US 11,230,624 B2 · Polycycloolefin monomers and catalyst activated by compound capable of generating photoacid as 3D printing materials

Abstract

Embodiments in accordance with the present invention encompass compositions containing a latent catalyst and a compound capable of generating a Bronsted acid with a counterion capable of coordinating and activating the latent catalyst along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to a suitable radiation to form a three-dimensional (3D) object. The catalyst system employed therein can be sensitive to oxygen and thus inhibits polymerization in ambient atmospheric conditions. The three-dimensional objects made by this process exhibits improved mechanical properties, particularly, high distortion temperature, impact strength, elongation to break, among others. Accordingly, compositions of this invention are useful as 3D inkjet materials for forming high impact strength objects of various sizes with microscale features lower than 100 microns, among various other uses.

A composition 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-C12)bicycloalkyl, (C6-C12)bicycloalkenyl(C1-C12)alkyl, (C7-C14)tricycloalkyl, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, (C2-C6)acyl, (C2-C6)acyloxy, hydroxy(C1-C16)alkyl, (C2-C6)acyloxy(C1-C16)alkyl, (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 I 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)a-O—, (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 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-C9)cycloalkyl or a (C6-C12)bicycloalkyl ring optionally containing one or more double bonds;
b) optionally one or more monomers of formula (IV):
wherein
is a single bond or a double bond;
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-C9)cycloalkyl or a (C6-C12)bicycloalkyl 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 and (C6-C10)aryl(C1-C6)alkyl;
c) a latent organo-transition metal catalyst comprising a metal selected from the group consisting of ruthenium and osmium;
and
d) a compound capable of releasing a Bronsted acid when subjected to photolytic conditions, said compound selected from the group consisting of:
a compound of the formula (V):
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 the formula (VI):
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.

31 more elements

Polycycloolefin monomers and catalyst activated by compound capable of generating photoacid as 3D printing materials

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Polycycloolefin monomers and catalyst activated by compound capable of generating photoacid as 3D printing materials

Life of this patent

Abstract

Claims20