US 11,732,086 B2
Two component mass polymerizable compositions containing polycycloolefin monomers and organoruthenium carbide precatalyst
Larry F Rhodes, Akron, OH (US); and Oleksandr Burtovyy, Akron, OH (US)
Assigned to PROMERUS, LLC, Akron, OH (US)
Filed by PROMERUS, LLC, Akron, OH (US)
Filed on Feb. 22, 2022, as Appl. No. 17/677,764.
Application 17/677,764 is a continuation of application No. 17/024,760, filed on Sep. 18, 2020, granted, now 11,286,338.
Claims priority of provisional application 62/901,853, filed on Sep. 18, 2019.
Prior Publication US 2022/0177640 A1, Jun. 9, 2022
This patent is subject to a terminal disclaimer.
Int. Cl. C08F 2/46 (2006.01); C08F 2/50 (2006.01); C08G 61/04 (2006.01); C08G 61/02 (2006.01); C08K 5/45 (2006.01); C08K 5/02 (2006.01); C08K 5/375 (2006.01); B01J 31/22 (2006.01); B33Y 70/00 (2020.01); B33Y 80/00 (2015.01)
CPC C08G 61/02 (2013.01) [B01J 31/2265 (2013.01); C08K 5/02 (2013.01); C08K 5/375 (2013.01); C08K 5/45 (2013.01); B01J 2231/543 (2013.01); B01J 2531/821 (2013.01); B33Y 70/00 (2014.12); B33Y 80/00 (2014.12); C08G 2261/148 (2013.01); C08G 2261/1424 (2013.01); C08G 2261/1426 (2013.01); C08G 2261/3327 (2013.01); C08G 2261/418 (2013.01)] 20 Claims
 
1. A two component composition comprising component A and component B, wherein component A contains a latent organo-ruthenium carbide catalyst and component B contains a photoactive or a thermoactive acid generator and either of the component A or the component B further comprising:
a) one or more monomers of formula (I):

OG Complex Work Unit Chemistry
wherein:
m is an integer 0, 1 or 2;
custom character 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-C12)bicycloalkyl, (C7-C14)tricycloalkyl, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, (C2-C6)acyl, (C2-C6)acyloxy, 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, (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 selected from the group consisting of phenyl, biphenyl and naphthyl, where the aryl is optionally 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; and
b) a photoactive compound selected from the group consisting of:
a compound of the formula (V):

OG Complex Work Unit Chemistry
wherein
X is hydrogen or 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; and
a compound of the formula (VI):

OG Complex Work Unit Chemistry
wherein
R32, R33 and R34 are the same or different and independently of each other selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-C12)alkyl, trichloromethyl, pentachloroethyl, linear or branched perhalo(C3-C12)alkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, perhalo(C6-C10)aryl, perhalo(C6-C10)arylperhalo(C1-C3)alkyl, substituted or unsubstituted five membered or six membered heteroaryl(C2-C4)alkenyl and substituted or unsubstituted (C6-C10)aryl(C2-C4)alkenyl provided that one of R32, R33 and R34 is trihalomethyl, pentahaloethyl, linear or branched perhalo(C3-C12)alkyl; and
wherein said latent organo-ruthenium carbide catalyst is of formula (II):

OG Complex Work Unit Chemistry
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;
Ar1 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
wherein substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl; and
wherein said component A and component B are in a clear liquid form having a viscosity below 100 centipoise at 25° C.