Additives useful in 3D printing technologies

A method for preparing an object by a 3D printing process based on dual polymerization, wherein the 3D printing process based on dual polymerization comprises the following steps:

• (1) a Part A photopolymerizable component of a resin is polymerized first by a light induced process to form an intermediate object, (2) the intermediate object is then further cured by a Part B polymerizable component of a resin comprising an amine composition, wherein the amine composition comprises at least one amine curing agent with the structure:
• where R is H or a C1-3 linear or branched alkyl;
• where A represents a C6-20 cyclic, polycyclic or acyclic linear or branched polyamine;
• where R1 and R2 are a C1-9 linear or branched alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent;
• and where n=1 to 6 and where m=1 to 3.

A method of forming a three-dimensional object comprising the following steps:

• a) getting in contact in an optically transparent build surface a polymerizable liquid in the presence of at least one of a reactive diluent, photoinitiator, and chain extender, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a blocked or reactive blocked oligomer or iii) a blocked or reactive blocked prepolymer;
• b) irradiating the build surface with light that passes through a radiation-transparent window to form a solid scaffold object;
• c) heating or microwaving the solid scaffold object to induce the polymerization of the at least one of a monomer, a blocked or reactive blocked oligomer or a blocked or reactive blocked prepolymer with an amine composition to form the three-dimensional object, wherein the amine composition comprises at least one amine curing agent with the structure:
• where R3 is H and R4 is C2-6 saturated alkyl linear or branched or where R3═R4═C1-6 saturated alkyl linear or branched, wherein the at least one amine curing agent is selected from the group consisting 4,4′-methylenebis(2-ethylcyclohexylamine), 4,4′-methylenebis(2-(n -propyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2-(iso-butyl)cyclohexylamine), 4,4′-methylenebis(2-(t-butyl)cyclohexylamine), 4,4′-methylenebis(2-(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(tert -pentyl)cyclohexylamine), 4,4′-methylenebis(2-(neo-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(iso-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec -isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(3-hexyl) cyclohexylamine), 4,4′-methylenebis(2-(neo-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpent-1-yl) cyclohexylamine), 4,4′-methylenebis(2-(4-methylpent-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpent-2-yl) cyclohexylamine), 4,4′-methylenebis(2-(2-methylpent-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 4,4′-methylenebis(2,6-diethylcyclohexylamine), 4,4′-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec -propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(iso -butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(tert -pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neo-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(iso-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec -pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n -hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neo -hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpent-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpent -2-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-methylpent-2-yl)cyclohexylamine), and 4,4′-methylenebis(2,6-di(2-methylpent-1-yl)cyclohexylamine).

A method of forming a three-dimensional object comprising the following steps:

• a) getting in contact in an optically transparent build surface a polymerizable liquid in the presence of at least one of a reactive diluent, photoinitiator, and chain extender, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a blocked or reactive blocked oligomer or iii) a blocked or reactive blocked prepolymer;
• b) irradiating the build surface with light that passes through a radiation-transparent window to form a solid scaffold object;
• c) heating or microwaving the solid scaffold object to induce the polymerization of the at least one of a monomer, a blocked or reactive blocked oligomer or a blocked or reactive blocked prepolymer with an amine composition to form the three- dimensional object, wherein the amine composition comprises at least one amine curing agent with the structure:
• where R is H or a C1-3 linear or branched alkyl;
• where A represents a C6-20 cyclic, polycyclic or acyclic linear or branched polyamine;
• where R1 and R2 are a C1-9 linear or branched alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent;
• and where n=1 to 6 and where m=1 to 3.

A method of forming a three-dimensional object comprising the following steps:

• a) getting in contact in an optically transparent build surface a polymerizable liquid in the presence of at least one of a reactive diluent, photoinitiator, and chain extender, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a blocked or reactive blocked oligomer or iii) a blocked or reactive blocked prepolymer;
• b) irradiating the build surface with light that passes through a radiation-transparent window to form a solid scaffold object;
• c) heating or microwaving the solid scaffold object to induce the polymerization of the at least one of a monomer, a blocked or reactive blocked oligomer or a blocked or reactive blocked prepolymer with an amine composition to form the three-dimensional object, wherein the amine composition comprises the reaction product of i) at least one amine curing agent with the structure:
• where R is H or a C1-6 linear or branched alkyl, where A represents a C6-20 cyclic, polycyclic or acyclic linear or branched polyamine, where n=1 to 6 and where m=1 to 3, with ii) at least one a,b-unsaturated carboxylic ester.