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WO2018185650A1 - Composite de polyuréthane - Google Patents

Composite de polyuréthane Download PDF

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Publication number
WO2018185650A1
WO2018185650A1 PCT/IB2018/052283 IB2018052283W WO2018185650A1 WO 2018185650 A1 WO2018185650 A1 WO 2018185650A1 IB 2018052283 W IB2018052283 W IB 2018052283W WO 2018185650 A1 WO2018185650 A1 WO 2018185650A1
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WIPO (PCT)
Prior art keywords
diisocyanate
temperature
nanoparticles
functionalized
process according
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Ceased
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PCT/IB2018/052283
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English (en)
Spanish (es)
Inventor
Herley CASANOVA
Luis Fernando Giraldo Morales
Lina Paola Higuita Conzalez
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Nexentia Sas
Universidad de Antioquia UdeA
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Nexentia Sas
Universidad de Antioquia UdeA
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Publication of WO2018185650A1 publication Critical patent/WO2018185650A1/fr
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

Definitions

  • the invention pertains to the field of composite materials, particularly to synthetic polymer composites of the polyurethane type.
  • the present invention relates to a composite comprising functionalized nanoparticles incorporated in a polyurethane matrix and their synthesis process.
  • the process comprises melting a diisocyanate in a reactor in an inert gas atmosphere; add a macrodiol controlling temperature and constant stirring until a prepolymer is obtained; add a chain extender and cure the polymer obtained.
  • functionalized nanoparticles are incorporated, which are made up of primary particles embedded in a protein matrix.
  • FIG. 1 Particle size distribution of calcium carbonate nanoparticles functionalized with protein.
  • FIG. 2 Scanning electron micrograph of 50% CaCC calcium carbonate nanoparticles, 50% Sodium caseinate.
  • FIG. 3 Scanning electron micrograph of polyurethane-calcium carbonate nanoparticles (0.5% nanoparticles).
  • FIG. 4 Scanning electron micrograph of polyurethane-calcium carbonate nanoparticles (2.0% nanoparticles).
  • polyurethanes are polyurethanes, polycarbonates and polyesters, given their biocompatibility, biodegradation and adjustable mechanical properties.
  • polyurethanes it is It is possible to achieve a wide variation in the mechanical and adhesive properties of the materials obtained, due to the diversity in the chemical composition of the monomers involved in their synthesis (ie isocyanates, alcohols, amines and chain extenders).
  • the thermoplastic properties of polyurethanes are associated with the presence of two microfases or microdomains, a hard one that gives it mechanical strength and a soft one that provides flexibility to the material and modular adhesive properties.
  • thermoplastic polyurethanes allow their application in the production of biomaterials for the total or partial replacement of tissues that are permanently subjected to compressive, shear or elongation forces. This is how thermoplastic polyurethanes have been used in the repair or replacement of heart muscles, nerves, blood vessels, bones and cartilage.
  • thermoplastic polyurethanes like other pure synthetic or natural polymers, have imbalances in their mechanical, adhesive or functional properties. This is why in nature proteins or polysaccharides usually bind to inorganic materials (eg calcium carbonate or phosphate) to generate composite materials or composites, which develop the elasticity of the natural polymer and the biological properties of the inorganic material (eg stimulation of cell growth and adhesion between tissues).
  • inorganic materials eg calcium carbonate or phosphate
  • Thermoplastic polyurethane composites have been developed for biomedical applications using calcium carbonate as filler material to promote cell growth, due to their better adhesive properties with respect to polyurethanes without added filler material (Ida Dulinska-Molaka, Malgorzata Lekka, Krzysztof J. Kurzydlowski Surface properties of polyurethane composites for biomedical applications Applied Surface Science 270 (2013) 553-560).
  • hydroxyapatite nanoparticles have been disclosed as biocompatible support material (La ⁇ s P. Gabriel, Maria Elizabeth M. dos Santos, André L. Jardini, Gilmara NT Bastos, Mé GBT Dias, Thomas J. Webster, Rubens Maciel Filho, Bio -based polyurethane for tissue engineering applications: How hydroxyapatite nanoparticles influence the structure, thermal and biological behavior of polyurethane composites Nanomedicine: Nanotechnology, Biology, and Medicine 13 (2017) 201-208), bone particles or bone substitute materials (eg calcium carbonate, calcium phosphate) for osteoimplants (US20050027033) and for orthopedic applications (US20100112032).
  • biocompatible support material La ⁇ s P. Gabriel, Maria Elizabeth M. dos Santos, André L. Jardini, Gilmara NT Bastos, Mé GBT Dias, Thomas J. Webster, Rubens Maciel Filho, Bio -based polyurethane for tissue engineering applications: How hydroxyapatite nanoparticle
  • the compound developed by Duliska-Molaka et al. (2013) used calcium carbonate microparticles with sizes between 3.1 and 84.4 micrometers at a concentration of 10%, and incorporated into the macrodiol (ie polycaprolactone diol) during the synthesis process, with the sole purpose of generating adequate adhesion of human cells derived from bone.
  • composition developed by Gabriel et al. (2017) used agglomerates of hydroxyapatite nanoparticles (150 nm) obtained by the sol-gel method at a concentration of 20% and incorporated into the polyurethane pre-polymer (obtained from the reaction between a polyol of the fruits of Acai and hexamethylene diisocyanate).
  • the composite material was developed for the purpose of improving the adhesive properties of fibroblasts, inhibiting inflammatory reactions in cells and promoting tissue formation functions in cells.
  • the present invention relates to a composite or composite material comprising functionalized nanoparticles incorporated in a polymeric polyurethane matrix.
  • Composite is understood as a material composed of two or more materials with significantly different physical or chemical properties.
  • the functionalized nanoparticles referred to in the present invention are primary particles of inorganic or organic nature embedded in a protein matrix (as shown in patent application WO2012 / 140626 and explained again herein), which form a nanoparticle of multicore type, where the protein matrix in turn acts as a functionalizing agent of the nanoparticle.
  • the functionalized nanoparticles are suspended non-aggregated in the aqueous phase and are smaller than 10Onm.
  • the functionalized nanoparticles have a particle size between 5 nm and 1000 nm, preferably between 10 nm and 500 nm.
  • the functionalized nanoparticles have a particle size between 50nm and 400nm, preferably between 150nm and 300nm. Increasing the particle size above these sizes can reduce the mechanical properties of the material.
  • Functionalized nanoparticles are formed by primary particles embedded in a protein matrix.
  • the primary particles have particle sizes less than 20nm. In one embodiment, the primary particles have a particle size between 3nm and 18nm. In another embodiment, the primary particles have a particle size between 5nm and lOnm.
  • the content of the primary particles in the functionalized nanoparticles is between 5% and 70%. In one embodiment, the content of the primary particles in the functionalized nanoparticles is between 20% and 50% or between 30% and 45%, where the remaining percentage corresponds to the protein matrix.
  • the primary particles may be inorganic compounds, minerals, metal oxides, non-metal oxides, iron oxides, zinc oxides, carbonates, phosphates, aluminosilicates.
  • the primary particles may be, among others, CaCC, CaMg (C03) 2, MgC0 3 , FeC0 3 , CaFe (C0 3 ) 2 , MnC0 3 , FeC0 3 , MgC0 3 , CaMn (C0 3 ) 2 , CaFe (C0 3 ) 2 , CaMg (C0 3 ) 2 , Ca 3 (P0 4 ) 2 , ZnO, Cu 2 0, CuO, CoO, Au 2 0 3 , Ti0 2 , Ni 2 0 3 , Ag 2 0, HgO, CrO, BaO, Cr 2 0 3 , PbO, FeO, Fe 2 0 3 , CaO, Li 2 0, SnO, Sn0 2 , BaS0 4 ,
  • the protein matrix is selected from dairy, meat and vegetable proteins.
  • the proteins can be whey protein, caseins, caseinate, beta lactalbumine, egg protein such as ovalbumin, sarcoplasmic and myofibrillar meat proteins, vegetable proteins such as soy protein, corn, rice, barley, He sang it, oatmeal, among others, and its combinations.
  • the protein matrix is selected from: calcium caseinate, sodium caseinate and whey protein.
  • the protein matrix of the functionalized nanoparticles can be in a concentration between 10% and 70% of the functionalized nanoparticle. In one embodiment of the invention, the protein matrix is in a concentration between 10% and 30% of the functionalized nanoparticle. In another embodiment of the invention, the protein matrix is in a concentration between 40% and 60% of the functionalized nanoparticle. In another embodiment, the protein matrix is in a concentration between 45% and 55% of the functionalized nanoparticle. Additionally, the functionalized nanoparticles can encapsulate water soluble active ingredients, which can be chemical or biological compounds susceptible to being encapsulated or associated with the nanoparticle and are selected from the group consisting of drugs, cells and biotechnological products.
  • the functionalized nanoparticles referred to in the present invention are incorporated into a polymeric polyurethane matrix, functioning as a reinforcing material.
  • the polyurethane is a thermoplastic polyurethane. Incorporating functionalized nanoparticles as reinforcement material to the polymeric material, it gives the material a better performance with respect to the material without reinforcement, because the constituents of a composite material have different chemical structures and compositions, and therefore, different physical properties. The result is a synergy of the properties of the initial materials.
  • the percentage of functionalized nanoparticles in the composition may be in the range of 0.1% m / m to 20.0% m / m.
  • the amount of functionalized nanoparticles in the composition is in a range of 0.5% m / m to 5.0% m / m.
  • the amount of functionalized nanoparticles in the composition is in the range of 0.5% m / m to 2.0% m / m.
  • the amount of functionalized nanoparticles in the composition is in the range of 0.6% m / m to 1.0% m / m.
  • the first requirement is to avoid aggregation of the nanoparticles; precisely because of the high area-volume ratio they have, the particles tend to aggregation avoiding the optimal interaction between reinforcement and polymer.
  • the control of nanoparticle aggregation is achieved by stabilizing the particles electrostatically or sterically during the production process.
  • the second requirement is to generate a good dispersion of the nanoparticulate material in the polymer matrix since this leads to an increase in interfacial area, favoring the interaction between the inorganic reinforcing molecules and the organic molecules of the polymer matrix.
  • this aspect lies one of the great challenges of materials science, since generating composite materials with nanoparticles well dispersed in the polymer matrix will depend on chemical factors such as the type of polymer and the type of nanoparticulate reinforcement material, as well as factors physical as the method of inclusion of nanoparticles.
  • the ratio in percentage by mass of the soft segment between 40 and 60% and that of the rigid segment between 60 and 40%.
  • the ratio between the chemical amount of isocyanate groups with respect to the moles of hydroxyl groups is between 0.9 and 1.2, in one embodiment the ratio is between 0.95 and 1.1; in another mode the ratio is between 1.0 and 1.05.
  • the percentage of nanoparticles incorporated into the polymer matrix is between 0.1% m / m and 20.0% m / m.
  • the synthesis process of the composition of the invention can be carried out by the pre-polymer method, where the addition of the nanoparticles is carried out by mixing them with each of the monomers.
  • the synthesis process of the composition of the present invention includes steps a) b) and c).
  • a first material where the functionalized nanoparticles are added in a diisocyanate which can be methylene diphenyl diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), butane diisocyanate (BDI) or mixtures thereof.
  • MDI methylene diphenyl diisocyanate
  • HMDI dicyclohexylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • BDI butane diisocyanate
  • a second material where the functionalized nanoparticles are mixed with a macrodiol which can be polytetramethylene oxide (PTMO), polycaprolactone diol (PCL), hydroxyl polyacrylate polyol; and a third material where the functionalized nanoparticles are added with the chain extender, which can be a low molecular weight diol selected from: ethylene glycol, butane diol (BDO), hexanediol, cyclohexane dimetanol, isosorbide diol.
  • BDO butane diol
  • hexanediol cyclohexane dimetanol
  • isosorbide diol isosorbide diol.
  • a diisocyte is initially melted at a temperature between 50 ° C and 80 ° C or at a temperature between 60 ° C and 70 ° C in an atmosphere with inert gas maintaining constant agitation between 150 and 500 rpm
  • the inert gas is selected from: nitrogen, helium, neon, argon, krypton, xenon, among others.
  • the temperature is increased to a value between 70 ° C and 100 ° C and a macrodiol is added under mechanical stirring at between 100 rpm and 500 rpm or between 200 rpm and 400 rpm until a pre-polymer is obtained.
  • an infrared spectroscopy analysis can be performed.
  • the temperature is increased to a value between 50 ° C and 80 ° C or to a value between 65 ° C and 70 ° C.
  • the reaction After completing the addition of the macrodiol, the reaction is brought to a temperature between 80 ° C and 100 ° C for 60 to 120 minutes with stirring between 200 rpm and 700 rpm or between 400 rpm and 500 rpm. In one embodiment of the process of the invention, once the macrodiol addition is complete, the reaction is brought to a temperature between 100 ° C and 130 ° C. In another embodiment of the process of the invention, the reaction is maintained for 80 to 110 minutes. c) add a chain extender
  • the curing stage of the composite can be carried out by any method known in the art.
  • the composition is placed on a Teflon sheet, where it is cured at a temperature between 100 ° C and 150 ° C or between 110 ° C and 130 ° C under an inert gas atmosphere.
  • the composition of the present invention is characterized as a biocompatible and biostable material.
  • the composition of the present invention is characterized in that it has the following properties (Table 1):
  • natural articular cartilage has a Young's modulus value of 18 MPa, while the present invention achieves values between 40 and 65 MPa.
  • the Surface Free Energy values of the natural cartilage are around 60 mN / m compared to 52 mN / m of the compound of the present invention, indicating a great similarity with the natural cartilage. That compared to the case of ultra high molecular weight polyethylene (used for prostheses) has a Surface Free Energy of 31 mN / m, which represents a value far removed from that measured for natural cartilage.
  • composition of the present invention can be used in the repair or replacement of cardiac muscles, nerves, blood vessels, bones, cartilage, fibrocartilage, meniscus, iliac crest, among others.
  • the present invention will be presented in detail through the following examples, which are provided for illustrative purposes only and not for the purpose of limiting its scope.
  • Example 1 Obtaining functionalized calcium carbonate nanoparticles in the form of dry powder of sodium carbonate and sodium caseinate A solution of 0.1 M sodium carbonate and 2.0% sodium caseinate was prepared. Similarly, a solution of calcium chloride was prepared at a concentration of 0.3 M. The solutions were quickly mixed using a high pressure homogenizer that allows the two solutions to enter the equipment separately to obtain carbonate nanoparticles. of functionalized calcium. The homogenizer working pressure was 28 MPa.
  • the multicore-type calcium carbonate nanoparticles and functionalized with protein obtained had an average size in intensity of 180 nm (FIG. 1), with primary particles between 10 and 30 nm (FIG. 2), according to the dynamic light scattering technique and transmission electron microscopy, respectively, with a 50% calcium carbonate and 50% protein content.
  • the nanoparticle suspension was subsequently filtered and washed with water twice, then dried at 60 ° C and obtained calcium carbonate nanoparticles as a dry powder.
  • Example 2 Obtaining functionalized calcium carbonate nanoparticles in the form of dry powder of calcium carbonate and sodium caseinate
  • Example 3 Obtaining functionalized calcium carbonate nanoparticles in the form of dry powder of calcium carbonate and sodium caseinate
  • Example 4 Obtaining calcium carbonate nanoparticles in the form of dry powder of calcium carbonate, sodium caseinate and quercetin
  • Example 2 Following the procedure of Example 1, functionalized 0.1M calcium carbonate nanoparticles stabilized with 1% sodium caseinate and 0.1% quercetin were obtained, had an average intensity size of 190nm, according to the dynamic light scattering technique , and did not settle for up to three months when measured in an automatic tensiometer equipped with an accessory to determine sedimentation.
  • the encapsulation efficiency of quercetin was 60% measured by the UV-Vis spectrophotometry technique.
  • BDO 1,4-butanediol
  • functionalized calcium functionalized calcium carbonate nanoparticles obtained according to Example 1
  • the microstructure of the composite obtained was observed by scanning electron microscopy (FIG. 3).
  • BDO 1,4-butanediol
  • 2.8 g of calcium carbonate nanoparticles obtained according to Example 1 functionalized with protein and initially dispersed was performed in the BDO.
  • the entire system was maintained at the temperature of 85 ° C for 5 minutes.
  • the compound was emptied into a Teflon dish and cured at 110 ° C for 4 hours in an oven with nitrogen recirculation.
  • the microstructure of the composite was observed by scanning electron microscopy (FIG. 4).
  • Example 7 Mechanical properties of the composite obtained by Example 5 and Example 6
  • the mechanical properties of composites obtained according to Example 5 and Example 6 were determined in an Instron 4202 universal machine using a load of 5 kN and a velocity of 10 mm / min at 25 ° C, using type IV specimens obtained by injection molding. Shore A hardness was measured using a PCT hardness tester at 25 ° C. Finally, the adhesion work was calculated from the surface-free energies obtained by van Oss theory by measuring the contact angles with diiodometry and water in a K12 tensiometer from Krüss. The results are illustrated in Table 2.

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Abstract

La présente invention concerne un composite de polyuréthane thermoplastique qui comprend des nanoparticules fonctionnalisées intégrées dans une matrice de polyuréthane et son procédé de synthèse. Le procédé consiste à faire fondre un diisocyanate dans un réacteur dans une atmosphère de gaz inerte; à ajouter un macrodiol jusqu'à obtenir un pré-polymère et à ajouter un extenseur de chaîne. Les nanoparticules fonctionnalisées peuvent être intégrées dans le diisocyanate, dans le macrodiol ou dans l'extenseur de chaîne.
PCT/IB2018/052283 2017-04-03 2018-04-03 Composite de polyuréthane Ceased WO2018185650A1 (fr)

Applications Claiming Priority (2)

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CONC2017/0003270 2017-04-03
CONC2017/0003270A CO2017003270A1 (es) 2017-04-03 2017-04-03 Composito de poliuretano

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WO2018185650A1 true WO2018185650A1 (fr) 2018-10-11

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Cited By (1)

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CN113956437A (zh) * 2021-10-28 2022-01-21 赛克赛斯生物科技股份有限公司 一种聚氨酯海绵及其制备方法与应用

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US20100112032A1 (en) * 2008-10-30 2010-05-06 Guelcher Scott A Bone/Polyurethane Composites and Methods Thereof
US7776600B2 (en) * 2002-04-18 2010-08-17 Carnegie Mellon University Method of manufacturing hydroxyapatite and uses therefor in delivery of nucleic acids
WO2016057684A1 (fr) * 2014-10-08 2016-04-14 Board Of Trustees Of The University Of Arkansas Régénération osseuse à l'aide de matériaux nanocomposites polymères biodégradables et applications associées

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