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US 11,230,566 B2Granted
Shelf life mass polymerizable polycycloolefin compositions as optical materials
AssigneePromerus, LLC
InventorOleksandr Burtovyy
Life of this patent
Estimating the term…
Abstract
Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium compound and a pyridine compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to suitable actinic radiation to form a substantially transparent film. Surprisingly, the compositions are very stable at ambient conditions to temperatures up to 80° C. for several days and undergo mass polymerization when subject only to actinic radiation. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as 3D printing materials, coatings, encapsulants, fillers, leveling agents, among others.
Claims20
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 selected from the group consisting of a compound of formula (II) and a compound of formula (III):
- wherein
- L is P(R)3, wherein each R is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl, (C3-C8)cycloalkyl and (C6-C10)aryl;
- R7 and R8 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 and linear or branched (C3-C6)alkyloxy;
- R9 is selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl, (C6-C10)aryl and (C6-C10)aryl(C1-C6)alkyl;
- Ar1, Ar2 and Ar3 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 selected from the group consisting of:
- a compound of formula (IVa), a compound of formula (IVb), a compound of formula (Va), a compound of formula (Vb) and a compound of formula (Vc):
- wherein
- n is an integer from 0 to 4;
- x is an integer from 2 to 5;
- y is an integer from 4 to 12;
- each R10 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl;
- R11 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 halogen;
- each R12 is independently selected from the group consisting of iso-propyl, iso-butyl tert-butyl, iso-amyl and branched (C5-C8)alkyl;
- and
- d) a photoactive compound of formula (VI):
- 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
- said composition is in a clear liquid form at room temperature.
30 more elements
A kit for forming a substantially transparent film 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-C3)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 selected from the group consisting of a compound of formula (II) and a compound of formula (III):
- wherein
- L is PR3, wherein each R is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl, (C3-C8)cycloalkyl and (C6-C10)aryl;
- R7 and R8 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 and linear or branched (C3-C6)alkyloxy;
- R9 is selected from the group consisting of methyl, ethyl, linear or branched (C3-C6)alkyl, (C6-C10)aryl and (C6-C10)aryl(C1-C6)alkyl;
- Ar1, Ar2 and Ar3 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;
- and
- c) a compound selected from the group consisting of:
- a compound of formula (IVa), a compound of formula (IVb), a compound of formula (Va), a compound of formula (Vb) and a compound of formula (Vc):
- wherein
- n is an integer from 0 to 4;
- x is an integer from 2 to 5;
- y is an integer from 4 to 12;
- each R10 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl;
- R11 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 halogen;
- each R12 is independently selected from the group consisting of iso-propyl, iso-butyl tert-butyl, iso-amyl and branched (C5-C8)alkyl;
- and
- d) a photoactive compound of formula (VI):
- 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.
29 more elements
Dependencies are inferred from the claim text.