US 11,987,716 B2
High impact strength 3D printing materials derived from polycycloolefin monomers and crosslinkers
Oleksandr Burtovyy, Akron, OH (US); Wei Zhang, Akron, OH (US); Leah Langsdorf, Akron, OH (US); and Larry F Rhodes, Akron, OH (US)
Assigned to PROMERUS, LLC, Akron, OH (US)
Filed by PROMERUS, LLC, Akron, OH (US)
Filed on May 22, 2023, as Appl. No. 18/200,028.
Application 18/200,028 is a continuation of application No. 17/471,768, filed on Sep. 10, 2021, granted, now 11,697,744.
Application 17/471,768 is a continuation of application No. 16/724,600, filed on Dec. 23, 2019, granted, now 11,142,662, issued on Oct. 12, 2021.
Claims priority of provisional application 62/830,867, filed on Apr. 8, 2019.
Claims priority of provisional application 62/783,347, filed on Dec. 21, 2018.
Prior Publication US 2023/0295452 A1, Sep. 21, 2023
This patent is subject to a terminal disclaimer.
Int. Cl. C08F 2/46 (2006.01); B33Y 70/00 (2020.01); C08F 2/50 (2006.01); C08G 61/04 (2006.01); C09D 11/101 (2014.01); C09D 11/108 (2014.01); C09D 11/38 (2014.01)
CPC C09D 11/38 (2013.01) [B33Y 70/00 (2014.12); C09D 11/101 (2013.01); C09D 11/108 (2013.01)] 20 Claims
 
1. A composition 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;
R1, R2, R3 and R4 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched (C4-C16)alkyl, (C6-C14)aryl and (C1-C6)alkyl; 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) an organo-ruthenium compound selected from the group consisting of:
a compound of formula (IIB):

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a compound of formula (IIIA):

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a compound of formula (IIIB):

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a compound of formula (IIIC):

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1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium;
wherein:
X is a halogen or an anionic ligand;
Y is selected from the group consisting of 0 and S;
Y′ is selected from the group conistng of OR9, SR9 and —N═CHC(O)O(C1-C6)alkyl, where R9 is selected from the group consisting of methyl, ethyl, linear or branched (C3-C6) alkyl, (C6-C10)aryl, methoxy, ethoxy, linear or branched (C3-C6) alkoxy, (C6-C10)aryloxy, and —OCH(CH3)C(O)N(CH3)(OCH3);
L is PR3 or O=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 isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
R8 is selected from the group consisting of methyl, ethyl, linear or branched(C3-C6)alkyl, (C6-C10)aryl, methoxy, ethoxy, linear or branched (C3-C6)alkoxy, (C6-C10)aryloxy, —NHCO(C1-C6)alkyl, —NHCO-perfluoro(C1-C6)alkyl, —SO2N((C1-C6)alkyl)2 and —NO2;
Ar1, Ar2 Ar3 and Ar4 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; and
c) a compound capable of releasing a Bronsted acid when subjected to photolytic conditions, said compound selected from the group consisting of:
a compound of formula (V):

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wherein Y is halogen; and
R30 and R31 are the same or different and independently of each other selected from the group consisting of hydrogen, 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 formula (VI):

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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, trihalomethyl, pentahaloethyl, 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 composition is in a clear liquid form at room temperature.