The present invention provides an isocyanate trimerization catalyst system, a precursor formulation, a method of trimerizing isocyanates, a rigid foam made therefrom, and a method of making such a foam. The trimerization catalyst system comprises: (a) imidazolium or imidazolinium cation; and (b) anion inducing isocyanate trimer; wherein the trimerization activation temperature of the trimerization catalyst system is less than or equal to 73°C. The precursor formulation comprises: (1) at least 25% by weight of a polyol, based on the weight of the precursor formulation; (2) less than 15% by weight of a trimerization catalyst system, based on the weight of the precursor formulation, the tripolymer The polymerization catalyst system comprises: (a) imidazolium or imidazolinium cation; and (c) anion inducing isocyanate trimer; wherein the trimerization activation temperature of the trimerization catalyst system is less than or equal to 73°C; and (3 ) optionally one or more surfactants, one or more flame retardants, water, one or more antioxidants, one or more auxiliary blowing agents, one or more carbamic acids an ester catalyst, one or more auxiliary trimerization catalysts, or a combination thereof. A method for trimerization of isocyanates comprising the steps of: (1) providing one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, oligomeric isocyanates, any salts thereof, and any mixture; (2) providing a trimerization catalyst system comprising: (a) an imidazolium or imidazolinium cation; and (b) an anion inducing trimer of isocyanate; (c) wherein said trimerization The trimerization activation temperature of the polymerization catalyst system is less than or equal to 73°C; (3) trimerizing the one or more monomers in the presence of the trimerization catalyst; (4) thereby forming one or more Isocyanurate terpolymer. A method of forming a PIR foam, comprising the steps of: (1) providing one or more monomers selected from the group consisting of isocyanate, diisocyanate, triisocyanate, oligomeric isocyanate, any salt thereof, and any a mixture; (2) providing a polyol; (3) providing a trimerization catalyst system comprising: (a) an imidazolium or imidazolinium cation; and (b) an anion inducing trimer of isocyanate; wherein The trimerization activation temperature of the trimerization catalyst system is less than or equal to 73°C; and (4) optionally providing one or more surfactants, one or more flame retardants, water, one or more An antioxidant, one or more auxiliary blowing agents, one or more urethane catalysts, one or more auxiliary trimerization catalysts, or a combination thereof; (5) making the one or more monomer, and said polyol, and optionally said one or more surfactants, and optionally said one or more flame retardants, and optionally said water, and optionally said The one or more antioxidants, and optionally the one or more auxiliary foaming agents, in the trimerization catalyst system, and optionally the one or more carbamates catalyst, and optionally said one or more auxiliary trimerization catalysts; (6) thereby forming said polyisocyanurate / polyurethane rigid foam. The PIR foam comprises: a trimerization catalyst system and optionally one or more surfactants, optionally one or more flame retardants, optionally water, optionally one or more Oxidizing agent, optional one or more auxiliary blowing agents, optional one or more additional urethane catalysts, and optional one or more auxiliary trimerization catalysts, or optional other The reaction product of one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, oligomeric isocyanates, any salts thereof, and any mixtures thereof with polyols in the presence of a trimerization catalyst system comprising imidazole Onium or imidazolinium cations, and isocyanate trimer-inducing anions, wherein the trimerization activation temperature of the trimerization catalyst system is less than or equal to 73°C. The PIR foam comprises: a trimerization catalyst system and optionally one or more surfactants, optionally one or more flame retardants, optional water, optionally one or more In the presence of an oxidizing agent, optionally one or more auxiliary blowing agents, optionally one or more additional polyurethane catalysts, and optionally one or more trimerization catalysts, or optionally a combination thereof, The reaction product of one or more monomers selected from the group consisting of isocyanates, diisocyanates, triisocyanates, oligomeric isocyanates, any salts thereof, and any mixtures thereof with polyols, the trimerization catalyst system comprising imidazolium or imidazoline Onium cations, and anions inducing isocyanate trimers, wherein at a depth of 12 mm from the raised surface of the rigid foam, the polyisocyanurate trimers of the polyisocyanurate / polyurethane foam The substance ratio (Abs1410 / Abs1595) is at least 5, as determined by ATR-FTIR spectroscopy.