US 11,795,285 B2 · Dual UV blockers containing stable photoactive mass polymerizable polycycloolefin compositions as optical materials

Abstract

Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium compound, a photosensitizer, one or more monomers which undergo ring open metathesis polymerization (ROMP) and at least two distinct types of UV blockers, where when said composition is exposed to suitable actinic radiation forms a substantially transparent film or a three dimensional object. Surprisingly, the compositions are very stable at ambient conditions to temperatures up to 80° C. for several weeks and undergo mass polymerization only when subjected to actinic radiation under inert atmosphere such as for example a blanket of nitrogen. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as 3D printing materials, coatings, encapsulants, fillers, leveling agents, among others.

A composition comprising:

a) one or more monomers of formula (I):
wherein:
m is an integer 0, 1 or 2;
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, perfluoro(C1-C12)alkyl, hydroxy(C1-C16)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C6)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C6)alkyl, 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, hydroxy, methoxy, ethoxy, linear or branched (C3-C6)alkyloxy, acetoxy, (C2-C6)acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C3-C6)alkyl, 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, acetoxy, (C2-C6)acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C3-C6)alkyl, phenyl and phenoxy;
b) an organo-ruthenium compound of formula (II):
wherein
c and d are integers from 0 to 5;
Z is oxygen or sulfur;
R7 is selected from the group consisting of hydrogen, (C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20)alkynyl and (C6-C10)aryl;
and
R8, R9, R10 and R11 are the same or different and each independently selected from the group consisting of hydrogen, halogen, (C1-C16)alkyl, (C1-C16)alkoxy, (C1-C16)perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C16)alkenyl, (C6-C14)aryl, (C6-C14)perfluoroaryl,
(C3-C12)heterocyclyl, —OR16, —NO2, —COOH, —COOR16, —CONR16R17, —SO2NR16R17, —SO2R16, —CHO, —COR16, wherein R16 and R17 are the same or different and each independently selected from the group consisting of (C1-C6)alkyl, (C1-C6)perfluoroalkyl, (C6-C14)aryl, (C6-C14)perfluoroaryl;
or wherein
two or more of R8, R9, R10 and R11 taken together with the carbon atoms to which they are attached to form a substituted or unsubstituted, fused (C4-C8)carbocyclic ring, or a substituted or unsubstituted, fused aromatic ring;
each R12, R13 and R14 may be the same or different and independently of the other selected from the group consisting of hydrogen, halogen, (C1-C16)alkyl, (C1-C16)alkoxy, (C1-C16)perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C16)alkenyl, (C6-C14)aryl, (C6-C14)perfluoroaryl, (C3-C12)heterocyclyl, —OR16, —NO2, —COOH, —COOR16, —CONR16R17, —SO2NR16R17, —SO2R16, —CHO, —COR16, wherein R16 and R17 are the same or different and each independently selected from the group consisting of (C1-C6)alkyl, (C1-C6)perfluoroalkyl, (C6-C14)aryl, (C6-C14)perfluoroaryl;
R15 is selected from the group consisting of (C1-C16)alkyl, (C1-C16)perfluoroalkyl, (C3-C16)cycloalkyl, (C6-C14)aryl, (C6-C14)perfluoroaryl and (C3-C12)heterocyclyl;
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 each of said substituents are independently selected from the group consisting of methyl, ethyl and linear or branched (C3-C6)alkyl;
c) a compound of formula (V):
wherein
n is an integer from 0 to 4;
each R32 is independently 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;
d) a compound of formula (VI):
wherein
R33 is selected from the group consisting of methyl, ethyl, linear or branched (C3-C12)alkyl and (C3-C12)cycloalkyl
each of R34 and R35 may be the same or different and independently selected from the group consisting of (C1-C10)alkyl, (C6-C18)aryl, (C6-C12)aryl(C1-C5)alkyl and (C1-C5)alkyl(C6-C12)aryl;
where each of alkyl is independently linear or branched and optionally portions of methylene on the alkyl is replaced with a group selected from the group consisting of —CO—, —O—, or —COO—;
and
e) a photoactive compound of formula (VII):
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.

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Dual UV blockers containing stable photoactive mass polymerizable polycycloolefin compositions as optical materials

Life of this patent

Dual UV blockers containing stable photoactive mass polymerizable polycycloolefin compositions as optical materials

Life of this patent

Abstract

Claims20