EP4281501A1 - Compositions durcissables - Google Patents

Compositions durcissables

Info

Publication number
EP4281501A1
EP4281501A1 EP22742964.4A EP22742964A EP4281501A1 EP 4281501 A1 EP4281501 A1 EP 4281501A1 EP 22742964 A EP22742964 A EP 22742964A EP 4281501 A1 EP4281501 A1 EP 4281501A1
Authority
EP
European Patent Office
Prior art keywords
curable composition
compound
group
resin composition
optionally substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22742964.4A
Other languages
German (de)
English (en)
Other versions
EP4281501A4 (fr
Inventor
Chin Siang NG
Pei-Chen Su
Alamelu Suriya SUBRAMANIAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanyang Technological University
Original Assignee
Nanyang Technological University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanyang Technological University filed Critical Nanyang Technological University
Publication of EP4281501A1 publication Critical patent/EP4281501A1/fr
Publication of EP4281501A4 publication Critical patent/EP4281501A4/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2251—Oxides; Hydroxides of metals of chromium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2289—Oxides; Hydroxides of metals of cobalt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2293—Oxides; Hydroxides of metals of nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory

Definitions

  • the present invention generally relates to curable compositions.
  • the present invention also relates to curable compositions useful for forming shape memory polymers.
  • SMP Shape memory polymer
  • vat photopolymerization has one of the fastest printing processes, as well as smoothest surface finishes.
  • the mechanical properties of the printed parts tend to be inferior when compared to other 3D printing methods.
  • One of the issues with vat photopolymerization is the increase in brittleness after post-treatment or long exposure of light and heat.
  • the use of additives in vat photopolymerization is also challenging due to a variety of reasons, such as the dispersion of particles and the detrimental effects on ultraviolet (UV) curing.
  • DLP Digital light processing
  • DLP printing suffers from poor dimensional and geometrical accuracy and therefore has shortcomings in medical applications where accuracy of internal structures for medical devices is important.
  • Photoabsorbing dyes are commonly used in UV curable resins to improve dimensional accuracies. They can be used to reduce the cure depth, thus preventing unwanted cure due to excessive UV exposures.
  • photoabsorbers tend to also increase the critical energy of the resin, which the minimum amount of energy needed for the resin to start curing. This could result in longer exposure time, as well as the overall printing time.
  • a curable composition comprising (i) a resin composition, wherein the resin composition comprises: a compound Cl having an X group and an optionally substituted aryl group; a compound C2 having an X group and an optionally substituted carbocyclyl group; a compound C3 having at least two X groups; and a photoinitiator, wherein X is acrylate or methacrylate.
  • a method of forming a shape memory polymer comprising exposing a curable composition disclosed herein to ultraviolet light.
  • a shape memory polymer comprising the curable composition disclosed herein, wherein the curable composition has been cured by ultraviolet light.
  • the curable compositions of the present disclosure allow for fast U V curing into shape memory polymers (SMP).
  • SMP shape memory polymers
  • the working temperature of the SMP may be brought closer to body temperature, even after extensive post-treatment is applied. This advantageously makes it easier to trigger its shape memory effect without having to heat the SMP to high temperatures. Further advantageously, the SMPs may have high recovery ratio of 99% at 40 °C.
  • the curable compositions of the present disclosure may further comprise metal oxides, such as zinc oxide.
  • metal oxides such as zinc oxide.
  • the addition of metal oxide not only speeds up the curing process, it also helps to improve the print quality of the product by reducing flashes. It also provides slight improvement in the mechanical properties at both room temperature and body temperature.
  • metal oxide also advantageously reduces the amount of energy needed to cure a layer of resin, while preventing excessive unwanted cure during the printing process.
  • the inclusion of metal oxide increases the toughness of the material, with some compromise on the tensile strength and Young’s Modulus.
  • the curable compositions of the present disclosure do not contain photoabsorbers, such as l-phenylazo-2-naphthol (Sudan I), l-[4-
  • alkyl includes within its meaning monovalent (“alkyl”) and divalent (“alkylene”) straight chain or branched chain saturated aliphatic groups having from 1 to 6 carbon atoms, eg, 1, 2, 3, 4, 5 or 6 carbon atoms.
  • alkyl includes, but is not limited to, methyl, ethyl, 1 -propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, amyl, 1,2- dimethylpropyl, 1,1 -dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1 -methylpentyl, 2- methylpentyl, 3 -methylpentyl, 2,2-dimethylbutyl, 3, 3 -dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl and the like.
  • Alkyl groups may be optionally substituted.
  • alkenyl refers to divalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon double bond and having from 2 to 6 carbon atoms, eg, 2, 3, 4, 5 or 6 carbon atoms.
  • alkenyl includes, but is not limited to, ethenyl, propenyl, butenyl, 1-butenyl, 2-butenyl, 2 -methylpropenyl, 1-pentenyl,
  • alkynyl refers to trivalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon triple bond and having from 2 to 6 carbon atoms, eg, 2, 3, 4, 5 or 6 carbon atoms.
  • alkynyl includes, but is not limited to, ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2- hexynyl, 3-hexynyl, 3 -methyl- 1-pentyny lor variants such as “aromatic group” or “arylene” as used herein refers to monovalent (“aryl”) and divalent (“arylene”) single, polynuclear, conjugated and fused residues of aromatic hydrocarbons having from 6 to 10 carbon atoms.
  • Such groups include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, and the like.
  • Carbocycle includes within its meaning any stable 3, 4, 5, 6, or 7-membered monocyclic or bicyclic or 7, 8, 9, 10, 11, 12, or 13-membered bicyclic or tricyclic, any of which may be saturated, partially unsaturated, or aromatic.
  • carbocycles include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, cyclooctyl, [3.3.0]bicyclooctane, [4.3.0]bicyclononane, [4.4.0]bicyclodecane (decalin), [2.2.2]bicyclooctane, fluorenyl, phenyl, naphthyl, indanyl, adamantyl, or tetrahydronaphthyl (tetralin).
  • carbocycles are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, and indanyl.
  • carbocycle When the term “carbocycle” is used, it is intended to include “aryl”. Carbocycles may be optionally substituted.
  • arylalkyl When compounded chemical names, e.g. “arylalkyl” and “arylimine” are used herein, they are understood to have a specific connectivity to the core of the chemical structure.
  • the group listed farthest to the right e.g. alkyl in “arylalkyl”
  • alkyl in “arylalkyl” is the group that is directly connected to the core.
  • an “arylalkyl” group for example, is an alkyl group substituted with an aryl group (e.g. phenylmethyl (i.e., benzyl)) and the alkyl group is attached to the core.
  • alkylaryl is an aryl group substituted with an alkyl group (e.g., p-methylphenyl (i.e., p-totyl)) and the aryl group is attached to the core.
  • alkyl group e.g., p-methylphenyl (i.e., p-totyl)
  • optionally substituted means the group to which this term refers may be unsubstituted, or may be substituted with one or more groups other than hydrogen provided that the indicated atom’ s normal valency is not exceeded, and that the substitution results in a stable compound.
  • Such groups may be, for example, halogen, hydroxy, oxo, cyano, miro, alkyl, alkoxy, haloalkyl, haloalkoxy, atyl-4-alkoxy, alkylthio, hydroxyalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, alkylsulfonylalkyl, arylsulfonyl, arylsuifonyloxy, atylsulfonylalkyl, alkyl sulfo namido, alkylamido, alkylsulfonamidoalkyl, alkylamidoalkyd, arylsulfonamido, arylcarboxamido, arydsulfonamidoalkyl, ary
  • substituted means the group to which this term refers is substituted with one or more groups other than hydrogen provided that the indicated atom’s normal valency is not exceeded, and that the substitution results in a stable compound.
  • groups may be, for example, halogen, hydroxy, oxo, cyano, nitro, alkyd, alkoxy , haloalkyl, haloalkoxy’, arylalkoxy, alkylthio, hydroxyalkvl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, aikylsulfonylalkyl, arylsulfonyl, arylsuifonyloxy, arylsulfonylalkyl, alkylsulfonamido, alkylamido,
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • FIG. 1 is a graph showing the cure depth versus exposure time for curable compositions with and without zinc oxide (ZnO).
  • FIG. 2 is a series of photographs comparing the printing quality of structures 3D-printed from curable compositions containing ZnO (right) and without ZnO (left) with small defining features (2mm, 3.2 mm and 6.0 mm circles/ squares and 2.2 mm, 3.5 mm and 6 mm diamonds).
  • FIG. 3 is an image showing a square array with different UV exposure for measuring cure depth.
  • FIG. 4a is a graph showing the cure depth versus energy input for different curable compositions with varying amounts of ZnO added.
  • Fig.4b is a graph showing the cure depth versus energy input for different curable compositions with varying amounts of ZnO added.
  • FIG. 4b is a series of graphs showing the critical energy and penetration depth for the different curable compositions with varying amounts of ZnO added.
  • FIG. 5 is a diagram of an overhanging structure used to measure unwanted cure in the vertical direction, with increasing bottom exposures from left to right.
  • FIG. 6 are microscopic images of the overhanging structure after certain amounts of bottom exposure.
  • FIG. 7a is a graph showing the measured versus theoretical flash height for the UV-curable resins with an exposure time of 1.5 seconds.
  • FIG. 7b is a graph showing the measured versus theoretical flash height for curable compositions with an exposure time of 2 seconds.
  • FIG. 8a is a graph showing the stress-strain curves of the curable compositions of Example
  • FIG. 8b is a series of graphs showing the tensile properties of the curable compositions of Example 1 60 minutes post curing.
  • FIG. 8c is a series of graphs showing the tensile properties of the curable compositions of Example 1 180 minutes post curing.
  • FIG. 9a is a graph showing the tensile properties of the curable compositions of Example 1 with no post curing.
  • FIG. 9b is a graph showing the cumulative normalized energy exposure during printing of the samples of Example 6.
  • FIG. 9c is a graph showing the total and normalized energy exposures of the samples of Example 6 without post curing.
  • FIG. 10a is a graph showing the programming of shape memory polymer in the shape of an octahedron cube, by compression the cube to 40% strain at 40 °C.
  • FIG. 10b is a graph measuring the recovery stress while the octahedron cube of Example 7 is maintained at 27% strain based on the position of the cube.
  • FIG. 10c is a graph measuring the recovery of the shape memory polymer in the shape of an octahedron cube, wherein the strain is returned to 0% based on the position at 40 °C.
  • FIG. lOd is a diagram of the shape memory polymer in the shape of an octahedron cube used in the shape memory effect analysis.
  • FIG. 11 is an image of a 3D-printed stent from ZnO-containing shape memory polymer, with a smallest feature size of 0.4 mm.
  • FIG. 12 are images of a 3D-printed stent printed with shape memory polymer without ZnO, before and after compression at 40 °C.
  • the present invention relates to a curable composition
  • a curable composition comprising (i) a resin composition, wherein the resin composition comprises: a compound Cl having an X group and an optionally substituted aryl group; a compound C2 having an X group and an optionally substituted carbocyclyl group; a compound C3 having at least two X groups; and a photoinitiator, wherein X is acrylate or methacrylate.
  • Compound Cl may be represented by the following Formula (I):
  • Ri is optionally substituted alkylene, or -Ri a -O-, wherein Ri a is optionally substituted alkylene;
  • R2 is optionally substituted aryl
  • R7 is H or methyl; and n represents an integer of 1 to 4.
  • Ri and Ri a may each be unsubstituted or substituted C1 to 6-alkylene (i.e. C1, C2, C3, C4, C5, or C6, alkylene).
  • n may be 1, 2, 3 or 4.
  • R2 may be unsubstituted or substituted aryl.
  • R 2 may be a substituted or unsubstituted C6- 12 aryl group (i.e. a C6, C7, C8, C9, C10, C11, or C12 aryl group).
  • R2 may be substituted or unsubstituted phenyl, biphenyl, naphthyl, or phenanthrenyl.
  • R2 may be an aryl group that is unsubstituted or substituted with one or more halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, arylalkoxy, alkylthio, hydroxyalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanovl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy , alkylsulfonylalkyl, arylsulfonyl, arylsulfonyloxy, arylsulfonylalkyl, alkylsulfonamido, alkylamido, alkylsulfonamidoalkyi, alkylamidoalkyl, arylsulfonamido, aiylcatboxamido, ai
  • R2 may be unsubstituted or substituted phenyl.
  • R 2 may be unsubstituted phenyl.
  • Compound Cl may be selected from one of the following compounds:
  • Compound Cl may be 2-phenoxyethyl acrylate (2PA):
  • Compound Cl may be 2-phenoxyethyl methacrylate:
  • Compound C2 may be represented by the following Formula (II):
  • R1 is optionally substituted alkylene
  • R3 is optionally substituted carbocyclyl
  • R8 is H or methyl; and n represents an integer of 0 to 4.
  • Ri may be unsubstituted or substituted C1 to 6-alkylene (i.e. C1, C2, C3, C4, C5, or C6, alkylene).
  • n may be 0, 1, 2, 3 or 4.
  • Ri may be alkylene unsubstituted or substituted with one or more halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, arylalkoxy, alkylthio, bydroxyalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkydsulfonyl, alkylsulfonyloxy, alkyl sulfonyl alkyl, aiylsulfonyl, arylsulfonyloxy, aiylsulfonylalkyl, alkylsulfonamido, alkylamido, alkylsulfonamidoalkyl, alkylaroidoalkyl, arylsulfonamido, aiylcarboxamido,
  • R3 may be unsubstituted or substituted carbocylclyl.
  • R? may be unsubstituted or substituted C3 to Ci 2 carbocyclyl group.
  • the carbocyclyl may be a saturated, or partially saturated, mono or bicyclic carbon ring that contains 3 to 12 carbon atoms.
  • the carbocyclyl may be a monocyclic ring containing 5 or 6 carbon atoms or a bicyclic ring containing 7 to 10 carbon atoms.
  • R? may be carbocyclyl group that is unsubstituted or substituted with one or more halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy , arydalkoxy, alkylthio, hydroxyalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, alkylsulfonylalkyl, aiylsulfonyl, arylsulfonyloxy, aiylsulfonylalkyl, alkylsulfonamido, alkylamido, alkylsulfonamidoalkyl, alkylamidoalkyl, arylsulfonamido, aiylcaibox
  • the optionally substituted carbocyclyl group may be a bicyclic C7 carbocyclyl substituted with at least 1 alkyl group.
  • the optionally substituted carbocyclyl group may be a bicyclic C7 carbocyclyl substituted with 1, 2, or 3 alkyl groups.
  • the alkyl groups may be selected from methyl, ethyl, propyl or butyl.
  • the optionally substituted carbocyclyl group may be a bicyclic C7 carbocyclyl substituted with 1, 2, or 3 methyl groups.
  • the optionally substituted carbocyclyl group may be a bicyclic C7 carbocyclyl substituted with 3 methyl groups.
  • Compound C2 may be selected from one of the following compounds:
  • Compound C2 may be isobomyl acrylate (IBOA):
  • IBOA Compound C2 may be isobornyl methacrylate:
  • Compound C3 be represented by the following Formula (III):
  • R5 is optionally substituted alkyl, alkenyl or alkynyl
  • R6 is H or
  • R 4a , Rrb and R 4c are each independently optionally substituted alkylene, or -R 4d -O-, wherein R 4d is optionally substituted alkylene;
  • R9a- R9b and R9c are each independently H or methyl .
  • Compound C3 may have at least 2 acrylate or methacrylate groups. Compound C3 may have at least 3 acrylate or methacrylate groups. Compound C3 may have 3 acrylate or methacrylate groups. Compound C3 may have at least 2 acrylate groups. Compound C3 may have at least 3 acrylate groups. Compound C3 may have 3 acsylate groups.
  • Rs may be unsubstituted or substituted Ci-6 alkyl (i.e. Ci, C 2 , C3, C4, C5, or C 6 alkyl), C 2 - 6 alkylene (i.e. C2, C3, C4, C5, or C6, alkenyl), or C2-6 alkynyl (i.e. C2, C3, C4, C5, or C6, alkynyl).
  • R5 may be unsubstituted or substituted methyl, ethyl, or propyl.
  • R5 may be alkyl, alkenyl or alkynyl unsubstituted or substituted with one or more halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, arylalkoxy, alkylthio, hydroxyalkvl, alkoxyalkyl, cvcloalkyl, cycloalkylalkoxy, alkanoyl, alkoxy carbonyl, alkydsulfonyl, alkylsulfonyloxy, alkyd sulfonyl alkyd, arylsulfonyl, arylsulfonyloxy, arylsulfonylalkyl, alkylsulfonamido, alkvlamido, alkylsulfonamidoalkyl, alkylamidoalkyl, arylsulfonamido, ai
  • R4a, R4b, R4c, R4d may each be unsubstituted or substituted C1 to 6-alkylene (i.e. Ci, C 2 , C3, C4, C5, or C6, alkylene).
  • R4a, R4b, R4c, R4d may be alkylene unsubstituted or substituted with one or more halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, arylalkoxy, alkydthio, hydroxyalkyd, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkydsulfonyl, alkylsulfonyloxy , alkydsulfonvlalkyd, arylsulfonyl, arylsulfonyloxy, arylsulfonylalkyl, alkylsulfonamido, alkylamido, alkylsulfonamidoalkyl, alkylamidoalkyl, arylsulfonamido, arylcar
  • Compound C3 may be trimethylolpropane ethoxylate triacrylate (TMPEOTA):
  • the photoinitiator may be bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (BAPO), or diphenyl 2,4,6- trimethylbenzoyl phosphine oxide.
  • BAPO bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
  • diphenyl 2,4,6- trimethylbenzoyl phosphine oxide may be bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (BAPO), or diphenyl 2,4,6- trimethylbenzoyl phosphine oxide.
  • the curable composition may further comprise metal oxide.
  • the metal of the metal oxide may be selected from the group consisting of aluminium, magnesium, chromium, iron, cobalt, nickel, and zinc.
  • the metal oxide may be zinc oxide.
  • the metal oxide may be in the form of nanoparticles.
  • the nanoparticles may have a particle size less than about 250 nm.
  • the particle size may be about 10 nm to about 250 nm, about 20 nm to about 250 nm, about 30 nm to about 250 nm, about 40 nm to about 250 nm, about 50 nm to about 250 nm, about 60 nm to about 250 nm, about 70 nm to about 250 nm, about 80 nm to about 250 nm, about 90 nm to about 250 nm, about 100 nm to about 250 nm, about 110 nm to about 250 nm, about 120 nm to about 250 nm, about 130 nm to about 250 nm, about 140 nm to about 250 nm, about 150 nm to about 250 nm, about 160 nm to about 250 nm, about 170 nm to about 250 nm, about 180 nm to about
  • the curable composition does not contain photoabsorber. In an embodiment, the curable composition does not contain l-phenylazo-2-naphthol (Sudan I), 1- [4-(phenylazo)phenylazo]-2-naphthol (Sudan III), or C28H31CIN2O3 (Rhodamine B).
  • the resin composition may comprises about 40 wt% to about 50 wt% of compound Cl, based on the total weight of the resin composition.
  • the resin composition may comprise 40 wt% to about 50 wt% of compound Cl, or about 41 wt% to about 50 wt%, about 42 wt% to about 50 wt%, about 43 wt% to about 50 wt%, about 44 wt% to about 50 wt%, about 45 wt% to about 50 wt%, about 46 wt% to about 50 wt%, about 47 wt% to about 50 wt%, about 48 wt% to about 50 wt%, about 41 wt% to about 50 wt%, about 41 wt% to about 50 wt%, about 59 wt% to about 50 wt%, about 40 wt% to about 49 wt%, about 40 wt% to about 48 wt%, about 40 wt% to about 47 wt%,
  • the resin composition may comprise about 30 wt% to about 50 wt% of compound C2, based on the total weight of the resin composition.
  • the resin composition may comprise about 30 wt% to about 50 wt% of compound C2, about 35 wt% to about 50 wt%, about 40 wt% to about 50 wt%, about 45 wt% to about 50 wt%, about 30 wt% to about 45 wt%, about 30 wt% to about 40 wt%, about 30 wt% to about 35 wt%, or about 40 wt%, about 45 wt%, about 50 wt%, or any value or range therebetween.
  • the resin composition may comprise about 15 wt% to about 25 wt% of compound C3, based on the total weight of the resin composition.
  • the resin composition may comprise about 15 wt% to about 25 wt% of compound C3, about 16 wt% to about 25 wt%, about 17 wt% to about 25 wt%, about 16 wt% to about 25 wt%, about 16 wt% to about 25 wt%, about 18 wt% to about 25 wt%, about 19 wt% to about 25 wt%, about 20 wt% to about 25 wt%, about 21 wt% to about 25 wt%, about 22 wt% to about 25 wt%, about 23 wt% to about 25 wt%, about 24 wt% to about 25 wt%, about 15 wt% to about 24 wt%, about 15 wt% to about 23 wt%, about 15 wt% to about 22 wt%, about
  • the weight ratio of resin composition to metal oxide is about 200: 1 to about 5:1, about 200:10 to about 5:1, about 200:20 to about 5:1, about 200:30 to about 5:1, about 200: 1 to about 200:30, about 200:1 to about 200:20, about 200: 1 to about 200:10, or about 200:1, about 200:10, about 200:20, about 200:30, about 200:40 (5:1), or any value or range therebetween.
  • the present disclosure also relates to a method of forming a shape memory polymer, the method comprising exposing a curable composition described above to ultraviolet light.
  • the shape memory polymer may further undergo a post-curing step.
  • the present invention also relates to a shape memory polymer formed or obtained or obtainable by the method disclosed herein.
  • the shape memory polymer may be configured to switch from a first shape to a second shape upon the shape memory polymer being heated to a temperature above a predetermined temperature and an external force; and wherein the shape memory polymer is configured to switch from the second shape to the first shape upon application of an external stimulus.
  • the predetermined temperature may be any value selected from a range of about 30°C to about 90 °C.
  • the present invention also relates to a device comprising the shape memory polymer disclosed herein.
  • the device may be a suture, stent or dental aligner.
  • the present invention also relates to a shape memory polymer comprising the curable composition disclosed herein, wherein the curable composition has been cured by ultraviolet light.
  • Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
  • Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO), 2-phenoxyethyl acrylate (2PA) and isobomyl acrylate (IBOA) were purchased from Tokyo Chemical Industry (TCI).
  • Trimethylolpropane ethoxylate triacrylate (TMPEOTA) with an average Mn of 428, ZnO nanoparticles (ZnONP) with particle size ⁇ 100 nm and Sudan I photoabsorber were purchased from Sigma-Aldrich.
  • the concentrations of ZnONP and Sudan I are determined with respect to the mass of the resin composition. For example in sample Zl, for every 100 g of resin composition, there was 1 g of ZnONP. Thus, the concentration of ZnONP is 1 wt/wt% with respect to the resin composition. Exemplary embodiments of a curable composition of the present invention are shown in
  • Z0 resin was prepared by combining 2PA, IBOA, TMPEOTA and BAPO together to form a mixture. The mixture is magnetically stirred for 1 hour at room temperature.
  • Zl, Z2.5 and Z5 were prepared by adding ZnONP into Z0, followed by magnetic stirring for 30 minutes and ultrasonication for 30 minutes to ensure dispersion of the ZnONP.
  • the shape memory polymer was 3D printed using an Asiga Max Digital Light Processing (DLP) printer (UV wavelength: 405 nm, intensity: 11 mW/cm 2 ).
  • DLP Asiga Max Digital Light Processing
  • the 3D printed SMP then underwent a post-curing step using Formlabs Form Cure, 60 minutes of U V radiation at 60 °C.
  • Figure 1 shows the cure depths of the curable compositions of Example 1 using the Asiga Max Digital Light Processing (DLP) printer (wavelength: 405 nm, intensity: 11 mW/cm 2 ).
  • DLP Digital Light Processing
  • ZnONP increases the initial rate of cure (Zl, Z2.5, Z5). It decreases the exposure time required to achieve the same layer thickness of 200 pm by 1 second, which is 28% faster than Z0. This is due to the nature of ZnONP acting as both a light scatterer and a photocatalyst.
  • ZnONP has a refractive index of 1.9 at 400 nm wavelength, which causes the UV rays to scatter within the printed layer.
  • ZnONP reduces excess unwanted cure, which is represented by the decrease in cure depth for exposure time greater than 5 seconds.
  • ZnO acts as an effective light blocking element for better printing accuracy without hindering the printing process.
  • the improvements in print quality can be observed in Figure 2, where the printed parts with ZnO (Figure 2, right) show less flashes (unwanted cure) on unsupported segments of the printed parts with small shape features compared to the neat formulation ( Figure 2, left).
  • Cure depth samples were prepared by printing a square array with different amounts of UV exposure. The samples were cured using the ASIGA MAX at 10 mW/cm 2 with varying exposure time.
  • Figure 3 shows a model of the square array of different height, which represents the amount of UV exposure each square receives. The thickness of each square was measured using a digital thickness gauge with a precision of 0.001 mm.
  • the cure depth measurements were taken from three randomised square arrays and plotted against the exposure time/energy.
  • a logarithmic equation (2) was estimated via Originlabs Nonlinear Curve Fit Tool.
  • the critical energy c and the depth of penetration p were derived from the constants from equation (2).
  • Figure 4a shows the cure depth against energy of curable compositions with various concentrations of ZnONP. Similar to the study on alumina nanowires, an increasing concentration of ZnONP resulted in a slower rate of increase in cure depth, thus lead to a decreasing trend of Dp. This could be the result of light absorption by ZnONP preventing the UV light from penetrating through the resin. The decrease in Dp can also be seen in sample SO.1.
  • the Ec of S0.1 is approximately 10 times higher than Z2.5. This means that S0.1 required more energy to start curing. Moreover, S0.1 was not able to print any samples with 2 s exposure time, unlike the other resins. S0.1 required more than 10 s to achieve the same cure height as the other resin with exposure time of 2 s. This suggests that ZnONP could be a good replacement of photoabsorbers for preventing excessive cure, while ensuring that the printing time is not compromised.
  • an overhanging structure as shown in Figure 5, was printed with the resins.
  • the structure contained hollow cuboids of 1.0 mm by 0.5 mm by 1.0 mm that can trap uncured resins during printing.
  • the trapped resin would experience multiple UV exposure due to light penetration and result in unwanted cure inside the hollow cuboid. The height of the unwanted cure is then measured for comparison.
  • the structure is printed with a slice thickness of 0.050 mm, with 1.5 seconds and 2 seconds of exposure time per layer. After the parts were printed, they were soaked in an ethanol bath for 5 minutes to remove any uncured resins and dried for another 5 minutes. Post-curing was done in Form Cure by Formlabs, at 60 °C for 15 minutes. The printed structure was viewed under the optical microscope and height of the hollow gaps were measured. The unwanted cure height was calculated by subtracting the average of the measured gap height with the actual gap height of 0.5 mm.
  • Figure 6 shows the microscopic images of the benchmarking samples printed with 2 seconds exposure time. Significant amount of flash can be seen in the Z0 samples in as compared to the Z1 and Z2.5 samples. As Z0 has the greatest transparency, the UV light during printing could penetrate through the cured layers. If the resin was trapped in the hollow gaps, it would be cured due to multiple UV exposures.
  • Equation (3) 0 refers to the plane where the 0.5 mm gap ends, as shown in Figures 7a and 7b. Equation (3) was then normalised into equation (4), and the summation of all the exposures lead to equation (5). Using equation (5), a theoretical value for the unwanted cure height was calculated and compared to the actual results.
  • O X ⁇ 0 1 O n - (5)
  • Example 1 The mechanical properties of the curable composition were further investigated using the samples of Example 1. Tensile tests were conducted with ASTMD638 Type V specimens, printed with 2 seconds exposure time (10 seconds for S0.1) and slice thickness of 0.050 mm. The specimens were lightly washed with ethanol after printing. Two sets of specimens were postcured in Form Cure at 60 °C for 60 minutes and 180 minutes separately. In addition, a third set of specimens were printed without post-curing. Known as green parts, these specimens were soaked in ethanol for 5 minutes, dried for 5 minutes and kept in a dark environment before being tested to prevent any further curing. The Instron 3366 with a fixed pulling rate of 2.5 mm/min was used.
  • Figures 8a and 8b shows the tensile properties of the post-cured specimens after 60 minutess. All the specimens exhibit both elastic and plastic deformation.
  • the yield strength which is the maximum stress in the elastic deformation, displays a decreasing trend with increasing concentration of ZnONP. This resulted in a decreasing trend in Young’s modulus as well.
  • the fracture strain which is the maximum strain before fracture, shows an increasing trend with increasing concentration of ZnONP. This also led to greater toughness for specimens containing ZnONP compared to Z0.
  • a compression Dynamic Mechanical Analyzer (DMA) test was performed to showcase the recovery force exerted by a programmed sample, as well as the maximum recovery that the sample can achieve.
  • An octahedron cube was printed using the Z0 ( Figure lOd) and was compressed up to 40% strain at 40 °C ( Figure 10a to 10c).
  • the compression plates were locked and die furnace was opened to cool down the sample. After cooling, the sample undergoes a temperature ramp up to 40 °C.
  • the recovery stress is measured as the strain is maintained at 27%.
  • the sample is cooled again after the run, before ramping the temperature to 40 °C again, this time to measure the recovery strain at very low applied force.
  • Example 8 Thermomechanical Properties of Strut
  • ZnO nanoparticles were able to reduce the penetration of UV light in resins during DLP printing, which helped to eliminate any unwanted curing in the vertical direction. Moreover, the layer exposure time needed for printing resins containing ZnO nanoparticles did not increase, in contrast to the effect of photoabsorbers. Unlike the printed part with Sudan I (SO.1), the integrity of the mechanical properties were maintained when ZnONP were added into the resin. The ZnO nanocomposites showed some toughening effects, with only a slight decrease in tensile strength and Young’s modulus.
  • the present invention relates to curable compositions which are useful in forming shape memory polymers.
  • the curable compositions of the present disclosure allow for fast U V curing into shape memory polymers (SMP).
  • SMP shape memory polymers
  • the working temperature of the SMP may be brought closer to body temperature, even after extensive post-treatment is applied. This advantageously makes it easier to trigger its shape memory effect without having to heat the SMP to high temperatures. Further advantageously, the SMPs may have high recovery ratio of 99% at 40 °C.
  • the curable compositions of the present disclosure may further comprise metal oxides, such as zinc oxide.
  • metal oxides such as zinc oxide.
  • the addition of metal oxide not only speeds up the curing process, it also helps to improve the print quality of the product by reducing flashes. It also provides slight improvement in the mechanical properties at both room temperature and body temperature.
  • metal oxide also advantageously reduces the amount of energy needed to cure a layer of resin, while preventing excessive unwanted cure during the printing process.
  • the inclusion of metal oxide increases the toughness of the material, with some compromise on the tensile strength and Young’s Modulus.
  • the curable compositions of the present disclosure do not contain photoabsorbers, such as l-phenylazo-2-naphthol (Sudan I), l-[4-

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Abstract

La présente invention concerne une composition durcissable comprenant (i) une composition de résine, la composition de résine comprenant : un composé C1 ayant un groupe X et un groupe aryle facultativement substitué ; un composé C2 ayant un groupe X et un groupe carbocyclyle facultativement substitué ; un composé C3 ayant au moins deux groupes X ; et un photo-initiateur, X étant un acrylate ou un méthacrylate. Les compositions durcissables de la présente invention peuvent être utilisées pour former des polymères à mémoire de forme. Dans un mode de réalisation privilégié, une composition durcissable comprenant de l'acrylate de 2-phénoxyéthyle, de l'acrylate d'isobornyle, du triacrylate d'éthoxylate de triméthylolpropane et des nanoparticules de ZnO est utilisée pour former un polymère à mémoire de forme.
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