Polymerizable compositions based on epoxides

Abstract

The invention relates to polymerizable compositions comprising (a) 3 to 80 wt. % of an epoxide or a mixture of epoxides of the general formula: in which, for type A: if n=2 Z denotes a cycloaliphatic or aromatic radical having 1 to 22, preferably 1 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2 and/or NR, or an aliphatic radical having 0 to 22, preferably 1 to 18 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, NR or SiR 2 , wherein at least one C atom must be replaced by SiR 2 , and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—, if n>2 Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2 and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—, and in which, for type B: Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2 and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—, and in which, for type A and type B: A denotes an aliphatic, cycloaliphatic or aromatic radical having 1 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2 and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—, B 1 , B 2 , D and E independently of one another denote an H atom or an aliphatic radical having 1 to 9 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2 and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—, n denotes 2-7, m denotes 1-10, p denotes 1-5, q denotes 1-5 and x denotes CH 2 , S or O, (b) 0 to 80 wt. % of an epoxide or a mixture of epoxides which differ from (a), (c) 3 to 85 wt. % of fillers, (d) 0.01 to 25 wt. % of initiators, retardants and/or accelerators, (e) 0 to 25 wt. % of auxiliaries, the percentage data in each case being based on the total weight of the composition. The new polymerizable compositions are particularly suitable as dental compositions.

1 . Polymerizable composition comprising 
 (a) 3 to 80 wt. % of an epoxide or a mixture of epoxides of the general formula:                          in which, for type A: 
 if n=2  
 Z denotes a cycloaliphatic or aromatic radical having 1 to 22, preferably 1 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2  and/or NR, or an aliphatic radical having 0 to 22, preferably 1 to 18 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, NR or SiR 2 , wherein at least one C atom must be replaced by SiR 2 , and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,  
 if n>2  
 Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2  and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,  
 and in which, for type B:  
 Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2  and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,  
 and in which, for type A and type B:  
 A denotes an aliphatic, cycloaliphatic or aromatic radical having 1 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2  and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,  
 B 1 , B 2 , D and E independently of one another denote an H atom or an aliphatic radical having 1 to 9 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR 2  and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,  
 n denotes 2-7,  
 m denotes 1-10,  
 p denotes 1-5,  
 q denotes 1-5 and  
 x denotes CH 2 , S or O,  
   (b) 0 to 80 wt. % of an epoxide or a mixture of epoxides which differ from (a),    (c) 3 to 85 wt. % of fillers,    (d) 0.01 to 25 wt. % of initiators, retardants and/or accelerators,    (e) 0 to 25 wt. % of auxiliaries,    the percentage data in each case being based on the total weight of the composition.    
     
     
         2 . Polymerizable composition as claimed in patent  claim 1 , characterized in that it comprises, as component (a), one or more of the following epoxides: 
 i) 2,2bis[4,1-phenylenoxy-3,1-propanediyl-3,4-epoxycyclohexylcarboxylic acid ester]propylidene                          ii) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]propylidene                          iii) 2,2-bis[3,4-epoxycyclohexylmethanediyl(4,1-phenylenoxy-3,1-propylcarboxylic acid ester)]propylidene                          iv) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-1,1,3,3-tetramethyldisiloxanyl-1,2-ethanediyl-3,4-epoxycyclohexyl]propylidene                          v) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3-oxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propylidene                          vi) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3,8-dioxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propylidene                          vii) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-[3,5,7-tris(ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]}propylidene                          viii) bis[methanediyl-oxy-3,1-propanediyl-3,4-epoxycyclohexylcarboxylic acid ester]tricyclo[5.2.1.0 2,6 ]decane                          ix) bis[methanediyl-oxy-3,1-propanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]tricyclo[5.2.1.0 2,6 ]decane                          x) bis[3,4-epoxycyclohexylmethanediyl-propanecarboxylic acid-1-oxy-methanediyl]tricyclo[5.2.1.0 2,6 ]decane                          xi) bis(methanediyl-oxy-3,1-propanediyl-1,1,3,3-tetramethyldisiloxanediyl-1,2-ethanediyl-3,4-epoxycyclohexyl)tricyclo[5.2.1.0 2,6 ]decane                          xii) bis{methanediyl-oxy-3,1-propanediyl-3-oxatricyclo[3.2.1.0 2,6 ]octyl-6-carboxyl}tricyclo[5.2.1.0 2,6 ]decane                          xiii) bis{methanediyl-oxy-3,1-propanediyl-3,8-dioxatricyclo[3.2.1.0 2,6 ]octyl-6-carboxyl}tricyclo[5.2.1.0 2,6 ]decane                          xiv) bis(methanediyl-oxy-(3-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl)-tricyclo[5.2.1.0 2,6 ]decane                          xv) 1,1,1-tris[methanediyl-oxy-methanediyl-3,4epoxycyclohexyl]propane                          xvi) 1,1,1-tris[methanediyl-oxy-1,3-propanediyl-1,1,3,3-tetramethyldisiloxanediyl-1,2-ethanediyl-3,4-epoxycyclohexyl]propane                          xvii) 1,1,1-tris{methanediyl-3-oxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propane                          xviii) 1,1,1-tris{methanediyl-3,8-dioxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propane                          xix) 1,1,1-tris[methanediyl-oxy-3,1-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]propane                          xx) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy-3,4-epoxycyclohexylcarboxylic acid ester]propane                          xxi) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy)-methanediyl-3,4-epoxycyclohexyl]propane                          xxii) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy)-propanediyl-1,1,3,3,-tetramethyldisiloxanyl-1,2-ethanediyl-3,4-epoxycyclohexyl]propane                          xxiii) 1,1,1-tris{methanediyl-oxy-bis(ethanediyloxy)-3-oxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propane                          xxiv) 1,1,1-tris{methanediyl-oxy-bis(ethanediyloxy)-3,8-dioxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propane                          xxv) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy)-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]propane                          xxvi) α,ω-bis[3,4-epoxycyclohexylethanediyl-1,1,3,3-tetramethyldisiloxanyl-3,1-propanediyl]polytetrahydrofuran                          xxvii) α,ω-bis{3-oxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxyl}polytetrahydrofuran                          xxviii) α,ω-bis{3,8-dioxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}polytetrahydrofuran                          xxix) α-ω(3-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl)polytetrahydrofuran                          
     
     
         3 . Polymerizable composition as claimed in patent  claim 1  or  2 , characterized in that it comprises, as the low-viscosity epoxide according to component b) 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl 3,4-epoxy-6-methyl cyclohexanecarboxylate, dicyclopentadiene dioxide, bis(3,4-epoxycyclohexylmethyl) adipate, 1,3,5,7-tetrakis(2,1-ethanediyl-3,4-epoxycyclohexyl) 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentakis(2,1-ethanediyl-3,4epoxycyclohexyl)-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,1,3,3-tetramethyl-1,3-bis(ethanediyl-3,4-epoxycyclohexyl)disiloxane and/or low molecular weight siloxanes functionalized with cycloaliphatic epoxides.  
     
     
         4 . Polymerizable composition according to at least one of patent  claims 1  to  3 , characterized in that it comprises, as fillers according to component c), quartz, ground glasses, silica gels or silicic acids or granules thereof.  
     
     
         5 . Polymerizable composition according to at least one of patent  claims 1  to  4 , characterized in that it comprises, as retardants, accelerators and/or initiators, Lewis acids or Broensted acids or compounds from which such as acids are formed by irradiation with UV light or visible light or by heat and/or pressure.  
     
     
         6 . Polymerizable composition according to at least one of patent  claims 1  to  5 , characterized in that it comprises, as auxiliaries, diols, diluents, stabilizers, inhibitors and/or pigments.  
     
     
         7 . Polymerizable composition according to at least one of patent  claims 1  to  6 , comprising 
 A a catalyst paste comprising the epoxides of components (a) and (b), a portion or all of the filler of component (c), if appropriate retardants or accelerators according to component (d) and if appropriate auxiliaries of component (e), and, spatially separated therefrom,  
 B a catalyst paste comprising an initiator according to component (d), if appropriate a portion of the filler of component (c) and if appropriate auxiliaries according to component (e).  
 
     
     
         8 . Epoxides, namely 
 i) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-3,4-epoxycyclohexylcarboxylic acid ester]propylidene                          ii) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]propylidene                          iii) 2,2-bis[3,4-epoxycyclohexylmethanediyl(4,1-phenylenoxy-3,1-propylcarboxylic acid ester)]propylidene                          iv) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-1,1,3,3-tetramethyldisiloxanyl- 1,2-ethanediyl-3,4-epoxycyclohexyl]propylidene                          v) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3-oxatricyclo[3.2.1.0 2,4 ]octyl-6-carboxy}propylidene                          vi) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3,8-dioxatricyclot[3.2.1.0 2.4 ]octyl-6-carboxy}propylidene                          vii) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-[3,5,7-tris(ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]}propylidene                          viii) bis[methanediyl-oxy-3,1-propanediyl-3,4-epoxycyclohexylcarboxylic acid ester]tricyclo[5.2.1.0 2.6 ]decane                          ix) bis[methanediyl-oxy-3,1-propanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]tricyclo[5.2.1.0 2,6 ]decane                          x) bis[3,4-epoxycyclohexylmethanediyl-propanecarboxylic acid-1-oxy-methanediyl]tricyclo[5.2.1.0 2,6 ]decane                          xi) bis(methanediyl-oxy-3,1-propanediyl-1,1,3,3-tetramethyidisiloxanediyl-1,2-ethanediyl-3,4-epoxycyclohexyl)tricyclo[5.2.1.0 2,6 ]decane                          xii) bis{methanediyl-oxy-3,1-propanediyl-3-oxatricyclo[3.2.1.0 2.6 ]octyl-6-carboxyl}tricyclol5.2.1.0 2.6 ]decane                          xiii) bis{methanediyl-oxy-3,1-propanediyl-3,8-dioxatricyclo[3.2.1.0 2.6  octyl-6-carboxyl}tricyclo[5.2.1.0 2.6 ]decane                          xiv) bis(methanediyl-oxy-(3-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl)-tricyclo[5.2.1.0 2.6 ]decane                          xv) 1,1,1-tris[methanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]propane                          xvi) 1,1,1tris[methanediyl-oxy-1,3-propanediyl-1,1,3,3-tetramethyldisiloxanediyl-1,2ethanediyl-3,4-epoxycyclohexyl]propane                          xvii) 1,1,1tris{methanediyl3-oxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxyl}propane                          xviii) 1,1,1-tris{methanediyl-3,8-dioxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxy}propane                          xix) 1,1,1-tris[methanediyl-oxy-3,1-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)1,3,5,7-tetramethylcyclotetrasiloxanyl]propane                          xx) 1,1,1-tristmethanediyl-oxy-bis(ethanediyloxy)-3,4-epoxycyclohexylcarboxylic acid ester]propane                          xxi) 1,1,1-trismethanediyl-oxy-bis(ethanediyloxy)-mnethanediyl-3,4-epoxycyclohexyl]propane                          xxii) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy)-propancdiyl-1,1,3,3-tetramethyldisiloxanyl-1,2-ethanediyl-3,4-epoxycyclohexyl]propane                          xxiii) 1,1,1-tris{methanediyl-oxy-bis(ethanediyloxy)-3-oxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxyl}propane                          xxiv) 1,1,1-tris{methanediyl-oxy-bis(ethanediyloxy)-3,8-dioxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxy}propane                          xxv) 1,1,1-tris[methanediyl-oxy-bis(ethanediyloxy)-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]propane                          xxvi) α,ω-bis[3,4-epoxycyclohexylethanedlyl-1,1,3,3-tetramnethyidisiloxanyl-3,1-propanediyl]polytetrahydrofuran                          xxviii) α,ω-bis{3-oxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxy}polytetrahydrofuran                          xxviii) α,ω-bis{3,8-dioxatricyclo[3.2.1.0 2.4 ]octyl-6-carboxyl}polytetrahydrofuran                          xxix) α,ω-bis(3-propanediyl-3,5,7-tris(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl)polytetrahydrofuran                          
     
     
         9 . Use of the polymerizable compositions according to at least one of patent  claims 1  to  7  or of the cycloaliphatic epoxides according to patent  claim 8  as coating compositions.  
     
     
         10 . Use of the polymerizable compositions according to at least one of patent  claims 1  to  7  or of the cycloaliphatic epoxides according to patent  claim 8  for gluing substrates.  
     
     
         11 . Use of the polymerizable compositions according to at least one of patent  claims 1  to  7  or of the cycloaliphatic epoxides according to patent  claim 8  as dental compositions.