —, —CO—, —OCO—, —R 6 —, —NR 4 —CO—NR 4 —, NR 4 —CO—O—, NR 4 —CO—NR 4 —CO—O—R 6 —, —CO—NR 4 —R 6 —, —R 6 —CO—O—R 6 —, —O—R 6 —. —S—R 6 —, —NR 4 —R 6 —, —SO 2 —R 6 —, —PO 2 —R 6 —, —CO—R 6 —, —OCO—R 6 —, —NR 4 —CO—R 6 —, NR 4 —R 6 —CO—O—, and NR 4 —CO—NR 4 —, wherein each R 4  is hydrogen, a C 1  to C 4  alkyl group, or aryl group, each R 6  is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms, with the proviso that Q-Z does not contain peroxidic linkages. 
     
     
         5 . The addition-fragmentation agent of  claim 1  where Q is an alkylene. 
     
     
         6 . The addition-fragmentation agent of  claim 5  wherein Q is an alkylene of the formula —C r H 2r —, where r is 1 to 10. 
     
     
         7 . The addition-fragmentation agent of  claim 1  where Q is a hydroxyl-substituted alkylene. 
     
     
         8 . The addition-fragmentation agent of  claim 1  where Q is —CH 2 —CH(OH)—CH 2 — 
     
     
         9 . The addition-fragmentation agent of  claim 1  where Q is an aryloxy-substituted alkylene. 
     
     
         10 . The addition-fragmentation agent of  claim 1  where R 5  is an alkoxy-substituted alkylene. 
     
     
         11 . The addition-fragmentation agent of  claim 1  wherein R 1 —X 1 — groups (and optionally R 2 —X 2 — groups) is selected from H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(OH)—CH 2 —O—, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C(CH 3 )═CH 2 )—CH 2 —O—, H 2 C═C(CH 3 )C(O)—O—CH(CH 2 OPh)-CH 2 —O—, H 2 C═C(CH 3 )C(O)—O—CH 2 CH 2 —N(H)—C(O)—O—CH(CH 2 OPh)-CH 2 —O—, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH—O—, H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(OH)—CH 2 —O—, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —O—, CH 3 —(CH 2 ) 7 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —O—, H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(—O—(O)C(H)═CH 2 )—CH 2 —O— and H 2 C═C(H)C(O)—O—CH 2 —CH(OH)—CH 2 —O—. H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(—O—(O)C(H)═CH 2 )—CH 2 —O—, and CH 3 —(CH 2 ) 7 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —O—. 
     
     
         12 . A polymerizable composition comprising the addition-fragmentation agent of  claim 1 , at least one free-radically polymerizable monomer, and an initiator. 
     
     
         13 . The polymerizable composition of  claim 12  comprising:
 a) 85 to 100 parts by weight of an (meth)acrylic acid ester of non-tertiary alcohol; 
 b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer; 
 c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer; 
 d) 0 to 5 parts vinyl monomer; and 
 e) 0 to 5 parts of a multifunctional (meth)acrylate; 
 based on 100 parts by weight total monomer, and 
 f) 0.1 to 10 parts by weight of the addition-fragmentation agent, based on 100 parts by weight of a) to e). 
 
     
     
         14 . The polymerizable composition of  claim 13  further comprising 0.01 to 5 parts of a multifunctional (meth)acrylate. 
     
     
         15 . The polymerizable composition of  claim 12  further comprising a free radical initiator. 
     
     
         16 . The polymerizable composition of  claim 15  wherein the initiator is a thermal initiator. 
     
     
         17 . A method of making the addition-fragmentation agent of  claim 1  comprising the step of reacting a compound of the formula: 
       
         
           
           
               
               
           
         
         wherein X 2  comprises an electrophilic or nucleophilic functional group, 
         X 3  is X 2 , X 1 —R 2  or X 1 —R 3 , and 
         n is 0 or 1; 
         with a compound of the formula: 
       
       
         
           
           
               
               
           
         
         wherein 
         A is a functional group that is co-reactive with functional group X 2 , R 4  is hydrogen, a C 1  to C 4  alkyl group, or aryl group; R 5  is a single bond or a divalent (hetero)hydrocarbyl linking group that joins the ethylenically unsaturated group to reactive functional group A. 
       
     
     
         18 . The method of  claim 17  wherein R 5  is selected from a single bond or a divalent linking group that joins an ethylenically unsaturated group to co-reactive functional group A. 
     
     
         19 . The method of  claim 17  wherein R 5  is selected from —O—. —S—, —NR 4 —, —SO 2 —, —PO 2 —, —CO—, —OCO—, —NR 4 —CO—, NR 4 —CO—O—, NR 4 —CO—NR 4 —, —R 6 — and combinations thereof, where R 6  is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms. 
     
     
         20 . The method of  claim 17  wherein the co-reactive functional group A is selected from hydroxyl, amino, oxazolinyl, oxazolonyl, acetyl, acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyl halide, vinyloxy, and cyclic anhydride groups. 
     
     
         21 . The method of  claim 17 ,
 where the reactive functional group X 2  is isocyanato functional group, the co-reactive functional group A comprises a secondary amino or hydroxyl group;   where the reactive functional group X 2  comprises a hydroxyl group, the co-reactive functional group comprises a carboxyl, ester, acyl halide, isocyanato, epoxy, anhydride, azlactonyl or oxazolinyl group;   where the reactive functional group X 2  comprises a carboxyl group, the co-reactive functional group A comprises a hydroxyl, amino, epoxy, isocyanate, or oxazolinyl group.