Photo-latent titanium oxo-chelate catalysts

Abstract

A titanium-oxo-chelate catalyst formulation, comprising: (i) at least one compound of the formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 independently of each other are for example hydrogen, halogen, C 1 -C 20 alkyl, C 6 -C 14 aryl which is unsubstituted or substituted; or R 1 , R 2 and R 3 and/or R 4 , R 5 and R 6 and/or R 7 , R 8 and R 9 and/or R 10 , R 11 and R 12 together with the C-atom to which they are attached each form a C 6 -C 14 aryl group which is unsubstituted or substituted; or R 1 and R 2 and/or R 4 and R 5 and/or R 7 and R 8 and/or R 10 and R 11 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring; at least one chelate ligand compound of the formula (IIa), (IIb) or (IIc), wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are defined as above for formula (I), is suitable as a photolatent catalyst formulation for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid.

1 - 16 . (canceled) 
     
     
         17 . A titanium-oxo-chelate catalyst compound of the formula (IA) or (IB) 
       
         
           
           
               
               
           
         
       
       wherein
 R 20 , R′ 20 , R″ 20 , R 21 , R′ 21  and R″ 21  independently of each other are hydrogen, halogen, C 1 -C 20 alkyl, which is unsubstituted or substituted by one or more OR 13  or COOR 13 , or are C 6 -C 14 aryl which is unsubstituted or is substituted by one or more C 1 -C 8 alkyl, halogen, OR 13  or NR 13 R 14 ; 
 provided that only one of R 20 , R′ 20  and R″ 20  in the group 
 
       
         
           
           
               
               
           
         
          and only one of R 21 , R′ 21  and R″ 21  in the group 
       
       
         
           
           
               
               
           
         
          can be hydrogen; 
         or R 20  and R′ 20  and/or R 21  and R′ 21  together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring, 
         R 22 , R 23 , R 24  independently of each other are hydrogen, halogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 6 -C 14 aryl, C 1 -C 8 alkanoyl, C 1 -C 8 alkanoyloxy, C 7 -C 15 aroyl, C 7 -C 15 aroyloxy, nitrile, nitro, C 1 -C 8 alkylthio, C 6 -C 14 arylthio or NR 37 R 38 ; 
         R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35  and R 36  independently of each other are hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 , or are C 6 -C 14 aryl which is unsubstituted or is substituted by one or more C 1 -C 8 alkyl, OR 13  or NR 13 R 14 ; 
         or two radicals R 25  and R 26  and/or two radicals R 28  and R 29  and/or two radicals R 31  and R 32  and/or two radicals R 34  and R 35  together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring; 
         provided that only one of R 25 , R 26 , R 27  in the group 
       
       
         
           
           
               
               
           
         
          and only one of R 28 , R 29 , R 30  in the group 
       
       
         
           
           
               
               
           
         
          and only one of R 31 , R 32 , R 33  in the group 
       
       
         
           
           
               
               
           
         
          and only one of R 34 , R 35 , R 36  in the group 
       
       
         
           
           
               
               
           
         
          can be hydrogen; and 
         provided that R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35  and R 36  are not simultaneously methyl; 
         R 13  and R 14  independently of each other are C 1 -C 8 alkyl; 
         R 37  and R 38  independently of each other are hydrogen, C 1 -C 8 alkyl or C 6 -C 14 aryl, or R 37  and R 38  together with the N-atom to which they are attached form a 5- or 6-form a 5- or 6-membered saturated or unsaturated ring, which ring optionally in addition to the N-atom comprises a further N-atom or O-atom. 
       
     
     
         18 . The titanium-oxo-chelate catalyst compound of  claim 17 , wherein two radicals R 25  and R 26  and/or two radicals R 28  and R 29  and/or two radicals R 31  and R 32  and/or two radicals R 34  and R 35  together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring. 
     
     
         19 . The titanium-oxo-chelate catalyst compound of  claim 18 , wherein the 5- to 7-membered carbocyclic ring(s) is/are selected from 
       
         
           
           
               
               
           
         
         wherein 
         R x2  is R 27 , R 36 , R 30  and/or R 33 , 
         R y2  is C 1 -C 20 alkyl, 
         n is an integer 1-5 and 
         m is an integer 1-4. 
       
     
     
         20 . The titanium-oxo-chelate catalyst compound of  claim 17 , wherein in formula (IA)
 R 20 , R′ 20 , R″ 20  independently of each other are hydrogen, halogen or C 1 -C 20  alkyl, which is unsubstituted or substituted by one or more OR 13  or COOR 13 ;   R 21 , R′ 21 , R″ 21  independently of each other are hydrogen, halogen or C 1 -C 20  alkyl, which is unsubstituted or substituted by one or more OR 13  or COOR 13 ;   R 22 , R 23 , R 24  independently of each other are hydrogen, C 1 -C 8  alkyl, C 1 -C 8  alkoxy, C 1 -C 8  alkanoyl, C 1 -C 8  alkanoyloxy, chloro, nitrile, nitro, C 1 -C 8  alkylthio, C 6 -C 14  arylthio or NR 37 R 38 ; and in formula (IB)   R 25 , R 26 , R 27  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ,   or two radicals R 25  and R 26  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 31 , R 32 , R 33  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ,   or two radicals R 31  and R 32  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 28 , R 29 , R 30  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ,   or two radicals R 28  and R 29  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 34 , R 35 , R 36  independently of each other are hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ,   or two radicals R 34  and R 35  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring.   
     
     
         21 . The titanium-oxo-chelate catalyst compound of  claim 20 , wherein in formula (IA)
 R 20 , R′ 20 , R″ 20  independently of each other are hydrogen, halogen or C 1 -C 8  alkyl;   R 21 , R′ 21 , R″ 21  independently of each other are hydrogen, halogen or C 1 -C 8  alkyl;   R 22 , R 23 , R 24  independently of each other are hydrogen, C 1 -C 8  alkyl, C 1 -C 8  alkoxy, C 1 -C 8  alkanoyl, C 1 -C 8  alkanoyloxy or NR 37 R 38 ;   and in formula (IB)   R 25 , R 26 , R 27  independently of each other are hydrogen, C 1 -C 8  alkyl,   or two radicals R 25  and R 26  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 31 , R 32 , R 33  independently of each other are hydrogen, C 1 -C 8  alkyl,   or two radicals R 31  and R 32  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 28 , R 29 , R 30  independently of each other are hydrogen, C 1 -C 8  alkyl,   or two radicals R 28  and R 29  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   R 34 , R 35 , R 36  independently of each other are hydrogen, C 1 -C 8 alkyl,   or two radicals R 34  and R 35  together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;   
     
     
         22 . The titanium-oxo-chelate catalyst compound of  claim 21 , wherein in formula (IA)
 R 20 , R′ 20 , R″ 20  independently of each other are hydrogen, fluoro or C 1 -C 8  alkyl;   R 21 , R′ 21 , R″ 21  independently of each other are hydrogen, fluoro or C 1 -C 8  alkyl,   R 22 , R 23 , R 24  independently of each other are hydrogen, C 1 -C 8  alkyl, C 1 -C 8  alkoxy, or NR 37 R 38 ; and in formula (IB)   R 25 , R 26 , R 27  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ;   R 31 , R 32 , R 33  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ;   R 28 , R 29 , R 30  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 ;   R 34 , R 35 , R 36  independently of each other are hydrogen, C 1 -C 8  alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 .   
     
     
         23 . The titanium-oxo-chelate catalyst compound of  claim 22 , wherein in formula (IA)
 R 20 , R′ 20 , R″ 20  are hydrogen, fluoro or methyl.   R 21 , R′ 21 , R″ 21  are hydrogen, fluoro or methyl.   R 22 , R 23 , R 24  independently of each other are hydrogen, methyl, methoxy or dimethylamino and in formula (IB)   R 25 , R 26 , R 27  independently of each other are hydrogen or C 1 -C 8  alkyl;   R 31 , R 32 , R 33  independently of each other are hydrogen or C 1 -C 8  alkyl;   R 28 , R 29 , R 30  independently of each other are hydrogen or C 1 -C 8  alkyl;   R 34 , R 35 , R 36  independently of each other are hydrogen or C 1 -C 8  alkyl.   
     
     
         24 . The titanium-oxo-chelate catalyst compound of  claim 23 , wherein in formula (IA)
 the groups R 20 , R′ 20 R″ 20 C— and R 21 R′ 21 R″ 21 C— are identical;   and in formula (IB)   the groups R 25 R 26 R 27 C— and R 31 R 32 R 33 C— are identical and/or the groups R 28 R 29 R 30 C— and R 34 R 35 R 36 C— are identical.   
     
     
         25 . A polymerizable composition comprising:
 (a) at least one component which is capable of a polyaddition or polycondensation reaction in the presence of a Lewis-acid type reactant; and   (b) a Titanium-oxo-chelate catalyst compound of  claim 17 .   
     
     
         26 . A polymerizable composition of  claim 25  comprising as component (a)
 (a1) at least one blocked or unblocked isocyanate or isothiocyanate component, and 
 (a2) at least one polyol. 
 
     
     
         27 . A polymerizable composition of  claim 25 , which comprises 0.001 to 15% by weight, preferably 0.01 to 5% by weight, of the titanium-oxo-chelate catalyst compound, based on the total composition. 
     
     
         28 . A coated substrate coated on at least one surface with the composition of  claim 25 . 
     
     
         29 . A polymerized or crosslinked composition of  claim 25 . 
     
     
         30 . A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, characterized in that a titanium-oxo-chelate catalyst compound as defined in  claim 17  is added to the compounds which are capable to crosslink in the presence of a Lewis acid and the resulting mixture is irradiated with electromagnetic radiation of a wavelength range of 200-800 nm. 
     
     
         31 . A process of  claim 30 , characterized in that instead of irradiating with electromagnetic radiation the mixture is subjected to a heat treatment, or the mixture is irradiated with electromagnetic radiation and simultaneously with or after the irradiation subjected to a heat treatment. 
     
     
         32 . A process of  claim 30  for the preparation of adhesives, sealings, coatings, potting components, printing inks, printing plates, foams, moulding compounds, or photostructured layers. 
     
     
         33 . The titanium-oxo-chelate catalyst compound of  claim 17  being a compound of the formula IB′ 
       
         
           
           
               
               
           
         
       
       wherein
 R′ 25 , R′ 26 , R′ 27  and R′ 28  independently of each other are hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by one or more OR 13  or COOR 14 , or are C 6 -C 14 aryl which is unsubstituted or is substituted by one or more C 1 -C 8 alkyl, OR 13  or NR 13 R 14 ; 
 or two radicals R′ 25  and R′ 26  together with the C-atom to which they are attached and/or or two radicals R′ 27  and R′ 28  together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring.