Single component mass polymerizable compositions containing polycycloolefin monomers and organoruthenium carbide precatalyst

A kit for forming a three dimensional object comprising:

• a) one or more monomers of formula (I):
• wherein:
• m is an integer 0, 1 or 2;
• is a single bond or a double bond;
• R1, R2, R3 and R4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C3-C16)alkyl, (C2-C16)alkenyl, perfluoro(C1-C12)alkyl, (C3-C12)cycloalkyl, (C6-C2)bicycloalkyl, (C7-C14)tricycloalkyl, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, (C2-C6)acyl, (C2-C6)acyloxy, (C6-C14)aryl, (C6-C14)aryl(C1-C6)alkyl, perfluoro(C6-C14)aryl, perfluoro(C6-C14)aryl(C1-C3)alkyl, (C6-C14)aryloxy, (C6-C14)aryl(C1-C6)alkoxy, tri(C1-C6)alkoxysilyl and a group of formula (A):
• —Z-Aryl (A)
• wherein:
• Z is a bond or a group selected from the group consisting of:
• (CR5R6)a, O(CR5R6)a, (CR5R6)aO, (CR5R6)a—O—(CR5R6)b, (CR5R6)a—O—(SiR5R6)b, (CR5R6)a—(CO)O—(CR5R6)b, (CR5R6)a—O(CO)—(CR5R6)b, and (CR5R6)a—(CO)—(CR5R6)b, where a and b are integers which may be the same or different and each independently is 1 to 12;
• R5 and R6 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C6)alkyl, methoxy, ethoxy, linear or branched (C3-C6)alkyloxy, (C2-C6)acyl, (C2-C6)acyloxy, phenyl and phenoxy;
• Aryl is phenyl or phenyl substituted with one or more of groups selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl, hydroxy, methoxy, ethoxy, linear or branched (C3-C6)alkyloxy, (C2-C6)acyl, (C2-C6)acyloxy, phenyl and phenoxy;
• or
• one of R1 or R2 taken together with one of R3 or R4 and the carbon atoms to which they are attached to form a (C5-C7)carbocyclic ring optionally containing one or more double bonds;
• b) optionally one or more monomers of formula (IV):
• wherein
• R16 and R17 are the same or different and each independently selected from the group consisting of hydrogen, methyl ethyl, linear or branched (C3-C6)alkyl, methoxy, ethoxy, linear or branched (C3-C6)alkyloxy, acetoxy, (C2-C6)acyl, phenyl and phenoxy;
• or
• R16 taken together with R17 and the carbon atoms to which they are attached to form a (C5-C7)carbocyclic ring optionally containing one or more double bonds;
• R18 is hydrogen, halogen, methyl, ethyl, linear or branched (C3-C16)alkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C6)alkyl, hydroxy, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, (C6-C10)aryloxy, (C6-C10)aryl(C1-C6)alkoxy, —O(CO)R19 and —O(CO)OR19, where R19 is methyl, ethyl, linear or branched (C3-C16)alkyl, (C6-C10)aryl or (C6-C10)aryl(C1-C6)alkyl;
• c) a latent organo-ruthenium carbide catalyst of formula (II) or formula (III):
• wherein:
• L is PR3, where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C5-C10)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;
• R7 is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
• R8 and R9 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C1-C6)alkyl, (C6-C10)aryl, methoxy, ethoxy, linear or branched (C1-C6)alkoxy, (C6-C10)aryloxy, —NHCO(C1-C6)alkyl, —NHCO-perfluoro(C1-C6)alkyl, —SO2N((C1-C6)alkyl)2 and —NO2;
• or
• R8 and R9 taken together with the carbon atom to which they are attached to form a (C3-C7)cycloalkyl ring;
• each R10 is independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C1-C6)alkyl;
• Ar1 and Ar2 are the same or different and each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
• wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl;
• d) a photoactive or a thermoactive acid generator;
• and
• e) a compound of the formula (V):
• wherein
• X is chlorine;
• R30 and R31 are the same or different and independently of each other selected from the group consisting of hydrogen, chlorine, methyl, ethyl, linear or branched (C3-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl and (C6-C10)-aryloxy.