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

Patent metadata

Field	Value
Publication number	US-11230624-B2
Application number	US-201916456018-A
Country	US
Kind code	B2
Filing date	Jun 28, 2019
Priority date	Jun 29, 2018
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

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.

First claim

What is claimed is:

1. 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;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 2 -C 16 )alkenyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 6 -C 12 )bicycloalkenyl(C 1 -C 12 )alkyl, (C 7 -C 14 )tricycloalkyl, methoxy, ethoxy, linear or branched (C 3 -C 16 )alkoxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, hydroxy(C 1 -C 16 )alkyl, (C 2 -C 6 )acyloxy(C 1 -C 1 6)alkyl, (C 6 -C 14 )aryl, (C 6 -C 14 )aryl(C 1 -C 6 )alkyl, perfluoro(C 6 -C 14 )aryl, perfluoro(C 6 -C 14 )aryl(C 1 -C 3 )alkyl, (C 6 -C 14 )aryloxy, (C 6 -C 14 )aryl(C 1 -C 6 )alkoxy, tri(C 1 -C 6 )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:
(CR 5 R 6 )a, O(CR 5 R 6 )a, (CR 5 R 6 )a-O—, (CR 5 R 6 )a—O—(CR 5 R 6 )b, (CR 5 R 6 )a—O—(SiR 5 R 6 )b, (CR 5 R 6 )a—(CO)O—(CR 5 R 6 )b, (CR 5 R 6 )a—O(CO)—(CR 5 R 6 )b, (CR 5 R 6 )a—(CO)—(CR 5 R 6 )b, where a and b are integers which may be the same or different and each independently is 1 to 12;
R 5 and R 6 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )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 (C 3 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy; or
one of R 1 or R 2 taken together with one of R 3 or R 4 and the carbon atoms to which they are attached to form a (C 5 -C 9 )cycloalkyl or a (C 6 -C 12 )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;
R 16 and R 17 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, acetoxy, (C 2 -C 6 )acyl, phenyl and phenoxy; or
R 16 taken together with R 17 and the carbon atoms to which they are attached to form a (C 5 -C 9 )cycloalkyl or a (C 6 -C 12 )bicycloalkyl ring optionally containing one or more double bonds;
R 18 is hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 16 )alkoxy, (C 6 -C 10 )aryloxy, (C 6 -C 10 )aryl(C 1 -C 6 )alkoxy, —O(CO)R 19 and —O(CO)OR 19 , where R 19 is methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 6 )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
R 30 and R 31 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl and (C 6 -C 10 )-aryloxy; and
a compound of the formula (VI):

wherein
R 32 , R 33 and R 34 are the same or different and independently of each other selected from the group consisting of halogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, trihalomethyl, pentahaloethyl, linear or branched perhalo(C 3 -C 12 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perhalo(C 6 -C 10 )aryl, perhalo(C 6 -C 10 )arylperhalo(C 1 -C 3 )alkyl, substituted or unsubstituted five membered or six membered heteroaryl(C 2 -C 4 )alkenyl and substituted or unsubstituted (C 6 -C 10 )aryl(C 2 -C 4 )alkenyl provided that one of R 32 , R 33 and R 34 is trihalomethyl, pentahaloethyl, linear or branched perhalo(C 3 -C 12 )alkyl; and wherein
said composition is in a clear liquid form at room temperature.

2. The composition according to claim 1 , wherein said composition comprising first and second monomer of formula (I) distinct from each other and one of said first and second monomers having a viscosity below 50 centipoise, and wherein said first monomer is completely miscible with said second monomer to form a clear solution.

3. The composition according to claim 1 , wherein said composition comprising a monomer of formula (I) wherein m is 1 and each of R 1 , R 2 , R 3 and R 4 are hydrogen.

4. The composition according to claim 3 , wherein said composition comprising a monomer of formula (IV) where R 18 is hydrogen.

5. The composition according to claim 1 , wherein said composition comprising first and second monomer of formula (I) distinct from each other, wherein said first monomer is of formula (I) wherein m is 1 and each of R 1 , R 2 , R 3 and R 4 are hydrogen; and wherein said second monomer is of formula (I) wherein m is 0, R 1 is decyl and each of R 2 , R 3 and R 4 are hydrogen.

6. The composition according to claim 1 , wherein the monomer of formula (I) is selected from the group consisting of:

7. The composition according to claim 1 comprising one or more monomers of formula (IV), which is selected from the group consisting of:

8. The composition according to claim 1 , wherein said one or more monomer of formula (I) is selected from the group consisting of:
tetracyclododecene (TD);
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexylTD);
2-decyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (DecylTD);
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);
5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);
5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; and
5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEt0-2-PhPh);
and wherein said monomer of formula (IV) is dicyclopentadiene (DCPD);
and mixtures in any combination thereof.

9. The composition according to claim 1 , wherein the latent catalyst is an organo-ruthenium compound se

Assignees

• Promerus Llc

Inventors

• Burtovyy Oleksandr
• Barchok Matthew L
• Zhang Wei
• Rhodes Larry F

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G2261/3325

  derived from other polycyclic systems · CPC title

• C09D11/10

  based on artificial resins · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title