Fabrication of solid materials or films from a polymerizable liquid
The disclosure describes a polymerizable liquid that includes a reactive oligomer and a reactive monomer. The polymerizable liquid is an energy polymerizable liquid hardenable by a single reaction mechanism forming a Photoplastic material. The disclosure further describes a method of producing the Photoplastic material and articles that can be made from the Photoplastic material.
1. A free radical polymerizable liquid for forming a three-dimensional object, the free radical polymerizable liquid comprising:
a reactive oligomer, the reactive oligomer being at least one of (i) a multi-functional methacrylate oligomer, and (ii) a multi-functional acrylate oligomer; and
a reactive monofunctional monomer, the reactive monofunctional monomer being at least one of (i) a monofunctional N-vinyl monomer, (ii) a monofunctional vinyl ether monomer, (iii) a monofunctional vinyl ester monomer, (iv) a monofunctional vinylamide monomer, (v) a styrene monomer, (vi) a monofunctional acrylamide monomer, (vii) a monofunctional (meth)acrylate monomer, (viii) a cyanoacrylate monomer, (ix) a monofunctional vinyl carbonate monomer, (x) a monofunctional acryloyl monomer, and (xi) a monofunctional vinyl carbamate monomer,
wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 10:1,
the free radical polymerizable liquid being an energy polymerizable liquid hardenable by a single reaction mechanism forming a photoplastic material.
2. The polymerizable liquid of claim 1 , further comprising a photoinitiator from about 0.01 percent to about 15 percent by weight.
3. The polymerizable liquid of claim 1 , wherein the polymerizable liquid has a toughness equal to or greater than a utilization curve defined by the expressions: 1) ultimate tensile strength (MPa)=−0.75×elongation+130 for elongations from about 15% to about 95%, 2) ultimate tensile strength (MPa)=4500/(elongation−25)−5 for elongations from about 95% to about 500%.
4. The polymerizable liquid of claim 1 , wherein the polymerizable liquid has a toughness equal to or greater than a utilization curve defined by the expressions: 1) ultimate tensile strength (MPa)=−1×elongation+120 for elongations from less than 105%, 2) ultimate tensile strength (MPa)=2000/(elongation+10)−3 for elongations from about 105% to about 550% 3) ultimate tensile strength (MPa)=0.5 for elongations greater than about 550%.
5. The polymerizable liquid of claim 1 , wherein the polymerized material reaches prescribed mechanical properties without supplied heat.
6. The polymerizable liquid of claim 1 , further comprising at least one of a non-reactive light absorbing pigment in an amount from about 0.001 percent to about 10 percent by weight, a filler, a polymerization inhibitor, and a polymerization catalyst.
7. The polymerizable liquid of claim 1 , further comprising a non-reactive light absorbing pigment in an amount from about 0.001 percent to about 10 percent by weight, and a filler.
8. The polymerizable liquid of claim 1 , wherein the oligomer and the monomer react by a same polymerization mechanism and have different reaction rates.
9. The polymerizable liquid of claim 1 , wherein the solubility of the monomer and oligomer change during polymerization, which assists homopolymerization of either the monomeric or oligomeric species.
10. The polymerizable liquid of claim 1 , wherein polymerization creates a material with more than one glass transition temperature.
11. The polymerizable liquid of claim 1 , wherein polymerization creates a material with two different glass transition temperatures, with a difference in Tg by at least 60 degrees C.
12. The polymerizable liquid of claim 1 , wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 25:1.
13. The polymerizable liquid of claim 12 , wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 30:1.
14. The polymerizable liquid of claim 1 , wherein the polymerizable liquid forms a print on a substrate.
15. The polymerizable liquid of claim 1 , wherein the polymerizable liquid is hardened to form a film or three-dimensional object by stereolithography (SLA), digital light projection (DLP), material jetting, or inkjet printing.
16. The polymerizable liquid of claim 15 , wherein the thickness of the inkjet film or the 3D printed layer is greater than about 30 um.
17. The polymerizable liquid of claim 1 , wherein when hardened the polymerizable liquid has adjustable mechanical properties resulting from changing the energy polymerization conditions.
18. The polymerizable liquid of claim 1 , wherein the polymerizable liquid is non-toxic.
19. The polymerizable liquid of claim 1 , wherein the oligomer has a molecular weight greater than about 1500 grams/mole.
20. The polymerizable liquid of claim 19 , wherein the oligomer has a molecular weight greater than about 4000 grams/mole.
21. The polymerizable liquid of claim 1 , wherein the monomer is a mono-functional N-vinyl, vinyl ester, or acryloyl selected from the group consisting of N-Vinylpyrrolidone, N-Vinylcaprolactam, N-Vinylformamide, Acryloyl morpholine or Vinyl cinnamate.
22. A method for forming a polymerizable liquid, the method comprising:
mixing together:
a reactive oligomer, the reactive oligomer being at least one of (i) a 1 or more functional N-vinyl oligomer, (ii) a 1 or more functional vinyl ether oligomer, (iii) a 1 or more functional vinyl ester oligomer, (iv) a 1 or more functional vinylamide oligomer, (v) a styrene oligomer, (vi) a 1 or more functional acrylamide oligomer, (vii) a 1 or more functional (meth)acrylate oligomer having a different reaction speed than the 1 or more functional (meth)acrylate monomer, (viii) a cyanoacrylate oligomer, (ix) a 1 or more functional vinyl carbonate oligomer, and (x) a 1 or more functional acryloyl oligomer, (xi) 1 or more functional vinyl carbamate oligomer; and
a reactive monomer, the reactive monomer being at least one of (i) a 1 or more functional N-vinyl monomer, (ii) a 1 or more functional vinyl ether monomer, (iii) a 1 or more functional vinyl ester monomer, (iv) a 1 or more functional vinylamide monomer, (v) a styrene monomer, (vi) a 1 or more functional acrylamide monomer, (vii) a 1 or more functional (meth)acrylate monomer of having a different reaction speed than the 1 or more functional (meth)acrylate oligomer, (viii) a cyanoacrylate monomer, (ix) a 1 or more functional vinyl carbonate monomer, (x) a 1 or more functional acryloyl monomer, and (xi) 1 or more functional vinyl carbamate monomer,
wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 10:1,
the polymerizable liquid being an energy polymerizable liquid hardenable by a single reaction mechanism to form a Photoplastic material.
23. The method of claim 22 , wherein the polymerizable liquid is hardened to produce a film or three-dimensional object by stereolithography (SLA), digital light/projection (DLP), material jetting (Inkjet Printing in 3D), or inkjet printing.
24. The method of claim 23 , wherein the film or three-dimensional object is a medical device or part of footwear or part of soft robotics.
25. The method of claim 23 , wherein the film or three-dimensional object is a hydrogel.
26. The method of claim 21 , wherein pixel or voxel polymerization is employed to produce different physical properties by altering the energy polymerization conditions.
27. The method of claim 22 , further comprising irradiating the polymerizable liquid with patterned irradiation.
28. The method of claim 22 , further comprising mixing in a photoinitiator in an amount from about 0.01 percent to about 15 percent by weight.
29. An article comprising:
an energy polymerizable liquid hardened by a single reaction mechanism forming a Photoplastic material, the energy polymerizable liquid being made from:
a reactive oligomer, the reactive oligomer being at least one of (i) a 1 or more functional N-vinyl oligomer, (ii) a 1 or more functional vinyl ether oligomer, (iii) a 1 or more functional vinyl ester oligomer, (iv) a 1 or more functional vinylamide oligomer, (v) a styrene oligomer, (vi) a 1 or more functional acrylamide oligomer, (vii) a 1 or more functional (meth)acrylate oligomer having a different reaction speed than the 1 or more functional (meth)acrylate monomer, (viii) a cyanoacrylate oligomer, (ix) a 1 or more functional vinyl carbonate oligomer, and (x) a 1 or more functional acryloyl oligomer, (xi) 1 or more functional vinyl carbamate oligomer; and
a reactive monomer, the reactive monomer being at least one of (i) a 1 or more functional N-vinyl monomer, (ii) a 1 or more functional vinyl ether monomer, (iii) a 1 or more functional vinyl ester monomer, (iv) a 1 or more functional vinylamide monomer, (v) a styrene monomer, (vi) a 1 or more functional acrylamide monomer, (vii) a 1 or more functional (meth)acrylate monomer of having a different reaction speed than the 1 or more functional (meth)acrylate oligomer, (viii) a cyanoacrylate monomer, (ix) a 1 or more functional vinyl carbonate monomer, (x) a 1 or more functional acryloyl monomer, and (xi) 1 or more functional vinyl carbamate monomer,
wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 10:1.
30. The article of claim 29 , wherein when hardened the polymerizable liquid has adjustable mechanical properties by changing the energy polymerization conditions.