High impact strength 3D printing materials derived from polycycloolefin monomers and crosslinkers

Patent metadata

Field	Value
Publication number	US-11142662-B2
Application number	US-201916724600-A
Country	US
Kind code	B2
Filing date	Dec 23, 2019
Priority date	Dec 21, 2018
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

Embodiments in accordance with the present invention encompass a composition 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) and one or more multi-functional crosslinkable molecules when said composition is exposed to a suitable radiation forms 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 selected from the group consisting of:
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX);
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX); and
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

2. A kit comprising a composition selected from the group consisting of:
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX);
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX); and
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

3. The kit according to claim 2 , wherein when said composition is exposed to radiation at 395 nm for a sufficient length of time it forms a three dimensional object.

4. The kit according to claim 2 , which contains a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

5. The kit according to claim 2 , which contains a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

6. A three dimensional object comprising the composition of claim 1 .

7. The composition according to claim 1 , which is:
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

8. The composition according to claim 1 , which is:
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 5-decylbicyclo[2.2.1]hept-2-ene (DecylNB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

9. The composition according to claim 1 , which is:
a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

10. The kit according to claim 2 , which contains a mixture of 2-phenethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (PETD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium and 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

11. A three dimensional object comprising the composition of claim 7 .

12. A three dimensional object comprising the composition of claim 8 .

13. A three dimensional object comprising the composition of claim 9 .

14. The kit according to claim 4 , wherein when said composition is exposed to radiation at 395 nm for a sufficient length of time it forms a three dimensional object.

15. The kit according to claim 5 , wherein when said composition is exposed to radiation at 395 nm for a sufficient length of time it forms a three dimensional object.

16. The kit according to claim 10 , wherein when said composition is exposed to radiation at 395 nm for a sufficient length of time it forms a three dimensional object.

Assignees

• Promerus Llc

Inventors

• Burtovyy Oleksandr
• Zhang Wei
• Langsdorf Leah
• Rhodes Larry F

Classifications

• C09D11/38 Primary

  characterised by non-macromolecular additives other than solvents, pigments or dyes · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08G2261/1526

  of Os, Ir, Pt, Ru, Rh or Pd · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title