Liquids
The present invention concerns the curing and hardening of liquids comprising unsaturated resins, a peroxide and a chelant capable of chelating at least one transition metal ion through three, four, or five nitrogen atoms, which chelants may each optionally be complexed with one or two transition metal ions, typically iron or manganese ions. The invention also provides methods and formulations for making associated compositions, compositions resultant from the curing of such liquids and associated kits comprising two or more compositions physically separated from one another, which may be used to provide curable liquids when mixed.
1 . A composition comprising:
(i) from 5 to 95% w/w of an unsaturated resin;
(ii) from 0.001 to 10% w/w of a peroxide;
(iii) from 0.00001 to 0.2% w/w of a chelant, which is of formula (III):
wherein:
each D is independently selected from the group consisting of thiazol-2-yl, thiazol-4-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-3-yl, pyrazol-1-yl, pyrrol-2-yl, imidazol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl and 1,2,3-triazol-4-yl, each of which may be optionally substituted by one or more groups independently selected from the group consisting of —F, —Cl, —Br, —OH, —OC 1 -C 4 alkyl, —NH—CO—H, —NH—CO—C 1 -C 4 alkyl, —NH 2 , —NH—C 1 -C 4 alkyl, and —C 1 -C 4 alkyl;
R1 and each R2 are independently selected from the group consisting of C 1 -C 24 alkyl, C 6-10 arylC 1 -C 6 alkyl, C 6-10 aryl, C 5 -C 10 heteroarylC 1 -C 6 alkyl, each of which may be optionally substituted by one or more groups selected from —F, —Cl, —Br, —OH, —OC 1 -C 4 alkyl, —NH—CO—H, —NH—CO—C 1 -C 4 alkyl, —NH 2 , —NH—C 1 -C 4 alkyl and —SC 1 -C 4 alkyl; and CH 2 CH 2 N(R8)(R9),
wherein N(R8)(R9) is selected from the group consisting of di(C 1-44 alkyl)amino; di(C 6-10 aryl)amino in which each of the aryl groups is independently optionally substituted with one or more C 1-20 alkyl groups; di(C 6-10 arylC 1-6 alkyl)amino in which each of the aryl groups is independently optionally substituted with one or more C 1-20 alkyl groups; NR7, in which R7 and the nitrogen atom N to which it is attached represent a heterocycloalkyl group optionally substituted with one or more C 1-20 alkyl groups, which is connected to the remainder of R1 or R2 through the nitrogen atom N; di(heterocycloalkylC 1-6 alkyl)amino, in which each of the heterocycloalkyl groups is independently optionally substituted with one or more C 1-20 alkyl groups; and di(heteroarylC 1-6 alkyl)amino, wherein each of the heteroaryl groups is independently optionally substituted with one or more C 1-20 alkyl groups;
R3 and R4 are independently selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkyl-O—C 1 -C 8 alkyl, C 6 -C 10 aryloxyC 1 -C 8 alkyl, C 6 -C 10 aryl, C 1 -C 8 hydroxyalkyl, C 6 -C 10 arylC 1 -C 6 alkyl and C 5 -C 10 heteroarylC 1 -C 6 alkyl, and —(CH 2 ) 0-4 C(O)OR5 wherein R5 is independently selected from: hydrogen, C 1 -C 8 alkyl and C 6-10 aryl; and
X is selected from C═O, —[C(R6) 2 ] 0-3 - wherein each R6 is independently selected from hydrogen, hydroxyl, C 1 -C 4 alkoxy and C 1 -C 4 alkyl
2 . The composition of claim 1 , wherein the resin is an unsaturated polyester resin or a vinyl ester resin.
3 . The composition of claim 1 , which comprises a complex comprising the chelant and a transition metal ion selected from the group consisting of transition metal ions of iron, manganese, vanadium and copper.
4 . The composition of claim 3 , wherein the complex is not well-defined.
5 . The composition of claim 3 , wherein the transition metal ion and the chelant are present in the composition in a molar ratio of transition metal ion:chelant of between about 0.1:1 and about 10:1.
6 . The composition of claim 3 , wherein the transition metal ion and the chelant are present in the composition in a molar ratio of transition metal ion:chelant of between about 0.3:1 and about 3:1.
7 . The composition of claim 3 , wherein the transition metal ion is selected from the group consisting of transition metal ions of iron and manganese.