Patent Application
20170225395
Additive manufacturing (also known as 3D printing, solid free-form fabrication, rapid prototyping and rapid manufacturing) includes several processes that produce three dimensional (3D) objects from a computer model by building up the object in a layer-by-layer manner. Examples of additive manufacturing processes include extrusion-based techniques (e.g., fused filament fabrication (FFF)), jetting, selective laser sintering/melting, laser engineered net shaping (LENS), powder-bed based 3D printing (e.g., powder/binder jetting), selective light modulation, electron-beam melting, and stereolithographic processes. These processes can fabricate objects from a variety of materials including metals, photopolymers, thermopolymers, and ceramics. For each of these processes, the digital representation of the 3D object is initially sliced into multiple layers. For each sliced layer, a computer provides the path instructions for the particular additive manufacturing system to print the given layer. The layers are then successively built up to form the final object.
In contrast to traditional manufacturing techniques such as injection or compression molding, the advantages of additive manufacturing include increased customizability, ease of use, orthogonality to existing manufacturing techniques, and accessibility to the additive manufacturing processes by a wide user base. Additive manufacturing has also become more available to the general public. For example, an extrusion-based technique, fused filament fabrication (FFF), has become accessible in private homes for printing the likes of toys, housewares, art pieces, and accessories for portable electronics.
In an extrusion-based additive manufacturing system, such as a fused filament fabrication (FFF) system, a 3D object can be printed from a digital representation of the object in a layer-by-layer manner by extruding a flowable material, such as a filament, through an extrusion tip carried by a print head of the system onto a substrate in an x-y plane. The extruded material fuses to previously deposited material and solidifies upon a drop in temperature. The position of the print head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is repeated to form a 3D object resembling the digital representation.
As another example, powder-based additive manufacturing processes deposit and modify powders. One example of a powder-based additive manufacturing process is the selective laser sintering process, where an object is constructed one layer at a time inside a thermally controlled process chamber, which is held at a temperature slightly below the melting point of the polymer system being used. A polymer powder is deposited in thin layers uniformly across a piston. A laser beam is scanned across the surface of a layer of powder, turning on and off to selectively sinter or fuse the polymer powder into a shape defined by a computer. After a given layer has been fused, the piston is lowered and a new layer of powder is added on top of the just completed layer. The new layer is then fused, based on the defined shape, and in this manner a 3D object can be fabricated from multiple layers.
As yet another example, selective light modulation (SLM) involves a photosensitive polymer precursor (often known as a ‘resin’) and a mechanism for exposing the photosensitive polymer precursor to electromagnetic radiation. The exposed photosensitive polymer precursor then undergoes a chemical reaction leading to polymerization and solidification (i.e., curing). In general, SLM methods include a vat to hold the photosensitive polymer precursor; a source of electromagnetic radiation (e.g., UV, near-UV, or visible light); a build platform; an elevator mechanism capable of adjusting the separation of the vat and the build platform; and a controlling computer. The source of electromagnetic radiation can be located above the vat, or below the vat. The source of the electromagnetic radiation can be a digital light processing (DLP), a digital micromirror device (DMD), a liquid crystal display (LCD), or a liquid crystal on silicon (LCOS).
As yet another example, in a jetting additive manufacturing process, a material is deposited from a nozzle which moves horizontally across the build platform. The material layers can then be cured or hardened using electromagnetic radiation and the object is built in a layer by layer manner.
Functional and responsive polymeric materials (i.e., smart materials) can be advantageously used in additive manufacturing processes. The smart materials can include piezoelectric materials, shape memory materials, magneto-strictive materials, pH-sensitive polymers, thermo-responsive polymers, chromogenic materials (liquid crystals and electrochromics), and thermoelectric materials. Of particular relevance to the length scales of 3D printed objects are smart polymers that enable translation of macroscopic inputs into molecular-level chemical outputs, such as those that are mechanically activated and chemically responsive. Importantly, this class of smart polymers has been realized through the development of “mechanophores,” molecules that are capable of mechanical-into-chemical energy transduction. The specific chemical outputs that have been demonstrated by various mechanophores provide a rich pool of capabilities including chemiluminescence, release of small molecules, generation of reactive sites for crosslinking within self-reinforcing materials, activation of metal catalysts, and mechanochromic indicators. However, despite the tremendous interest in development of mechanoresponsive “smart” materials, mechanophores have not been used in additive manufacturing.
Thus, an exciting and potentially transformative area of growth is the integration of “smart” functional polymeric materials with 3DP technologies. As these areas merge, the capabilities afforded by designer polymer synthesis can be incorporated into rapidly customizable objects and devices. The present disclosure seeks to fulfill these needs and provides further related advantages.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In one aspect, this disclosure features an additive manufacturing method that includes depositing onto a substrate a material including a blend of a mechanochromic molecule and a matrix polymer; and fusing the material to provide an article. The mechanochromic molecule has a first end and a second end and includes at least one polymer chain covalently bound to each end.
In another aspect, this disclosure features an additive manufacturing method that includes exposing a mixture that includes a mechanochromic initiator having at least two initiation groups, a first monomer capable of being covalently bound to each of the initiation groups of the mechanochromic initiator, and a second monomer capable of forming a matrix polymer to a stimulus; and polymerizing the monomers to provide a polymerized article.
In yet another aspect, this disclosure features an article, including a blend of a mechanochromic molecule and a first matrix polymer. The mechanochromic molecule has a strained moiety capable of rearranging to a colored moiety; the mechanochromic molecule further has a first end and a second end and includes at least one polymer chain covalently bound to each end.
The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings.
In general, materials that are specially designed to be stimuli-responsive are referred to as “smart” materials. As used herein, “mechanically activated” is used herein to indicate a mechanical stimulus and “chemically responsive” is used herein to indicate a chemical response or output (to any variety of stimulus). Thus, mechanically activated, chemically responsive smart materials, are realized through the incorporation of molecules that undergo chemical reactions in response to mechanical forces, and are referred to as “mechanophores.” A type of mechanophore is a mechanochromic molecule, which is a compound that changes color upon exposure to mechanical force.
The present disclosure provides an additive manufacturing method, including depositing onto a substrate a material including a blend of a mechanochromic molecule and a matrix polymer; and fusing the material to provide an article. The mechanochromic molecule has a first end and a second end and includes at least one polymer chain covalently bound to each end.
The material including a blend of a mechanochromic molecule and a matrix polymer can change color when the material is subjected to mechanical stress (e.g., pulling, compressing, bending). The color change can be reversible, such that when the material that has undergone a color change it can revert to its initial non-colored state over time, when the mechanical stress has been removed. The material can find numerous applications, such as in pressure sensors and tensile stress sensors.
At various places in the present specification, substituents of compounds of the disclosure are disclosed in groups or in ranges. It is specifically intended that the disclosure include each and every individual subcombination of the members of such groups and ranges. For example, the term “C1-6 alkyl” is specifically intended to individually disclose methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.
It is further appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment.
Conversely, various features of the disclosure which are, for brevity, described in the context of a single embodiment, can also be provided separately or in any suitable sub combination.
As used herein, the term “substituted” or “substitution” refers to the replacing of a hydrogen atom (H) with a substituent other than H. For example, an “N-substituted piperidin-4-yl” refers to replacement of the H atom from the NH of the piperidinyl with a non-hydrogen substituent such as, for example, alkyl.
As used herein, “depositing/deposition” refers to setting down of a material onto a substrate or a material supported by a substrate.
As used herein, “blend” refers to a mixture of two or more components.
As used herein, “mechanochromic molecule” refers to a molecule that changes color upon exposure to mechanical force. In some embodiments, the color change is reversible, such that a color appears over a period of time upon application of a mechanical force and disappears over a period of time upon removal of the mechanical force. In some embodiments, upon application of a mechanical force, the molecule can change from colored to colorless. As used herein, the mechanochromic molecule is the entire molecule, which can include any covalently bound polymers. The mechanochromic moiety is a portion of the mechanochromic molecule that provides the color changing property, such as a spiropyran core, a naphthopyran core, or a spirooxazine core.
As used herein, “matrix polymer” refers to a polymer that surrounds the mechanochromic molecules (i.e., the matrix polymer provides a matrix for the mechanochromic molecules).
As used herein, “strained moiety” refers to a portion of a molecule having a stress that raises its internal energy. The stress can take the form of torsional strain, ring strain, and/or steric strain.
As used herein, “conjugated” refers to the overlay of one p-orbital with another across an intervening sigma bond. In transition metals, d-orbitals can be involved. A conjugated system has a region of overlapping p-orbitals, bridging the intervening single bonds. Delocalization of pi electrons across all the adjacent aligned p-orbitals can occur, where the pi electrons do not belong to a single bond or atom, but to a group of atoms.
As used herein, “colored” refers to a molecule that absorbs in the visible wavelength range of about 380 to 780 nm.
As used herein, “selective laser sintering” refers to an additive manufacturing technique that uses a laser as the power source to sinter (i.e., heat and fuse) powdered material (e.g., a polymer, or a polymer blend).
As used herein, “fused filament fabrication” (FFF) refers to an additive manufacturing technique that lays down material in layers. In fused filament fabrication, a plastic filament is unwound from a coil and supplies material to produce a part. FFF is also known as ASTM F2792-12A Material Extrusion.
As used herein, “jetting” refers to an additive manufacturing technique that is similar to inkjet document printing, but instead of jetting drops of ink onto paper, drops of polymer are jetted onto a tray, and a stimulus (e.g., light and/or heat) is used to cure the layers.
As used herein, “initiation group” refers to a functional group that reacts with a monomer to form an intermediate compound capable of linking successively with a number of other monomers into a polymeric compound.
As used herein, “mechanochromic initiator” refers to a mechanochromic chemical species that reacts with a monomer to form an intermediate compound capable of linking successively with a number of other monomers into a polymeric compound.
As used herein, “rearrangement/rearranging” refers to a chemical reaction where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule.
As used herein, “intimately mixed” refers to a homogeneous mixture of two or more components.
As used herein, “macrophase separation” refers to a macroscopic phase separation, usually between immiscible polymers. Macrophase separation results in homogeneous regions spanning 0.1 to 1 mm.
As used herein, “microphase separation” refers to mixtures of two or more polymers that separate to form periodic nanostructures. The nanostructures can take the form of lamellae (i.e., layers), hexagonally packed cylinders, gyroid phases, etc. The nanostructures can range in size from 1 to 100 nm.
As used herein, “integrally embedded” refers to a first material that is directly formed together with one or more materials. The first material can be partially integrated or fully integrated within the one or more materials. In some embodiments, the one or more materials may be optically translucent, so as to permit viewing of any color changes that occur, while still encompassing and protecting a mechanochromic first material.
As used herein, “vat polymerization” refers to an additive manufacturing technique where 3-dimensional objects are formed by photopolymerization. Specifically, a projector projects an image with light onto a vat of monomers of polymer precursors in solution, which when exposed to light, polymerizes the monomers or polymer precursors into a solid polymer. The solid polymer is deposited in a layer by layer fashion to form a 3-dimensional object.
As used herein, “ink jet printing” refers to an additive manufacturing technique where curable liquid monomer or polymer precursors is deposited in a layer-by-layer manner and cured onto a build tray.
As used herein, the term “alkyl” refers to a saturated hydrocarbon group which is straight-chained (e.g., linear) or branched. Example alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, t-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), and the like. An alkyl group can contain from 1 to about 30, from 1 to about 24, from 2 to about 24, from 1 to about 20, from 2 to about 20, from 1 to about 10, from 1 to about 8, from 1 to about 6, from 1 to about 4, or from 1 to about 3 carbon atoms.
As used herein, the term “alkylene” refers to a linking alkyl group.
As used herein, the term “aryl” refers to monocyclic or polycyclic (e.g., having 2, 3, or 4 fused rings) aromatic hydrocarbons such as, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, and indenyl. In some embodiments, aryl groups have from 6 to about 20 carbon atoms.
As used herein, the term “arylene” refers to a linking aryl group.
As used herein, the term “halo” or “halogen” includes fluoro, chloro, bromo, and iodo.
As used herein, “alkenyl” refers to an alkyl group having one or more double carbon-carbon bonds. The alkenyl group can be linear or branched. Example alkenyl groups include ethenyl, propenyl, and the like. An alkenyl group can contain from 2 to about 30, from 2 to about 24, from 2 to about 20, from 2 to about 10, from 2 to about 8, from 2 to about 6, or from 2 to about 4 carbon atoms.
As used herein, “alkenylene” refers to a linking alkenyl group.
As used herein, “alkynyl” refers to an alkyl group having one or more triple carbon-carbon bonds. The alkynyl group can be linear or branched. Example alkynyl groups include ethynyl, propynyl, and the like. An alkynyl group can contain from 2 to about 30, from 2 to about 24, from 2 to about 20, from 2 to about 10, from 2 to about 8, from 2 to about 6, or from 2 to about 4 carbon atoms.
As used herein, “alkynylene” refers to a linking alkynyl group.
As used herein, “alkoxy” refers to an —O-alkyl group. Example alkoxy groups include methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), t-butoxy, and the like.
As used herein, “haloalkyl” refers to an alkyl group having one or more halogen substituents. Example haloalkyl groups include CF3, C2F5, CHF2, CCl3, CHCl2, C2Cl5, and the like.
As used herein, “haloalkoxy” refers to an —O-(haloalkyl) group.
As used herein, “aryl” refers to monocyclic or polycyclic (e.g., having 2, 3 or 4 fused rings) aromatic hydrocarbons such as, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl, and the like. In some embodiments, aryl groups have from 6 to about 20 carbon atoms.
As used herein, “arylene” refers to a linking aryl group.
As used herein, “heteroalkyl” refers to an alkyl group having at least one heteroatom such as sulfur, oxygen, or nitrogen.
As used herein, “heteroalkylene” refers to a linking heteroalkyl group.
As used herein, a “heteroaryl” refers to an aromatic heterocycle having at least one heteroatom ring member such as sulfur, oxygen, or nitrogen. Heteroaryl groups include monocyclic and polycyclic (e.g., having 2, 3 or 4 fused rings) systems. Any ring-forming N atom in a heteroaryl group can also be oxidized to form an N-oxo moiety. Examples of heteroaryl groups include without limitation, pyridyl, N-oxopyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolyl, isoquinolyl, thienyl, imidazolyl, thiazolyl, indolyl, pyrryl, oxazolyl, benzofuryl, benzothienyl, benzthiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2,4-thiadiazolyl, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, indolinyl, and the like. In some embodiments, the heteroaryl group has from 1 to about 20 carbon atoms, and in further embodiments from about 3 to about 20 carbon atoms. In some embodiments, the heteroaryl group contains 3 to about 14, 3 to about 7, or 5 to 6 ring-forming atoms. In some embodiments, the heteroaryl group has 1 to about 4, 1 to about 3, or 1 to 2 heteroatoms.
As used herein, “heteroarylene” refers to a linking heteroaryl group.
As used herein, the term “random copolymer” is a copolymer having an uncontrolled mixture of two or more constitutional units. The distribution of the constitutional units throughout a polymer backbone can be a statistical distribution, or approach a statistical distribution, of the constitutional units. In some embodiments, the distribution of one or more of the constitutional units is favored. For a polymer made via a controlled polymerization (e.g., RAFT, ATRP, ionic polymerization), a gradient can occur in the polymer chain, where the beginning of the polymer chain (in the direction of growth) can be relatively rich in a constitutional unit formed from a more reactive monomer while the later part of the polymer can be relatively rich in a constitutional unit formed from a less reactive monomer, as the more reactive monomer is depleted. To decrease differences in distribution of the constitutional units, comonomers in the same family (e.g., methacrylate-methacrylate, acrylamide-acrylamido) can be used in the polymerization process, such that the monomer reactivity ratios are similar.
As used herein, the term “constitutional unit” of a polymer refers to an atom or group of atoms in a polymer, comprising a part of the chain together with its pendant atoms or groups of atoms, if any. The constitutional unit can refer to a repeat unit. The constitutional unit can also refer to an end group on a polymer chain. For example, the constitutional unit of polyethylene glycol can be —CH2CH2O— corresponding to a repeat unit, or —CH2CH2OH corresponding to an end group.
As used herein, the term “repeat unit” corresponds to the smallest constitutional unit, the repetition of which constitutes a regular macromolecule (or oligomer molecule or block).
As used herein, the term “end group” refers to a constitutional unit with only one attachment to a polymer chain, located at the end of a polymer. For example, the end group can be derived from a monomer unit at the end of the polymer, once the monomer unit has been polymerized. As another example, the end group can be a part of a chain transfer agent or initiating agent that was used to synthesize the polymer.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The mechanochromic molecule or mechanophore of the present disclosure is a molecule that can provide a chemical response (e.g., a color change) upon exposure to a mechanical stimulus. The mechanochromic molecule includes a strained moiety, such as a spirocyclic moiety, that can rearrange to a colored moiety upon exposure to a mechanical stimulus. In some embodiments, the rearrangement of the strained moiety to a colored moiety can relieve a strain in the mechanochromic molecule. In some embodiments, the colored moiety is a conjugated planar moiety.
The mechanochromic moiety has a first end and a second end and includes at least one polymer chain covalently bound to each end. The first end is on one side of the strained moiety, and the second end is on the opposite side of the strained moiety (i.e., the mechanochromatic moiety is intermediate the polymer chains covalently coupled to each end of the moiety). The mechanochromic moiety is covalently bound to two or more polymers, where at least one polymer is located at each end of the mechanochromic moiety. The two or more polymers can be the same or different. The two or more polymers can have the same or different molecular weights. Examples of polymers include polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, the polymer can be a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
The mechanochromic moiety can be conjugated to the polymer in any of a variety of ways known to a person of ordinary skill in the art. For example, the mechanochromic moiety can be conjugated to the polymer via a linkage such as —OC(O)—, —C(O)O—, —NHC(O)—, —O—, —NH—, —NR—, —S—, S(O), —SO2—, —OSiO—, —OP(O)(OH)—, and/or —OP(O)(NR2)—.
The mechanochromic molecule can have a weight average molecular weight (Mw) of from about 30 to about 200 kDa.
In some embodiments, the mechanochromic moiety includes a spiropyran moiety, a naphthopyran moiety (e.g., an indenonaphthopyran moiety), or a spirooxazine moiety. Examples of the rearrangement of these moieties (e.g., spiro to conjugated forms) are shown below.
Spiropyran Moiety
In some embodiments, R1 and R2 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R1 and R2 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl.
In some embodiments, R1 and R2 are each independently selected from C1-6 alkyl.
In some embodiments, R1 and R2 are each H.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H and a polymer, provided that at least one of R3, R4, R5, R6, or R7 is a polymer.
In any of the embodiments above pertaining to R3, R4, R5, R6, or R7: in certain embodiments, one of R3, R4, R5, R6, or R7 is a polymer; in certain embodiments, two of R3, R4, R5, R6, or R7 are each independently a polymer; in certain embodiments, three of R3, R4, R5, R6, or R7 are each independently a polymer; in certain embodiments, four of R3, R4, R5, R6, or R7 are each independently a polymer; and in certain embodiments, R3, R4, R5, R6, and R7 are each independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer, or
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer, or
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer, or
In some embodiments, R8, R9, R10, and R11 are each independently selected from H and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer, or two adjacent R8, R9, R10, or R11 together with the carbons to which they are attached form aryl or heteroaryl, provided that at least said aryl or heteroaryl is substituted with one or more polymers or at least one of the remaining R8, R9, R10, and R11 not part of said aryl or heteroaryl is a polymer.
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer.
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer.
In some embodiments, R8, R9, R10, and R11 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer.
In some embodiments, R8, R9, R10, and R11 are each independently selected from H and a polymer, provided that at least one of R8, R9, R10, or R11 is a polymer.
In any of the embodiments above pertaining to R8, R9, R10, and R11: in certain embodiments, one of R8, R9, R10, and R11 is a polymer; in certain embodiments, two of R8, R9, R10, and R11 are each independently a polymer; in certain embodiments, three of R8, R9, R10, and R11 are each independently a polymer; and in certain embodiments, R8, R9, R10, and R11 are each independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R12 and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R12 and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R12 and R13 are each independently selected from H and C1-6 alkyl.
In some embodiments, R12 and R13 are each independently selected from C1-6 alkyl.
In some embodiments, R12 and R13 are each H.
It is understood that any of the above embodiments for the definitions of R1 and R2; R3, R4, R5, R6, and R7; R8, R9, R10, and R11; and R12 and R13 can be combined to provide the structures as illustrated in Scheme 1.
For example, in some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
Naphthopyran Moiety
wherein in Scheme 2:
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer.
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer.
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer.
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer.
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer.
In any of the embodiments above pertaining to R1, R2, R3, R4, R5, and R6: in certain embodiments, one of R1, R2, R3, R4, R5, and R6 is a polymer; in certain embodiments, two of R1, R2, R3, R4, R5, and R6 are each independently a polymer; in certain embodiments, three of R1, R2, R3, R4, R5, and R6 are each independently a polymer; in certain embodiments, four of R1, R2, R3, R4, R5, and R6 are each independently a polymer; in certain embodiments, five of R1, R2, R3, R4, R5, and R6 are each independently a polymer, and in certain embodiments, R1, R2, R3, R4, R5, and R6 are each independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer, or
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer, or
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer, or
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer, or
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer.
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer.
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer.
In some embodiments, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently selected from H and a polymer, provided that at least one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer.
In any of the embodiments above pertaining to R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16: in certain embodiments, one of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is a polymer; in certain embodiments, two of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a polymer; in certain embodiments, three of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a polymer; in certain embodiments, four of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a polymer; and in certain embodiments, five of R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R17 and R18 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R17 and R18 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R17 and R18 are each independently selected from H and
C1-6 alkyl.
In some embodiments, R17 and R18 are each independently selected from C1-6 alkyl.
In some embodiments, R17 and R18 are each H.
It is understood that any of the above embodiments for the definitions of R1, R2, R3, R4, R5, and R6; R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16; and R17 and R18 can be combined to provide the structures as illustrated in Scheme 2.
For example, in some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer;
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer;
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
In some embodiments, R1, R2, R3, R4, R5, and R6 are each independently selected from H and a polymer, provided that at least one of R1, R2, R3, R4, R5, and R6 is a polymer, or
Spirooxazine Moiety
wherein in Scheme 3:
In some embodiments, R1 and R2 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R1 and R2 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl.
In some embodiments, R1 and R2 are each independently selected from C1-6 alkyl.
In some embodiments, R1 and R2 are each H.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer, or
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer.
In some embodiments, R3, R4, R5, R6, and R7 are each independently selected from H and a polymer, provided that at least one of R3, R4, R5, R6, and R7 is a polymer.
In any of the embodiments above pertaining to R3, R4, R5, R6, and R7: in certain embodiments, one of R3, R4, R5, R6, and R7 is a polymer; in certain embodiments, two of R3, R4, R5, R6, and R7 are each independently a polymer; in certain embodiments, three of R3, R4, R5, R6, and R7 are each independently a polymer; in certain embodiments, four of R3, R4, R5, R6, and R7 are each independently a polymer; and in certain embodiments, each of R3, R4, R5, R6, and R7 is independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer, or
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer, or
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer, or
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer, or
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer.
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, C1-6 haloalkoxy, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer.
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H, C1-6 alkyl, and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer.
In some embodiments, R8, R9, R10, R11, R12, and R13 are each independently selected from H and a polymer, provided that at least one of R8, R9, R10, R11, R12, and R13 is a polymer.
In any of the embodiments above pertaining to R8, R9, R10, R11, R12, and R13: in certain embodiments, one of R8, R9, R10, R11, R12, and R13 is a polymer; in certain embodiments, two of R8, R9, R10, R11, R12, and R13 are each independently a polymer; in certain embodiments, three of R8, R9, R10, R11, R12, and R13 are each independently a polymer; in certain embodiments, four of R8, R9, R10, R11, R12, and R13 are each independently a polymer; in certain embodiments, five of R8, R9, R10, R11, R12, and R13 are each independently a polymer; and in certain embodiments, each of R8, R9, R10, R11, R12, and R13 is independently a polymer. The polymers can be the same or different. The polymers can have the same or different molecular weights. The polymers can each be independently selected from, for example, polycarbonates, polyamides, polyethers, polyurethanes, polyolefins, polyacrylates, and/or polyacrylamides. For example, each polymer can be independently selected from a poly(ε-caprolactone), an polylactic acid (PLA), an acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, a nylon, and/or a polyethylene glycol.
In some embodiments, R14 is selected from H, C1-6 alkyl, C1-6 alkoxy, aryl, heteroaryl, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R14 is selected from H, C1-6 alkyl, C1-6 alkoxy, halo, C1-6 haloalkyl, and C1-6 haloalkoxy.
In some embodiments, R14 is selected from H and C1-6 alkyl.
In some embodiments, R14 is C1-6 alkyl.
In some embodiments, R14 is H.
It is understood that any of the above embodiments for the definitions of R1 and R2; R3, R4, R5, R6, and R7; R8, R9, R10, R11, R12, and R13; and R14 can be combined to provide the structures as illustrated in Scheme 3.
For example, in some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R1 and R2 are each independently selected from H and C1-6 alkyl;
In some embodiments, R14 is selected from H and C1-6 alkyl.
The mechanochromic molecule can be blended with a matrix polymer, which can be any polymer that can be used in additive manufacturing. For example, the matrix polymer can include an acrylonitrile butadiene styrene, a poly(lactic acid), a polyamide, a polycarbonate, a polyether, a polyurethane, a polyolefin, a polyacrylate, a polyacrylamide, and/or a polyethylene glycol. In some embodiments, the matrix polymer can include two or more polymers. The mechanochromic molecule can be blended into the matrix polymer in an amount of about 0.001% to 10% (e.g., about 0.01% to 10%, about 0.1% to 10%, about 1% to 10%, about 0.01% to 5%, about 0.1 to 5%, about 1% to 5%) by weight of the mechanochromic molecule. For example, the blend can include about 10% by weight of the mechanochromic molecule.
When the mechanochromic molecule is blended into a matrix polymer, the mechanochromic molecule and the matrix polymer can adopt different morphologies. For example, the mechanochromic molecule and the matrix polymer can be intimately mixed, such that a homogeneous mixture is obtained. In some embodiments, the mechanochromic molecule and the first matrix polymer exhibit macrophase separation. In certain embodiments, the mechanochromic molecule and the first matrix polymer exhibit microphase separation.
Referring to
In some embodiments, the filament can have a diameter of about 1.5 mm to 3.0 mm and/or a length of from 1 to 100 feet. In some embodiments, the filament diameter can vary along a length. The filament can be made, for example, by milling a blend of a mechanochromic molecule and a matrix polymer, then extruding the milled blend to form a filament. The filament can be used, for example, in extrusion-based processes such as FFF, as shown in
In some embodiments, the powder can have a diameter of about 10 μm to 100 μm (e.g., about 20 μm to 100 μm, about 20 μm to 80 μm, or about 20 μm to 60 μm). A population of powder can have a relatively homogenous diameter that varies by less than 20 percent (e.g., less than 10 percent, less than 5 percent, or less than 2 percent). In some embodiments, a population of powder can have particles of different sizes. The powder can be made, for example, by milling a blend of a mechanochromic molecule and a matrix polymer. The powder can be used, for example, in selective laser sintering processes.
In some embodiments, rather than forming a blend with a mechanochromic molecule and one or more matrix polymers and then producing an article from the blend via additive manufacturing. The blend can be formed from the polymerization of mechanochromic molecule precursors (i.e., a mechanochromic initiator and one or more types of monomers to form the mechanochromic molecule) and the polymerization of matrix polymer precursors (i.e., initiators and one or more types of monomers to form the matrix polymer). In some embodiments, the blend can be formed in situ from mechanochromic molecule precursors and from matrix polymer precursors during additive manufacturing.
For example, the additive manufacturing method can include exposing to a stimulus a mixture including a mechanochromic initiator having at least two initiation groups, one or more monomers capable of being covalently bound to each of the initiation groups of the mechanochromic initiator, and one or more monomers capable of forming a matrix polymer. The stimulus can activate the mechanochromic initiator and start the polymerization of the one or more monomers (capable of being covalently bound to each of the initiation groups of the mechanochromic initiator) at each of the two initiator groups on the mechanochromic initiator. The stimulus can also activate a separate initiator for the matrix polymer, and form the matrix polymer by polymerization of the one or more monomers capable of forming a matrix polymer. In some embodiments, the polymerization can take place in a vat containing mixture of the mechanochromic initiator, one or more monomers capable of being covalently bound to each of the initiation groups of the mechanochromic initiator, and one or more monomers capable of forming a matrix polymer, in a selective light modulation additive manufacturing process (discussed above), where a stimulus can be projected onto the mixture, polymerization of the monomers can occur at the stimulus-exposed surface, and a polymerized article can be built up in a layer by layer manner. Thus, a polymerized article can be made from the vat of polymer precursors by in situ polymerization. The polymerized article can then be removed from the mixture. In some embodiments, rather than placing the mixture and polymerizing the mixture in a vat, the mixture can be sprayed from a nozzle by a jetting process as shown in
The stimulus to trigger polymerization of the mechanochromic molecule and the matrix polymer can take a variety of forms, such as an electromagnetic radiation (e.g., UV, near-UV, or visible light of from about 250 to 800 nm) and/or heat of up to 50° C., over a period of time of, for example, 1 to 30 seconds (e.g., 1 to 15 seconds, 1 to 20 seconds, 5 to 25 seconds, or 5 to 20 seconds).
In some embodiments, the one or more monomers capable of forming a matrix polymer, when polymerized, provide a matrix polymer selected from polyamide, polycarbonate, polyether, polyurethane, polyolefin, polyacrylate, polyacrylamide, and/or polyethylene glycol. In some embodiments, the one or more monomers capable of forming a matrix polymer, when polymerized, provide a matrix polymer selected from acrylonitrile butadiene styrene, poly(lactic acid), and/or poly(ε-caprolactone).
In some embodiments, the mechanochromic initiator is a spiropyran moiety, a naphthopyran moiety (e.g., an indenonaphthopyran moiety), or a spirooxazine moiety, each having a first end and a second end, and at least two reactive functional groups, where at least one reactive functional group is located at each end of the mechanochromic initiator. In some embodiments, the functional group is an alkene, an acrylate, or an alpha-haloester.
In some embodiments, the one or more monomers capable of being covalently bound to each of the initiation groups of the mechanochromic initiator, when polymerized, provides a polymer covalently bound through each of the initiation groups of the mechanochromic initiator. The polymer covalently bound through each of the initiation groups of the mechanochromic initiator can be polyamide, polycarbonate, polyether, polyurethane, polyolefin, polyacrylate, polyacrylamide, and/or polyethylene glycol. In some embodiments, the polymer covalently bound through each of the initiation groups of the mechanochromic initiator is selected from acrylonitrile butadiene styrene, poly(lactic acid), and/or poly(ε-caprolactone).
The additive manufacturing method of the present disclosure can include, for example, selective laser sintering (e.g., for the fusing step), fused filament fabrication (e.g., for the depositing and fusing steps), and jetting the material by material jetting, binder jetting, or inkjet printing (e.g., for the deposition step).
The additive manufacturing method can use commercially available 3D printers, such as those based on filament extrusion technology that can fabricate parts from thermoplastics such as polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS), which can be adapted to print advanced polymers including stimulus-responsive materials of the present disclosure.
For example, the additive manufacturing method can include a system including a filament as described above and a melt extrusion printer. The filament can be used in the printer without damage to the mechanochromic molecules and/or without significant changes to mechanical properties (e.g., tensile modulus, yield strength, strain to break, flexural modulus) of the matrix polymer.
As another example, the additive manufacturing method can include a selective laser sintering method, which can use the powder as described above to make an article without damage to the mechanochromic molecules and/or without significant changes to mechanical properties of the matrix polymer.
A variety of articles or devices can be made using the materials described in the present disclosure via additive manufacturing processes. For example, a tensile indication device, including a mechanochromic molecule and a matrix polymer, or mechanochromic regions embedded within a matrix polymer, where a portion or all of the device exhibit color changes in response to mechanical stimulus (e.g., a mechanical stress such as a pressure, pulling, bending, twisting, etc.) can be prepared using the methods of the present disclosure. The color change can be reversible, such that the device can revert to its initial color over time, when the mechanical stimulus is removed.
In some embodiments, the article can be a personal care article, a sensor, an implant, a prosthetic, a protective equipment, and/or a transportation article. For example, the personal care article can be a toothbrush. The sensor can be a bridge sensor, a mechanical stress sensor. The implant can be a dental implant. The protective equipment can be a helmet. The transportation article can be a tire.
The articles made from the materials of the present disclosure using additive manufacturing processes can have numerous advantages. For example, a toothbrush having bristles formed of a mechanochromic molecule and a matrix polymer can change color if a user applies too much pressure when brushing teeth. The color change can be reversible so that the toothbrush can reusable.
In some embodiments, the amount of mechanical stress that is applied to an article can be quantified. For example, the color of a mechanochromic region in an article that has been subjected to mechanical stress can be compared to a calibration curve, which can correlate mechanical stress to color intensity, thereby providing an estimate of the mechanical stress that was applied. As another example, the amount of mechanical stress that is applied to an article can be compared to the amount of mechanical stress that is applied to another article by comparing the color intensity and/or region of color change of the two articles, where increased color intensity and/or region of color change indicates a greater amount of mechanical stress.
In some embodiments, the article/device can include a mixture of regions, such as regions that are mechanochromic and regions that can change color when exposed to heat and/or light.
In some embodiments, the article including the mechanochromic molecule or a portion of an article including the mechanochromic molecule is integrally embedded in a host polymer (e.g., a second matrix polymer) to form a device, such that the embedded article or the embedded portion of the article cannot be removed from the second matrix polymer without destroying the initial structure. The device including the host polymer can be simultaneously made by an additive manufacturing process such that there is little segregation and/or defects between the embedded article and the host polymer.
When the mechanochromic molecule is blended into a matrix polymer and incorporated into an article, the mechanochromic molecule and the matrix polymer can be intimately mixed, such that a homogeneous mixture is obtained. In some embodiments, the mechanochromic molecule and the first matrix polymer exhibit macrophase separation when incorporated into an article. In certain embodiments, the mechanochromic molecule and the first matrix polymer exhibit microphase separation when incorporated into an article.
The following examples are provided to illustrate, not limit, the invention.
Example 1 describes the synthesis and characterization of filaments including poly(ε-caprolactone) and a spiropyran mechanophore using a commercial fused filament fabrication printer. Tensile test specimens containing various spiropyran concentrations, spiropyran control molecules, multiple materials, or mechanoresponsive regions embedded within the specimen were prepared and subjected to tensile testing. The materials exhibit distinct color changes that were attributed to mechanochemical isomerization of the spiropyran mechanophore. Example 2 describes the 3D printing of mechanoresponsive polymers. Mechanoresponsive regions within tensile or fracture test specimens were activated upon tensile elongation. A prototype force sensor was developed. The force sensor enabled the rapid visual determination of the amount of force being applied to the specimen.
The ability to incorporate mechanochemically-responsive units into materials amenable to 3DP techniques to produce printed objects with well-defined shapes and regions capable of chemo-mechanical coupling was evaluated. Mechanochromic spiropyran systems were studied, because of the ease of determining qualitative activation in these systems. Upon application of force across the Cspiro—O bond, isomerization of the spiropyran to its highly colored merocyanine isomer can be accomplished (
A thermoplastic polymer was used with FFF printing, where the polymer filament was first melted in an extrusion head and subsequently deposited according to the software provided to the printer. Thus, two spiropyran moieties, 1 and 3 (shown in
Filament was prepared using a single screw melt extruder. Average filament diameters ranged from about 1.55 to 1.85 mm, with variation along the filament typically being less than ±0.05 mm. To ensure the most accurate diameter, each sample of filament was measured with calipers in multiple places along the section to be used for printing and the average diameter was used in the print parameters.
The custom filaments were then used to print tensile testing specimens using a commercial dual-extrusion head FFF printer. Printing was initially performed using only one of the extrusion heads set at a temperature of 110° C., a non-heated build plate, and a print speed of 20 mm/s. Due to the relatively flexible nature of the filament, disabling retraction (a setting that reverses the drive gear in the extruder head to pull the filament back into the nozzle, which is used to combat filament oozing) was key to being able to successfully print full specimens without the filament jamming. During the printing, no thermal activation of the spiropyran was observed.
General Considerations
Dry toluene was obtained from a Glass Contour solvent purification system. The monomer ε-caprolactone was dried over 4 Å molecular sieves for 48 h prior to use. House N2 was passed through a drying tube before use. All other reagents and solvents were used as obtained from commercial sources. 1H spectra were recorded on Bruker AVance 300 and 500 MHz spectrometers. Chemical shifts are reported in delta (δ) units, expressed in parts per million (ppm) downfield from tetramethylsilane using the residual protio-solvent as an internal standard (CDCl3, 1H: 7.26 ppm). GPC setup consisted of: a Shimadzu pump, three in-line MZ Analysentechnik columns, DAWN Heleos II multi-angle laser light scattering and T-rEX refractive index detectors (Wyatt Technology Corporation), and DMF (0.01 M LiBr) as the mobile phase.
Abbreviations
DMF=N,N-dimethylformamide; GPC=gel permeation chromatography; Oct=2-ethylhexanoate
Synthetic Procedures
Synthesis of Polymers:
Initiators 1 and 3 were prepared as described in O'Bryan, G. et al., ACS Appl. Mater. Inter. 2010, 2, 1594 and Raymo, F. M.; Giordani, S. J. Am. Chem. Soc. 2001, 123, 4651. Synthesis of polymer 2 was carried out following a procedure as described in O'Bryan, G. et al., ACS Appl. Mater. Inter. 2010, 2, 1594.
Polymer 4 was prepared with an analogous procedure to that of 2. Specifically, a flame-dried and N2-purged three-neck round bottom flask fitted with a reflux condenser was charged with initiator 3 (268 mg, 0.76 mmol, 1.0 mol. equiv.) and a stir bar. To the reaction flask was then added ε-caprolactone (29.4 mL, 265 mmol, 350 mol. equiv.) and dry toluene (30.0 mL). Finally, Sn(Oct)2 (80 μL, 0.251 mmol, 0.33 mol. equiv.) was added and the reaction solution was brought to refluxing temperature. After 24 h, the reaction solution was cooled to 40° C., diluted with toluene (˜150 mL), and stirred until the polymer was fully dissolved. The polymer solution was then precipitated into cold MeOH, after which the precipitate was dried under reduced pressure. The product was obtained as a brown solid in 96% yield (29.0 g).
Polymer 2 was characterized by 1H NMR in CDCl3. GPC characterization of Polymer 2 showed a Mw of 90 kDa, PDI 1.16. Polymer 4 was characterized by 1H NMR in CDCl3. GPC characterization of Polymer 4 showed a Mw of 65 kDa, PDI 1.43. Makerbot Flexible Filament (C) was characterized by 1H NMR in CDCl3. GPC characterization of Makerbot Flexible Filament (C) showed a Mw of 63 kDa, PDI 1.29.
Filament Production:
Polymers 2 and 4 were mixed with C (Makerbot Flexible Filament cut into small pieces), melted with a heat gun, and manually mixed with a spatula. The resulting mixture was cut into small pieces with scissors and put into a coffee grinder with dry ice. The polymer was ground into small particles/powder and made into filament via melt extrusion (at 63° C.) with a Filabot Wee filament extruder. The filament 2100 was produced without blending any commercial filament.
3D Printing:
3D structures were designed using Sketchup 2013 computer aided design (CAD) software and converted to .stl files using a Sketchup extension. The .stl files were imported into Replicator G (version 0040) and gcode (for Makerbot-type printers) was generated using either Sli3er 0.X (for single material prints) or Skeingforge 50 (for multi-material prints) slicing programs. For multi-material prints, gcode from each .stl file was merged in Replicator G. A Flashforge Creator dual head FFF 3D printer (firmware 7.2) was used to read the gcode and print the 3D object. Objects were printed onto a non-heated Plexiglas build plate. The extrusion nozzle was heated to 110° C. All print speeds were set to 20 mm/s, with a travel speed of 50 mm/s and retraction disabled when applicable. All objects were printed with 2 shells, a fill density of 1 (100% fill), and a layer height of 0.25 mm. Filament diameters were determined prior to each print by measuring with calipers.
Mechanical Testing:
Tensile testing of printed specimens was performed on an Instron 5500R load frame controlled using Bluehill 2 software. Load was measured with a 5 kN load cell. Tests were conducted using a crosshead rate of 100 mm/min. Dimensions of each specimen were measured with calipers prior to testing to ensure accurate calculation of stress and strain for each sample. Three specimens were tested for a given filament type.
To examine the basic mechanical properties of the materials and ensure a controlled environment for elongation, tensile testing was completed on an Instron load frame. In all cases in which 2 was present, color change from brown to purple was observed upon elongation and necking of the sample, signifying mechanochemical activation of the spiropyran. While the intensity of the resulting color was directly related to the amount of 2 used in the blend, the greatest contrast between virgin and elongated (activated) materials was observed for blends having lower loading of spiropyran, due to the lighter color of the unactivated material (
Binary materials were then prepared that highlight the capabilities of 3DP in contrast with other types of traditional manufacturing methods, such as injection or compression molding. A dual-responsive tensile test specimen including discrete regions of mechanoresponsive 250 and control filament 450 was printed in a single session by using two extrusion heads, each loaded with one of the filament types. With a dual extrusion technique, the active print head alternates such that only one head is printing at a time. The test specimen body was comprised mainly of 450 which was used as a housing around two surface channels of 250 that spanned the length of the printed specimen (
The use of 3DP was then explored to prepare objects in which a rectangular region of mechanoresponsive 250 was completely encased by C100 (
Thus, Example 1 demonstrates the successful 3D printing of mechanoresponsive polymers. The basic mechanical properties of the different structures prepared with various filament formulations showed some variation, but were within the range of reported values for poly(ε-caprolactone). With the use of a dual-head FFF printer, dual-responsive materials with segregated stimuli-responsive regions were produced, in which only one component activated in response to elongational force but both did so when exposed to UV irradiation. The use of 3DP enabled rapid production of binary materials such as encased mechanoresponsive materials within commercial or control polymers. These materials would generally be difficult or impossible to prepare with other manufacturing techniques.
Example 2 provides smart materials that respond with changes in chemical properties. “Chemically activated” is used herein to indicate a chemical stimulus and “chemically responsive” is used herein to indicate a chemical response or output (to any variety of stimulus). Here, mechanically activated, chemically responsive smart materials, which incorporated molecules that underwent chemical reactions in response to mechanical forces, were used. These mechanically-activated molecules or moieties are referred to herein as “mechanophores.”
A mechanochromic spiropyran (SP) was used, which provided easily discernable chemical output based upon a distinct color change. As shown in
The fabrication of SP/PCL filaments was demonstrated, and the filaments were applicable for FFF and the mechanophoric properties were preserved during the additive manufacturing process. Spatially-controlled mechanical activation and chemical response were demonstrated using a dual-filament system to produce sample “smart parts” for mechanical testing. Experimental results to characterize the behavior of the “smart parts” under crack opening were presented. Finally, 3D printed sensors based on mechanophoric smart part technology were also presented.
Custom PCL including covalently incorporated SP (SP/PCL) was synthesized. The custom polymer was mixed with commercial PCL filament (Makerbot Flexible Filament) to decrease the spiropyran content of the material. Samples were produced with 1%, 3%, 5%, 10%, 20%, or 50% w/w SP/PCL filament blended with commercial filament. The SP mechanophore accounts for a small fraction of the SP/PCL filament, such that using 1% w/w of SP/PCL filament in the blend results in a final concentration of SP mechanophores of 0.005% w/w relative to total PCL. The samples were melted with a heat gun and manually mixed with a spatula. The melting and mixing process was repeated at least once more to ensure visual homogeneity. An aliquot of the mixed sample was melted and formed into a 1.5 cm long “cigar” shape. Samples were manually elongated with pliers to observe the mechanochemical color change. The elongated samples were additionally subjected to 365 nm ultraviolet (UV) irradiation from a hand held UV lamp to observe the photochromism of the SP (Minkin 2004).
The mechanoresponsive SP/PCL and commercial PCL filament (chopped into pieces 2-3 cm in length) were mixed at the desired weight percentage. They were then melted together and mixed manually with a spatula. After cooling, the mixture was cut into small pieces and ground into a powder containing smaller pieces no bigger than 5 mm in diameter using an electronically controlled burr mill containing dry ice. The resulting material was filamentized using a Filabot Wee filament extruder set at 63° C.
3D objects were designed using Sketchup 2013 computer aided design (CAD) software and converted to .stl files using a Sketchup extension. Part descriptions were exported in .STL format and imported into Replicator G version 0040 (Replicator G is a program that is used to manipulate and move the 3D object on the build plate, interface with the slicing programs, control/drive the 3D printer, etc.) and G-code (for Makerbot-type printers) was generated using the Skeinforge 50 slicing program. For multi-material prints, G-code from each .STL file was merged in Replicator G. In reading the G-code scripts and 3D printing the objects, a dual head Flashforge Creator FFF printer (with firmware 7.2) was used. A non-heated Plexiglas build plate was used as the printing surface. The extrusion nozzle was heated to 110° C. All print speeds were set to 20 mm/s, with a travel speed of 20 mm/s. All parts were printed with 2 shells, a fill density of 1 (100% fill), and a layer height of 0.25 mm.
Mechanoresponsive material (50% blend) in the shape of the letters “UW” was encased within a tensile test specimen of commercial filament (
The geometry of the notched specimen prepared for Mode-I loading (opening mode) is shown in
The force sensor was comprised of commercial filament with embedded mechanoresponsive material (50% blend) as depicted in
As the SP mechanophore was not as readily available as the bulk PCL and requires several synthetic steps to produce, the minimum SP concentration needed to be able to observe the mechanochromic response visually without additional analytical techniques was explored. To decrease the SP concentration, the mechanoresponsive polymer was blended with commercial PCL. The mechanochromism was observable using 3% w/w of the SP/PCL filament, but was not very distinct until the blend reached 10% w/w of SP/PCL (
The incorporation of the mechanoresponsive material into a tensile testing specimen was conducted to explore its activation. The mechanoresponsive material can be incorporated into complex architectures. As shown in
According to the theory of linear elasticity, crack tips are regions where the stress and strain are infinite. Later work shows that although infinite stress and strain are not realistic, the crack tip is the region where each is greatest. Under Mode-I fracture, yield zone forms at the tip of a crack in polymers just like in metals as explained by Anderson (2005). In agreement with this, the state of the specimen before, during, and after the test can be seen in
In order to demonstrate a potential application of the mechanoresponsive material, a proof-of-concept force sensor was developed. An asymmetric tensile test specimen was prepared with embedded regions of SP/PCL. A standard “dogbone” specimen displayed a nearly flat stress-strain relation, thus a linear variation of cross section was introduced with the goal of requiring increased load to continue stretching the sample. A linear variation in the width of the specimen successfully produced a stress-strain curve that had a very nearly constant non-zero slope over a wide range of loads (
In addition to being able to simply count the number of activated regions, which correlated with the peak load, it could be observed in the post-elongated specimen that the mechanoresponsive regions that activated first were also darker than the regions that activated at a later time (
In summary, 3D printing of mechanoresponsive polymers using an entry-level AM system is demonstrated. Mechanoresponsive regions within tensile or fracture test specimens were activated upon tensile elongation. To demonstrate the potential applications of this material, a prototype force sensor was developed. The force sensor enabled the rapid visual determination of the amount of force being applied to the specimen.
While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
This application claims the benefit of U.S. Patent Application No. 62/033,590, filed Aug. 5, 2014, and U.S. Patent Application No. 62/049,275, filed Sep. 11, 2014, the disclosure of each of which is hereby incorporated by reference in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US15/43777 | 8/5/2015 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62033590 | Aug 2014 | US | |
| 62049275 | Sep 2014 | US |
