US20140142207A1 - Ultra low density biodegradable shape memory polymer foams with tunable physical properties - Google Patents

Ultra low density biodegradable shape memory polymer foams with tunable physical properties Download PDF

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US20140142207A1
US20140142207A1 US13/797,631 US201313797631A US2014142207A1 US 20140142207 A1 US20140142207 A1 US 20140142207A1 US 201313797631 A US201313797631 A US 201313797631A US 2014142207 A1 US2014142207 A1 US 2014142207A1
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acid
composition
hydroxyl
foams
monomer
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US13/797,631
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Pooja Singhal
Thomas S. Wilson
Elizabeth Cosgriff-Hernandez
Duncan J. Maitland
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Texas A&M University System
Lawrence Livermore National Security LLC
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Texas A&M University System
Lawrence Livermore National Security LLC
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Assigned to LAWRENCE LIVERMORE NATIONAL SECURITY, LLC reassignment LAWRENCE LIVERMORE NATIONAL SECURITY, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SINGHAL, Pooja, WILSON, THOMAS S.
Assigned to U.S. DEPARTMENT OF ENERGY reassignment U.S. DEPARTMENT OF ENERGY CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Priority to CA2874471A priority patent/CA2874471C/fr
Priority to PCT/US2013/041894 priority patent/WO2013177081A1/fr
Priority to EP13794314.8A priority patent/EP2855555B8/fr
Assigned to THE TEXAS A&M UNIVERSITY SYSTEM reassignment THE TEXAS A&M UNIVERSITY SYSTEM ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COSGRIFF-HERNANDEZ, Elizabeth, MAITLAND, DUNCAN J.
Publication of US20140142207A1 publication Critical patent/US20140142207A1/en
Priority to US15/269,516 priority patent/US9840577B2/en
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Definitions

  • This invention relates to shape memory polymers and specifically to shape memory polymers and polymer foams having enhanced characteristics of degradability, control over cell structure, and density.
  • SMPs Shape memory polymers
  • Thermally responsive SMPs that use heat energy for their actuation can be deformed from their primary shape to a secondary shape above their actuation temperature. This secondary shape can then be “fixed” by cooling the deformed shape to below the material's actuation temperature. When they are heated to above their actuation temperature on demand, they recover their “remembered” primary shape.
  • Polyurethane based SMP foams were initially proposed by Hayashi et. al—Japanese patent 5049591 (1991). Other related patent applications were also filed in this field by Applicants, U.S. patent application Ser. No.
  • shape memory materials are useful in diverse applications like shape adaptive sportswear (helmets, suits), housing (thermal sealing of doors and windows) and robotics (conformal grip design). Also these materials are being investigated for use in automobile and aerospace industries for self healing automobile bodies and morphing aircraft wings.
  • shape memory foam based biomedical devices for minimally invasive surgeries are being developed, see El Feninat, F., Laroche, G., Fiset, M. & Mantovani, D. Shape memory materials for biomedical applications. Advanced engineering materials 4, 91-104 (2002); Sokolowski, W., Metcalfe, A., Hayashi, S., Yahia, L. H.
  • Shape memory polymer stent with expandable foam a new concept for endovascular embolization of fusiform aneurysms. Biomedical Engineering, IEEE Transactions on 54, 1157-1160 (2007).
  • a network structure consisting of high density of covalent crosslinks, is preferable for good mechanical properties and improved shape memory behavior (high recovery force, high shape recovery), particularly for very low density foams.
  • E porous and E neat are the Young's moduli and porous and neat are the densities, of porous and neat/unfoamed materials respectively.
  • Controlling the cell structure of foams is another key requirement in generation of commercial grade SMP foams, and we propose manipulating viscosity of the foaming solution for the same.
  • the effect of viscosity on foam cell structure has been studied in detail for foam emulsions; Kim, Y. H., Koczo, K. & Wasan, D. T. Dynamic Film and Interfacial Tensions in Emulsion and Foam Systems. Journal of colloid and interface science 187, 29-44 (1997) and Shah, D., Djabbarah, N. & Wasan, D.
  • compositions and/or structures of degradable SMPs ranging in form from neat/unfoamed to ultra low density materials of down to 0.005 g/cc density. These materials show controllable degradation rate, actuation temperature and breadth of transitions along with high modulus and excellent shape memory behavior.
  • FIG. 1 is a synthesis outline for making a trifunctional hydroxyl monomer with ester linkages from triethanol amine and 3-hydroxybutyrate.
  • FIG. 2 is a synthesis outline for making a tetrafunctional hydroxyl monomer with ester linkages from Citric Acid and 1,3 Propane diol.
  • FIGS. 3A , 3 B and 3 C are displays pictures of cell structure of low density degradable shape memory polymer foams of the invention.
  • FIG. 4 is a graphical plot showing the “Trend of variation in the prepolymer rheology with increase in the OH/NCO ratio of the prepolymer”.
  • FIGS. 5A through 5F show “Variation in cell structure achieved based on the viscosity of the foaming prepolymer”.
  • FIG. 6 is a graphical plot illustrating the mechanism of obtaining lower density foams via use of successively higher boiling point blowing agents.
  • the present invention consists of compositions and methods for degradable shape memory polymer (SMP) and foams from those polymers. It is also methods for controlling the properties of these SMPs.
  • SMP shape memory polymer
  • the invention may be expressed in four broad embodiments that include:
  • compositions and/or structures of degradable SMPs ranging in form from neat/unfoamed to ultra low density materials of down to 0.005 g/cc density.
  • compositions that show controllable degradation rate, actuation temperature and breadth of transitions along with high modulus and excellent shape memory behavior.
  • the materials disclosed here are degradable, with good mechanical properties and shape memory behavior at very low densities.
  • One of the ingredients for making these materials is a multifunctional hydroxyl, amine, or carboxylic acid containing monomer of small molecular weight (e.g. 200-1500 g), having degradable (for e.g. ester, ether, amide, urethane) linkages.
  • degradable for e.g. ester, ether, amide, urethane
  • FIG. 1 Using a branched monomer (3 or more branches in structure) with hydroxyl end groups and reacting it with a difunctional monomer with an acid group on one end and a hydroxyl group on the other end. Reaction of the hydroxyl group of branched monomer and acid group of difunctional monomer will form an ester linkage releasing a water molecule. This will extend the branches of the original branched hydroxyl monomer with ester linkages, keeping the hydroxyl group as its terminal/end group.
  • a branched monomer (3 or more branches in structure) with hydroxyl end groups and reacting it with a difunctional monomer with an acid group on one end and a hydroxyl group on the other end. Reaction of the hydroxyl group of branched monomer and acid group of difunctional monomer will form an ester linkage releasing a water molecule. This will extend the branches of the original branched hydroxyl monomer with ester linkages, keeping the hydroxyl group as its terminal/end group.
  • branched monomer with acid end groups can be reacted with a difunctional monomer containing hydroxyl end groups. This will similarly form a multifunctional monomer having ester linkage with the end groups of hydroxyl functionality.
  • Steps described in (2) and (3) may be accomplished in succession to controllably increase the number of degradable functional groups in each arm of the monomer, which in turn provides a means to control degradation kinetics.
  • some of the possible multifunctional hydroxyl monomers include Triethanol amine (TEA), Hydroxy propyl ethylene diamine (HPED), Glycerol, Pentaerythritol or Trimethylolpropane, Bis-tris methane, Bis-tris propane, 1,2, 4 Butane triol, Miglitol, Trimethylolethane and Tris(hydroxymethyl)aminomethane.
  • TEA Triethanol amine
  • HPED Hydroxy propyl ethylene diamine
  • Glycerol Pentaerythritol or Trimethylolpropane
  • Bis-tris methane Bis-tris propane
  • 1,2, 4 Butane triol 1,2, 4 Butane triol
  • Miglitol Trimethylolethane
  • Tris(hydroxymethyl)aminomethane Tris(hydroxymethyl)aminomethane.
  • Some of the possible monomers with one acid and (at least one) hydroxyl group, that can react with above multifunctional hydroxyl groups include L-Threonic acid, Tricine, Shikimic acid, 3-Hydroxybutyrate, ⁇ -Caprolactone, Lactic acid, and Glycolic acid.
  • multifunctional carboxylic acids can include 1,4-benzoquinonetetracarboxylic acid, Ethylenediamine-N,N′-disuccinic acid, furantetracarboxylic acid, hydroxycitric acid, citric acid, Nitrilotriacetic acid, Aconitic acid, isocitric acid and Propane-1,2,3-tricarboxylic acid.
  • Some of the possible diol monomers that can react with above multifunctional carboxylic acids by scheme 2 include Polyethylene glycol, 1,3-Propanediol, 1,4-Butanediol, 1,5-Pentanediol, 1,2-Propanediol, 1,2-Butanediol, 2,3-Butanediol, 1,3-Butanediol, 1,2-Pentanediol, Etohexadiol and 2-Methyl-2,4-pentanediol.
  • Triethanol amine is end capped with 3-Hydroxybutyrate (HB) as shown in FIG. 1 .
  • Anhydrous pyridine is used to initiate the formation of an ester link between the hydroxyl end groups of TEA and the activated carboxyl group of the HB.
  • the precipitated dicyclohexylurea is then removed with vacuum filtration and the polymer solution is washed with distilled water. Solvent is then removed by rotary evaporation, followed by the drying of the polymer in vacuum.
  • a tetrafunctional hydroxyl monomer is prepared by end capping Citric acid (CA) with 1,3 Propane diol, as shown in FIG. 2 .
  • CA and Propane diol are reacted together at 160° C. under stirring for 15 minutes. The temperature is subsequently decreased to 140° C. and reaction mixture is stirred for 1 hour. The resulting prepolymer is purified by precipitation in water and then it is freeze dried. While the idea of making these highly crosslinkable short-branch multifunctional monomers using 1,3 Propane diol is new, a similar synthesis procedure involving citric acid and its derivatives has been adopted by Yang et. al. and group 29 .
  • PCT Polycaprolactone triol
  • branched monomers with end hydroxyl functionality are then reacted with small molecular weight diisocyanate monomers.
  • small molecular weight diisocyanate monomers include (but are not limited to), Hexamethylene diisocyanate (HDI), Tri-methyl Hexamethylene diisocyanate (TMHDI) and Isophorone diisocyanate for aliphatic options and monomers such as Toluene diisocyanate, Methylene diphenyl diisocyanate for aromatic options.
  • hydroxyl monomers without degradable linkages are chosen such that their steric hindrance and mobility is comparable to that of monomers with degradable linkages. These non-degradable branched hydroxyl monomers are then substituted for the degradable branched hydroxyl monomers in appropriate amounts.
  • Controlling the length of the network active chains in the polymer structure can define the breadth of the transition of the materials from their glassy to rubbery state. The wider the distribution of lengths of network active chains in the polymer, the broader will be the transitions of glass transition temperature, modulus etc. A narrow distribution on the other hand, will give sharper transitions.
  • One of the ways to achieve this is by controlling the length of each branch of the multifunctional monomers, for e.g. by controlling the number of hydrolysable linkages in each branch.
  • controlling or keeping the same number of degradable linkages in each arm of the multifunctional monomers will give a sharper drop in mass and more reproducible mass loss pattern with respect to time during the degradation of the material.
  • a more broad distribution of the number of degradable linkages in each arm, or in each network active chain segment across the sample, will lead to a more spread out/or broader drop in mass with respect to time.
  • a prepolymer is made with excess isocyanate in the desired ratio of hydroxyl monomers based on degradability and actuation temperature requirements.
  • the solutions are mixed until a clear, single phase is formed, possibly requiring the use of a Flacktek/Thinky speed mixer or an equivalent high speed mixing technique, based on the content of more hydrophilic moieties, such as Poly caprolactone triol and Triethanol amine.
  • the prepolymers are then allowed to cure over a 2-3 day period. Typically prepolymer viscosities in the range of 2 Pa ⁇ s to 60 Pa ⁇ s post cure, can potentially yield viable foams.
  • the balance hydroxyl monomers in the desired ratio of functionality and degradability are mixed together with surfactants, tin and amine based catalysts, and water.
  • Water here accounts for a percentage of hydroxyl monomers via urea formation and assists in the chemical blowing of foam.
  • This hydroxyl premix is added to the prepolymer with excess isocyanate in calculated amounts, and mixed vigorously, optionally in a speed mixer, for a few seconds.
  • a physical blowing agent or a combination of physical blowing agents
  • solution is mixed again. Thereafter the foam is allowed to rise in an oven at 90° C. The high temperature helps in maximizing the generation of CO 2 via the chemical blowing reaction in the foaming solution.
  • multifunctional monomers with other functional end groups that are reactive with isocyanates such as amines and carboxylic acids etc.
  • these materials can be modified by use of a variety of additives and/or fillers, such as contrast agents, plasticizers, dyes, pigments, carbon nanotubes etc., to enhance/change its physical, mechanical, optical, electrical, or magnetic properties.
  • additives and/or fillers such as contrast agents, plasticizers, dyes, pigments, carbon nanotubes etc.
  • several post synthesis processes for reticulation etc. such as hydrolysis, oxidation, application of pressure, heat or mechanical treatment, can be performed on the foams to modify their physical structure.
  • Degradable foams were made by using Polycaprolactone triol as the degradable hydroxyl monomer made from grafting caprolactone moieties on Trimethylolpropane by the first scheme detailed above (used as received from Sigma Aldrich, Mw 300 g), Triethanol amine as the non-degradable hydroxyl monomer to control the rate of degradation, and Hexamethylene diisocyanate.
  • NCO premix or prepolymer with excess diisocyanate, is made by mixing the components as per Table 1.
  • the mixing is performed in a Flacktek speed mixer or an equivalent vigorous mixing technique as both Polycaprolactone triol and Triethanol amine are not readily miscible in Hexamethylene diisocyanate.
  • the NCO premix is stored under Nitrogen atmosphere and allowed to cure over a period of 2-3 days. The viscosity of the solution increases as reaction occurs between hydroxyl and isocyanate groups, reaching a value in the range of 2-60 Pa ⁇ s.
  • an OH premix is made by mixing the components as per Table 1 (amounts given for a single foam batch, and can be scaled up for more batches).
  • NCO premix and OH premix are poured together in the amounts per Table 1, and mixed vigorously in a Flacktek (or equivalent mixer) for 10 sec at 3400 rpm speed.
  • Enovate is added to the foaming solution and mixed again for 5 sec at 3400 rpm in Flacktek mixer.
  • the solution is then transferred to the oven at 90° C. and allowed to rise up. Cell structures of resulting foams are shown in FIGS. 3A , 3 B and 3 C.
  • FIG. 3A shows EA0PCT100FW96, (0% TEA @ 0.45 OH/NCO).
  • FIG. 3B shows TEA30PCT70FW96 (30% TEA @0.45 premix OH/NCO).
  • FIG. 3C shows TEA60PCT40FW96 (60% TEA @0.42 premix OH/NCO).
  • the cell structure of the foams made from the polymer composition described above may be achieved by control over the viscosity of excess isocyanate prepolymer.
  • a larger cell size is obtained at lower viscosity of prepolymer and as the viscosity is increased, the cell size gradually decreases.
  • the viscosity can be manipulated while still keeping the net composition of the polymer the same. Hence finer control of foam cell structure is possible.
  • This technique is based on the fact that at a lower viscosity of the prepolymer, the rate of drainage of the polymer solution from the foam cell lamella is higher, and also the resistance to foam cell expansion with a given internal bubble pressure is lower, for a longer period of time until the gelation of the polymer occurs.
  • the viscosity can also be manipulated by adding some inert liquid phase solvents in the system.
  • Foams with controlled cell structure were made by using Hydroxy propyl ethylene diamine, Triethanol amine as the hydroxyl monomers, and Hexamethylene diisocyanate. The viscosity of the foaming solution was varied to achieve a controlled change in cell structure of the foams.
  • NCO premix or prepolymer with excess diisocyanate, is made by mixing the components as per Table 2. Since this composition readily forms a single phase solution, very vigorous mixing is not required. Using a mechanical vortex or shaking by hand worked well for creating a clear solution. The NCO premix is then allowed to cure over a period of 2-3 days. The viscosity of the solution increases as reaction between hydroxyl and isocyanate groups takes place reaching a value in the range of 2-60 Pa's for various formulations in Table 2 (viscosity values shown in FIG. 4 ).
  • an OH premix is made by mixing the components as per Table 2 (amounts given for a single foam batch, and can be scaled up for more batches).
  • NCO premix and OH premix are poured together in the amounts per Table 2, and mixed vigorously in a Flacktek (or equivalent mixer) for 10 sec at 3400 rpm speed. Then Enovate is added to the foaming solution and mixed again for 5 sec at 3400 rpm in Flacktek mixer. The solution is then transferred to the oven at 90° C. and allowed to rise up. Cell structure is shown in FIG. 4 .
  • FIGS. 5A , 5 B, 5 C, 5 D, 5 E and 5 F show variation in cell structure achieved based on the viscosity of the foaming prepolymer. Variation in cell structure is achieved based on the viscosity of the foaming prepolymer.
  • the net formulation of 44% Hydroxy Propyl Ethylene Diamine, 11% Triethanol Amine and 41% water, based on % equivalents, was used with Hexamethyene diisocyante at 104 isocyanate index for all cases. Scale bar 400 um.
  • Surfactants DC-1990 and DC-5169, and catalysts BL-22 and T-131 are used as received from Air Products, Inc. Actual weights of chemicals added in grams are given.
  • Variation in the duration and speed of mixing the foaming solution is another method of controlling the cell structure of foams disclosed here.
  • a higher duration or speed of mixing of the foaming solution gives finer cell size with denser foams because the forces acting on the material during mixing can break up the larger bubbles. Further, due to the viscous heating during mixing, part of the blowing gas can be lost, and also the reaction can speed up causing gelation to occur faster. This leaves less time for the foam to blow up causing denser foams with smaller cell structure.
  • the foam structure can be non-uniform or the foams can eventually collapse due to phase separation of hydroxyl and isocyanate moieties, and their inability to react fast enough.
  • the addition of the hydroxyl premix can be done in two steps, a) First mixing the balance hydroxyl monomers with the isocyanate premix for longer time on the order of a few minutes, b) then catalysts, water and physical blowing agents added to foaming solution and mixed for a shorter time on the order of a few seconds.
  • Increase in the amount of surfactants and/or catalysts can also help in decreasing the cell size by increasing the stabilization of the cells and increasing the rate of reaction respectively.
  • Foams of very low density are made by use of successively higher boiling point blowing agents. This strategy is based on the process of foam blowing. For a pure liquid, formation of foam cells during blowing is dependent on the concentration of gas present in the foaming solution at any given time. As the gas concentration increases, it is only above a critical concentration that Rapid Self Nucleation (RSN) begins to occur—see Klempner, D., Sendijarevic, V., Sendijarevi c, V. & Aseeva, R. M. Handbook of polymeric foams and foam technology . (Hanser Gardner Publications, 2004) and LaMer, V. Kinetics in phase transitions.
  • RSN Rapid Self Nucleation
  • blowing agents include HFC 245-fa (Boiling Point 15.3° C.), Micro care CF: Blend of 40% HFC 365-mfc and 60% HFC 4310-mee (Boiling Point 45° C.) and HFE 7100 (Boiling Point 61° C.). While this method decreases the density of the foam by introduction of higher amount of gas phase, the cell structure can also get changed in this process leading to larger cells because of a higher gas pressure inside the cells. For maintaining a small cell size, simultaneous increase in the surfactant levels needs to be done to decrease the surface tension and stabilize the small cell size. Instead of using multiple blowing agents, a process of introducing a given blowing agent to the foaming solution, at specified time intervals, can also be engineered with the same result.
  • particulate nucleating agents is another way in which we can catalyze the generation of bubbles and potentially lower the possibility of formation of voids or large increase in cell size.
  • the presence of porogens can assist in keeping the individual cell size from growing larger, both by nucleation of bubbles, and by increasing the viscosity of the foaming solution. Also, they can be leached out of the foam post cure, further lowering the foam bulk density.
  • Another foam processing technique that can achieve densities down to 0.005 g/cc, while maintaining a good shape memory behavior, is to pull vacuum on the foam while the foam is rising, and allow it to cure under vacuum.
  • Another technique for making highly crosslinked low density foams is to use two or higher functionality carboxylic acids in place of water as the blowing agent.
  • One carboxylic acid group reacts with one isocyanate group to release a carbon-dioxide molecule while forming an amide bond. This is twice the production of blowing gas compared to water with the same amount of isocyanate, making it a promising technique.
  • Further higher functionality of carboxylic acids, such as Citric Acid form covalent crosslinks in the foam, as opposed to physical crosslinks with urea from the use of water, and assist in making a highly covalently crosslinked network structure per our material design criteria.
  • Density/porosity of the materials can be controlled either for a specific density/porosity, or a continuous gradient or another pattern in the variation density/porosity across a sample. This can be done e.g. by using one or more of the techniques in the method 3) above on a single piece of foam, and/or by combining different foams of varying density/porosity gradients as desired.
  • cell size and cell size distribution of a foam sample can be engineered, e.g. by using one or more of the methods in the 2) above on the same foam, and/or by combining different foams of varying cell sizes and distribution to achieve respective gradients as desired.
  • the degree of cell openness of the foams can be controlled, for e.g. via changing the synthesis process, such as the amount and type of surfactants and catalysts etc. or using post processing methods for removal of membranes, such as hydrolysis, oxidation, heat or mechanical treatment etc.
  • the material By exercising control of one or more of density/porosity, cell size, cell size distribution, cell openness etc. with a desired pattern of variation of respective properties throughout the bulk of the material, the material can be optimized for use in multiple applications. For e.g. when a foam sample is actuated in a media, the rate of diffusion of the media in the foam can be controlled by controlling the density/cell sizes/cell openness etc. throughout the foam sample.
  • Improved cell opening is achieved, in another embodiment by the use of high z metal nano- or micro-particles, including but not limited to tungsten, tantalum, platinum and, palladium. These particles can serve the dual purpose of a) assisting in the cell opening during the foaming process, and/or b) providing x-ray contrast for imaging in the foam devices.
  • Metals typically have a surface oxide layer which provides them with a high surface energy and therefore allowing them to be wetting with the foam formulation.
  • a surface modification of the metal particles with a low surface energy coating such as a fluorinated coupling agent (e.g. fluorosiloxane, fluorosilane, fluorocarbon, fluoropolymer) helps to destabilize the membrane during the foaming process by decreasing the extent of its wetting with the foaming solution.
  • a fluorinated coupling agent e.g. fluorosiloxane, fluorosilane, fluorocarbon, fluoropolymer
  • the size of the particulate is another important parameter since the particles may be more effective in destabilizing the foam cell membranes as the membrane thickness approaches particle size. Selection of the particle size can be used to tune the specific area at which the membranes are destabilized during foaming. The onset of destabilization is expected to occur approximately at the point when particle size equals membrane thickness.
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US11407851B2 (en) 2016-12-02 2022-08-09 The Texas A&M University System Chemically modified shape memory polymer embolic foams with increased X-ray visualization
JP2020500604A (ja) * 2016-12-02 2020-01-16 ザ テキサス エーアンドエム ユニバーシティ システムＴｈｅ Ｔｅｘａｓ Ａ＆Ｍ Ｕｎｉｖｅｒｓｉｔｙ Ｓｙｓｔｅｍ Ｘ線可視化を高めた化学修飾形状記憶ポリマー塞栓フォーム
JP7171570B2 (ja) 2016-12-02 2022-11-15 ザ テキサス エーアンドエム ユニバーシティ システム Ｘ線可視化を高めた化学修飾形状記憶ポリマー塞栓フォーム
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EP2855555A4 (fr) 2016-05-11
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US9670308B2 (en) 2017-06-06
WO2013177081A1 (fr) 2013-11-28
EP2855555A1 (fr) 2015-04-08
EP2855555B8 (fr) 2020-03-04
US9840577B2 (en) 2017-12-12
US20170002130A1 (en) 2017-01-05
CA2874471A1 (fr) 2013-11-28
CA2874471C (fr) 2021-08-03

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