Two component mass polymerizable compositions containing polycycloolefin monomers and organoruthenium carbide precatalyst
Embodiments in accordance with the present invention encompass a two component composition containing in one component a latent organo-ruthenium carbide catalyst, and in another component a photoactive acid generator or a thermally active acid generator, and either of the components containing a mixture of photoactive compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said components are mixed together and exposed to a suitable radiation (or heat) to form a three-dimensional (3D) object. The three-dimensional objects so formed exhibits improved mechanical properties, particularly, high heat 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.
1. A two component composition comprising component A and component B, wherein component A contains a latent organo-ruthenium carbide catalyst and component B contains a photoactive or a thermoactive acid generator and either of the component A or the component B further 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 7 -C 14 )tricycloalkyl, methoxy, ethoxy, linear or branched (C 3 -C 16 )alkoxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, 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 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 selected from the group consisting of phenyl, biphenyl and naphthyl, where the aryl is optionally 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 7 )carbocyclic ring optionally containing one or more double bonds; and
b) a photoactive compound selected from the group consisting of:
a compound of the formula (V):
wherein
X is hydrogen or chlorine;
R 30 and R 31 are the same or different and independently of each other selected from the group consisting of hydrogen, chlorine, 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, trichloromethyl, pentachloroethyl, 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 latent organo-ruthenium carbide catalyst is of formula (II):
wherein:
L is PR 3 , where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C 5 -C 10 )alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;
R 7 is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
Ar 1 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
wherein substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl; and
wherein said component A and component B are in a clear liquid form having a viscosity below 100 centipoise at 25° C.
2. The composition according to claim 1 , wherein either of the component A or the component B further comprising one or more monomers of formula (IV):
wherein
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 7 )carbocyclic 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.
3. The composition according to claim 1 , wherein either of the component A or the component B 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 at 25° C., and wherein said first monomer is completely miscible with said second monomer to form a clear solution.
4. 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.
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 2 , wherein one or more monomers of formula (IV) is selected from the group consisting of:
8. The composition according to claim 2 , wherein said one or more monomer of formula (I) is selected from the group consisting of:
tetracyclododecene (TD);
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 (NBEtO-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 organo-ruthenium carbide catalyst of formula (II) is having:
L is PR 3 , where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl;
Ar 1 and R 7 are the same or different and each independently of each other selected from the group consisting of 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl and 2,4,6-trimethylphenyl.
10. The composition according to claim 1 , wherein the organo-ruthenium carbide catalyst of formula (II) is selected from the group consisting of:
11. The composition according to claim 1 , wherein the composition comprises a photoactive compound
which is a compound of the formula (V):
wherein
X is hydrogen or chlorine;
R 30 and R 31 are the same or different and independently of each other selected from the group consisting of hydrogen, chlorine, methyl, ethyl, isopropyl, methoxy, ethoxy, propoxy and phenoxy.
12. The composition according to claim 11 , wherein the photoactive compound is selected from the group consisting of:
13. The composition according to claim 1 , wherein the photoactive or thermoactive acid generator is of the formula (VIII 1 ) or of the formula (IX):
wherein
n is an integer from 0 to 5;
An ⊕ is selected from the group consisting of Cl ⊕ , Br ⊕ , I ⊕ , BF 4 ⊕ , B(C 6 F 5 ) 4 ⊕ ,
PF 6 ⊕ , n-C 4 F 9 SO 3 ⊕ , CF 3 SO 3 ⊕ and p-CH 3 (C 6 H 4 )—SO 3 ⊕ ;
R 35 , R 36 and R 37 are the same or different and independently of each other selected from the group consisting of chlorine, methyl, ethyl, linear or branched (C 3 -C 20 )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, (C 6 -C 10 )-aryloxy, (C 6 -C 10 )-thioaryl and (C 6 -C 10 )-thioaryl-(C 6 -C 10 )diarylsulfonium salt.
14. The composition according to claim 13 , wherein the photoactive or thermoactive acid generator is selected from the group consisting of:
where R 35 and R 36 are the same or different and each independently selected from linear or branched (C 10 -C 13 )alkyl; and
15. The composition according to claim 1 , which is selected from the group consisting of:
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing tolylcumyliodonium-tetrakis pentafluorophenylborate and toluene;
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing a mixture of tolylcumyliodonium-tetrakis pentafluorophenylborate and toluene;
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing a mixture of 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene and tolylcumyliodonium-tetrakis pentafluorophenylborate; and
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, dicyclopentadiene, 1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one; and component B containing a mixture of tolylcumyliodonium-tetrakis pentafluorophenylborate and 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene.
16. A kit for forming a three dimensional object comprising component A and component B, wherein component A contains a latent organo-ruthenium carbide catalyst and component B contains a photoactive or a thermoactive acid generator and either of the component A or the component B further 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 7 -C 14 )tricycloalkyl, methoxy, ethoxy, linear or branched (C 3 -C 16 )alkoxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, (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 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 7 )carbocyclic ring optionally containing one or more double bonds;
b) optionally one or more monomers of formula (IV):
wherein
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 7 )carbocyclic 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; and
c) a compound of formula (V):
wherein
X is hydrogen or chlorine;
R 30 and R 31 are the same or different and independently of each other selected from the group consisting of hydrogen, chlorine, 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;
wherein said latent organo-ruthenium carbide catalyst is of formula (II):
wherein:
L is PR 3 , where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C 5 -C 10 )alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;
R 7 is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
Ar 1 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
wherein substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl; and
wherein said component A and said component B are in a clear liquid form having a viscosity below 100 centipoise at 25° C.
17. The kit according to claim 16 , which contains a compound of formula (V) selected from the group consisting of:
18. The kit according to claim 16 , wherein the photoactive acid generator is selected from the group consisting of:
where R 35 and R 36 are the same or different and each independently selected from linear or branched (C 10 -C 13 )alkyl; and
19. The kit according to claim 16 , which contains a mixture selected from the group consisting of:
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing tolylcumyliodonium-tetrakis pentafluorophenylborate and toluene;
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing a mixture of tolylcumyliodonium-tetrakis pentafluorophenylborate and toluene;
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, 1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, and component B containing a mixture of 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene and tolylcumyliodonium-tetrakis pentafluorophenylborate; and
component A containing a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene, dicyclopentadiene, 1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-ruthenium carbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one; and component B containing a mixture of tolylcumyliodonium-tetrakis pentafluorophenylborate and 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene.
20. A three dimensional object comprising the composition of claim 1 .