Curable compositions
Provided herein are curable compositions useful for, among other things, making three-dimensional parts by additive manufacturing. The compositions when cured exhibit a surprising balance of improved tensile strength and percent elongation.
1 . A three dimensionally printable curable composition comprising:
a polybutadiene urethane (meth)acrylate in an amount of about 25 to about 35 percent by weight;
a maleated isoprene (meth)acrylate in an amount of about 25 to about 35 percent by weight;
a (meth)acrylate monomer wherein the (meth)acrylate monomer is present in an amount greater than either of the polybutadiene urethane (meth)acrylate or the maleated isoprene (meth)acrylate; and
a photoinitiator, wherein the percent by weight is based on the total composition, and wherein when three dimensionally printed cured products of the composition exhibit at least one of the following physical properties: percent elongation of greater than about 115, modulus of greater than about 3, tensile strength of greater than about 2 and tear strength of greater than about 10 kN/m and after exposure to an elevated temperature condition and/or radiation in the electromagnetic spectrum at a second wavelength, the composition exhibits at least one of the following physical properties: percent elongation of greater than about 115, modulus of greater than about 30, tensile strength of greater than about 9 Mpa·s and tear strength of greater than about 28 KN/m.
2 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate comprises at least two (meth)acrylate functional groups.
3 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate has a molecular weight of at least about 17,000.
4 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate has a molecular weight of about 35,000.
5 . The composition of claim 1 wherein the maleated isoprene (meth)acrylate has a melt viscosity of at least about 30 Pas at a temperature of 38° C.
6 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate has a melt viscosity of at least about 190 Pas at a temperature of 38° C.
7 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate has a Tg of about −60° C.
8 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate has a flash point of about 195° C.
9 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate comprises 1,3-butadiene-2-methyl-homocopolymer, maleated, 2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl esters.
10 . The composition of claim 1 , wherein the maleated isoprene (meth)acrylate and the polybutadiene urethane (meth)acrylate are present in a by weight ratio of about 1:1.
11 . The composition of claim 1 , wherein the (meth)acrylate monomer is selected from one or more of tetrahydrofurfural acrylate, hydroxyethylacrylate, hydroxypropyl acrylate, isobornyl acrylate, isobornyl methacyrlate, lauryl acrylate, lauryl methacrylate, tetraethyleneglycol dioctanoate, butylene glycol diacrylate, diethylene glycol diacrylate, hexandiol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylol propane ethoxylate triacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, trimethylol propane triacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, cyclic trimethylolpropane formal acrylate, difunctional tricyclodecanedimethanol diacrylate, 2-phenoxyethyl acrylate and their corresponding (meth)acrylate monomers.
12 . The composition of claim 1 , wherein the (meth)acrylate monomer is isobornyl acrylate or isobornyl methacrylate.
13 . The composition of claim 1 , wherein the (meth)acrylate monomer is present in an amount greater than about 25 to about 75 percent by weight, based on the total weight of the composition.
14 . The composition of claim 1 , wherein the polybutadiene urethane (meth)acrylate has a Tg of about −20° C.
15 . The composition of claim 1 , wherein after exposure to radiation in the electromagnetic spectrum at a first wavelength, the composition exhibits at least one of the following physical properties: percent elongation of greater than about 115, modulus of greater than about 3, tensile strength of greater than about 5 and tear strength of greater than about 10 KN/m and after exposure to an elevated temperature condition and/or radiation in the electromagnetic spectrum at a second wavelength, the composition exhibits at least one of the following physical properties: percent elongation of greater than about 115, modulus of greater than about 30, tensile strength of greater than about 6 Mpa·s and tear strength of greater than about 28 KN/m.
16 . The composition of claim 1 , wherein the composition exhibits a second modulus after exposure to an elevated temperature condition and/or radiation in the electromagnetic spectrum at a second wavelength that is about 10 times greater than a first modulus after exposure to radiation in the electromagnetic spectrum.
17 . A method of preparing a three-dimensional printed part made by additive manufacturing, comprising the steps of:
A) performing additive manufacturing using a curable composition of claim 1 to form a three-dimensional part on a build substrate, said three-dimensional printed part made according to data indicating a pre-determined pattern; and
B) optionally, removing the three-dimensional printed part of formed in step A from the build substrate.
18 . A method of preparing a three-dimensional printed part made by additive manufacturing, comprising the steps of:
A) providing a build surface;
B) providing a curable composition of claim 1 , a portion of which is deposited on the build surface according to data indicating a pre-determined pattern;
C) exposing the portion of the curable composition to radiation in the electromagnetic spectrum to form a three-dimensional printed part;
D) optionally, exposing the three-dimensional printed part formed in step C to a second energy source; and
E) optionally, removing the so-formed part from the build substrate.