CN110396205A - A kind of Pickering High Internal Phase Emulsion, 3D printing porous support materials and preparation method thereof - Google Patents
A kind of Pickering High Internal Phase Emulsion, 3D printing porous support materials and preparation method thereof Download PDFInfo
- Publication number
- CN110396205A CN110396205A CN201910621012.9A CN201910621012A CN110396205A CN 110396205 A CN110396205 A CN 110396205A CN 201910621012 A CN201910621012 A CN 201910621012A CN 110396205 A CN110396205 A CN 110396205A
- Authority
- CN
- China
- Prior art keywords
- high internal
- internal phase
- printing
- porous support
- emulsion
- 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.)
- Granted
Links
Classifications
-
- 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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/24—Collagen
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Biophysics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
Abstract
The present invention relates to a kind of Pickering High Internal Phase Emulsion and 3D printing porous support materials prepared therefrom and preparation methods.The present invention is using nano-hydroapatite particles as emulsion stabilizer, gelatin, collagen, Geniposide are dissolved in the continuous phase that lotion is constituted in deionized water, organic solvent is dispersed phase, through emulsification treatment, cross-linking reaction, form the Pickering High Internal Phase Emulsion of oil-in-water type, so that lotion continuous phase is fixed, after obtaining gel stent finally by 3D printing, solvent volatilization removal dispersed phase and drying and obtain connection, the adjustable porous support materials in aperture between a kind of hole.The present invention is using emulsion template method and combines 3D printing technique, the porous support materials being prepared have many advantages, such as between high porosity, hole that connection, aperture is adjustable, good biocompatibility, nontoxic to organism, have a wide range of applications in biomedical materials field.
Description
Technical field
The invention belongs to biomedical materials fields, and in particular to a kind of Pickering High Internal Phase Emulsion, with its preparation
3D printing porous support materials and preparation method.
Background technique
Porous support materials are a kind of materials with tridimensional network, and a large amount of gaps are contained in inside, are had unique
The characteristics such as bigger serface, low-density, high porosity, these characteristics make porous support materials in field of biomedicine, especially
It is that field of tissue engineering technology has a very wide range of applications.Therefore, it is highly desirable to construct a kind of suitable for the more of tissue repair
Hole timbering material.The ideal porous support materials for tissue repair should have the feature that good mechanically performance
Bear environmental stress, cytotoxic, good biocompatibility can drug loads, sustained release and high porosity are to ensure
The transport of cytotrophy substance and metabolic waste.
Currently, the method for being used to prepare biological stephanoporate bracket material, as phase separation method, foaming, pore-foaming agent method, solvent pour
Casting etc., although porous timbering material can be prepared, poor connectivity, aperture are difficult between these material adjacent holes
Degradation speed is slow in vivo for control and material, significantly limits it in the application of field of tissue engineering technology.Recently, sharp
It is prepared with High Internal Phase Emulsion (high internal phase emulsions, HIPEs) is template with abundant duct knot
The porous support materials of structure become a kind of unique technology of preparing.High Internal Phase Emulsion is that a kind of internal phase volume score is higher than 74%
Lotion is mutually template within, and causing foreign minister's polymerizing curable can be prepared by simple solvent evaporative removal template
With interconnected cellular structure, porosity height and low density macropore timbering material.
Most of traditional stabilizer of High Internal Phase Emulsion is surfactant, and not only dosage is more, malicious during the preparation process
Property it is big, side effect is high, and stability difference and not reproducible utilization, be extremely unfavorable for answering in field of biomedical materials
With.Therefore, draw in recent years in the method that amphiphilic solid nanoparticles and micro particles replace surfactant to carry out stable emulsion
Concern is played, this kind of High Internal Phase Emulsion stable with solids is known as Pickering lotion.Stablize High Internal Phase Emulsion with tradition
Surfactant is compared, and not only dosage is few, can avoid the cytotoxicity of surfactant as emulsion stabilizer for solids, and
And have many advantages, such as irreversible interface particle self assembly performance, stability height and excellent mechanical property, it is highly suitable for
Field of biomedical materials.
Chinese patent CN105968402A, which is disclosed, a kind of to be prepared as template using Pickering High Internal Phase Emulsion
3D porous support materials, although the porous support materials good biocompatibility of this method preparation, mechanical property is good, gathers
Acrylamide itself is difficult to degrade, needed after introducing human body based on the porous support materials of polyacrylamide by second operation come
Removal, will cause the secondary damage of human body, in addition, the product propylene amide after polyacrylamide Partial digestion has toxicity, it is right
The nervous system of organism is harmful.A kind of natural polymer subbase 3D that aperture is controllable is disclosed in Chinese patent CN108201636A
The preparation method of porous compound support frame, using Pickering emulsion template method, using amination gelatin nanoparticle as stabilizer,
Using natural polymer as substrate, it is prepared for a kind of 3D porous compound support frame that aperture is controllable, still, this method needs to combine twice
Go solvent method that amination gelatin nanoparticle is made, the preparation process complex process, the dialysis time period is longer, production cost compared with
It is high；In addition, subsequent processes might have remaining acetone, to life in the preparation process of amination gelatin nanoparticle
Object is harmful.Chinese patent CN107362392A discloses a kind of Nano-hydroxyapatite/Carboxymethyl Chitosan/polylactic
Acetic acid micro-nano hydridization carried stent and its bionics method for preparation, this method is using nanometer hydroxyapatite, carboxymethyl chitosan as water
Phase, as lotion continuous phase；It is oily phase with the dichloromethane solution of polylactic-co-glycolic acid, as emulsion dispersion phase；With penta 2
Aldehyde is the carboxymethyl chitosan in the fixed continuous phase of crosslinking agent, uses icariin for carrier medicament, utilizes high-speed emulsifying machine knot
Bonding solvent evaporation and Freeze Drying Technique prepare Bone Defect Repari three-dimensional bionic hydridization carried stent, although it is mutual that hole is prepared
Connection, the uniform carried stent in aperture, but the crosslinking agent glutaraldehyde wherein used has toxicity, to organism nocuousness.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of Pickering High Internal Phase Emulsions and prepared therefrom
3D printing porous support materials and preparation method, preparation is simple for this, and mild condition is with short production cycle, to organism
Nontoxic, aperture connection and aperture are adjustable inside resulting materials.
In order to solve the above technical problems, the invention is realized by the following technical scheme:
Design a kind of Pickering High Internal Phase Emulsion, including aqueous portion and oil phase part point；The aqueous portion includes water, with
And the following raw material contained in every 3.0mL water: gelatin 0.5-5.0g, collagen 0.4-0.8g, Geniposide 0.01-0.05g and
Hydroxyapatite 0.8-1.5g；The oil phase part point is gathered in oneself including what is contained in methylene chloride and every 10mL methylene chloride
Ester (PCL) 0.06-1.02g.
Preferably, the volume ratio between the aqueous portion and oil phase part point is (2-4): 10, more preferable 3:10.
Preferably, containing polycaprolactone 0.1-0.8g in every 10mL methylene chloride of the oil phase part point.
Preferably, containing following raw material: gelatin 1.0-3.0g, collagen in every 3mL water of the aqueous portion
0.5-0.7g, Geniposide 0.02-0.04g and hydroxyapatite 1.02-1.20g.
Preferably, the hydroxyapatite is nanometer hydroxyapatite.
Design a kind of preparation method of above-mentioned Pickering High Internal Phase Emulsion, comprising the following steps: by the polycaprolactone
It is distributed in methylene chloride, forms oil phase part point after being uniformly dispersed；By the gelatin, collagen, Geniposide and hydroxy-apatite
Stone is distributed in water, forms aqueous portion after being uniformly dispersed；It takes the oil phase part point and aqueous portion mixing to be uniformly dispersed, places
After carrying out cross-linking reaction, oil-in-water Pickering High Internal Phase Emulsion is formed, it is spare.
A kind of 3D printing porous support materials are designed, is prepared, is had through printing by above-mentioned Pickering High Internal Phase Emulsion
Body is beaten according to the model set the following steps are included: the Pickering High Internal Phase Emulsion is imported into 3D printer
Print, obtains 3D printing timbering material, drying process.
Beneficial effects of the present invention:
(1) present invention uses nanometer hydroxyapatite (Ca10(PO4)6(OH)2Abbreviation HAP) stabilization as Pickering lotion
Agent, its chemical composition and structure is similar to the ingredient of the bone of organism, tooth, nontoxic to organism, harmless, without carcinogenic work
With biocompatibility and bioactivity are fine, have good osteoconductive, biocompatibility and biology living in vivo
Property.Moreover, the hydroxyapatite particle of addition can make the mechanical performance of bracket more preferable, because when support force, more
Stress be transferred to from PCL matrix on rigid hydroxyapatite particle so that the mechanical performance of bracket enhances.
(2) mechanical performance of 3D printing porous support materials of the present invention, pore size, pore structure and material can lead to
The concentration of the changes of contents and nano-hydroapatite particles of overregulating polymer PC L is changed, different conducive to meeting
Application demand.The porous support that different PCL contents is prepared it can be seen from attached drawing 1,2,3 and 4, as PCL content mentions
Height, the aperture of porous support and pore throat size reduce, and the pore wall thickness of bracket increases, and pore structure is increasingly more complete.This be because
For the lotion being prepared under higher PCL concentration, the polymer film between adjacent emulsion droplet is thicker, and emulsion viscosity increases, lotion
Stability increase, so that aperture and pore throat size reduce after the solvent evaporates, pore wall thickness increases.
(3) 3D printing porous support materials of the present invention have the biggish pore structure closely arranged, can by electron microscope
To see, the aperture in most of hole falls in 10 μm -20 μm of section, and is connection between Kong Yukong, this kind of structure is in biology
It is very beneficial for sticking and rising in value for cell in vivo, is conducive to the transport of nutriment and metabolic waste, in bio-medical field
There is huge application value.
(4) present invention prepares porous support materials using High Internal Phase Emulsion combination 3D printing technique, can be according to reality
Using needing to prepare the timbering material without shape, size, raw material can be saved in a particular application and realize that personalization is fixed
System.
(5) present invention carries out cross-linking reaction to collagen, gelatin using natural biological crosslinking agent Geniposide, improves material
Mechanical property while, do not generate to the harmful substance of organism.
(6) it after directly preparing Pickering High Internal Phase Emulsion in the present invention, carries out 3D printing and obtains timbering material, operate
Step is simple, and preparation is simple for this, and mild condition is with short production cycle, has biggish application and popularization value.
Detailed description of the invention
Fig. 1 is that the SEM of 1 3D printing porous support materials section of embodiment schemes.
Fig. 2 is that the SEM of 2 3D printing porous support materials section of embodiment schemes.
Fig. 3 is that the SEM of 3 3D printing porous support materials section of embodiment schemes.
Fig. 4 is that the SEM of 4 3D printing porous support materials section of embodiment schemes.
Specific embodiment
Below with reference to embodiment to further detailed description of the present invention, embodiments of the present invention are not limited thereto.
Embodiment 1
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.1 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.08g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 2
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.2 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.08g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 3
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.4 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.08g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 4
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.8 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.08g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 5
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.8 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.02g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 6
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.8 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.14g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
Embodiment 7
A method of 3D printing porous support materials are prepared with Pickering High Internal Phase Emulsion, comprising the following steps:
(1) 0.8 g polycaprolactone (PCL) is weighed to be added in 10 ml methylene chloride, under room temperature after magnetic agitation dispersion 30min,
Form oil phase part point；It is added in addition, weighing 1.5g gelatin, 0.6g collagen, 0.03g Geniposide and 1.20g hydroxyapatite
Into 3 mL deionized waters, after 30 min are dispersed with stirring under room temperature, aqueous portion is formed；Above-mentioned oil phase part point is measured with liquid-transfering gun
It is added in aqueous portion (volume ratio between aqueous portion and oil phase part point is 3:10), shakes 10 with vortex vortex mixer
After placing cross-linking reaction 24 hours, it is spare to form oil-in-water emulsion by min.
(2) oil-in-water emulsion after above-mentioned steps (1) obtain cross-linking reaction 24 hours is imported into the note of 3D printer
In emitter, start to print according to the model of setting, after printing, obtains 3D printing timbering material；Then resulting 3D is beaten
It prints timbering material and carries out freeze-drying process 24 hours to get the porous branch of 3D printing prepared to Pickering High Internal Phase Emulsion
Frame material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be effective substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of Pickering High Internal Phase Emulsion, including aqueous portion and oil phase part point, it is characterised in that: the aqueous portion
Including the following raw material contained in water and every 3.0mL water: gelatin 0.5-5.0g, collagen 0.4-0.8g, Geniposide
0.01-0.05g and hydroxyapatite 0.8-1.5g；The oil phase part point is including in methylene chloride and every 10mL methylene chloride
The polycaprolactone 0.06-1.02g contained.
2. Pickering High Internal Phase Emulsion according to claim 1, it is characterised in that: the aqueous portion and oil phase part
/ volume ratio be (2-4): 10.
3. Pickering High Internal Phase Emulsion according to claim 2, it is characterised in that: the aqueous portion and oil phase part
/ volume ratio be 3:10.
4. Pickering High Internal Phase Emulsion according to claim 1, it is characterised in that: every 10mL of the oil phase part point
Contain polycaprolactone 0.1-0.8g in methylene chloride.
5. Pickering High Internal Phase Emulsion according to claim 1, it is characterised in that: every 3mL water of the aqueous portion
In contain following raw material: gelatin 1.0-3.0g, collagen 0.5-0.7g, Geniposide 0.02-0.04g and hydroxyapatite
1.02-1.20g。
6. Pickering High Internal Phase Emulsion according to claim 1, it is characterised in that: the hydroxyapatite is nanometer
Hydroxyapatite.
7. the preparation method of any one of the claim 1-6 Pickering High Internal Phase Emulsion, which is characterized in that including following
Step: the polycaprolactone is distributed in methylene chloride, and oil phase part point is formed after being uniformly dispersed；By the gelatin, collagen egg
White, Geniposide and hydroxyapatite are distributed in water, form aqueous portion after being uniformly dispersed；Take the oil phase part point and water phase portion
Divide mixing to be uniformly dispersed, place after carrying out cross-linking reaction, forms oil-in-water Pickering High Internal Phase Emulsion.
8. a kind of 3D printing porous support materials, by any one of the claim 1-6 Pickering High Internal Phase Emulsion through printing
It is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910621012.9A CN110396205B (en) | 2019-07-10 | 2019-07-10 | Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910621012.9A CN110396205B (en) | 2019-07-10 | 2019-07-10 | Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110396205A true CN110396205A (en) | 2019-11-01 |
| CN110396205B CN110396205B (en) | 2020-07-31 |
Family
ID=68324357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910621012.9A Active CN110396205B (en) | 2019-07-10 | 2019-07-10 | Pickering high internal phase emulsion, 3D printing porous scaffold material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110396205B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110810537A (en) * | 2019-11-27 | 2020-02-21 | 江南大学 | Method for preparing high internal phase emulsion by using emulsified edible oil |
| CN111760074A (en) * | 2020-07-17 | 2020-10-13 | 华南农业大学 | Preparation method of lignin-chitosan porous scaffold material |
| CN113306271A (en) * | 2021-06-22 | 2021-08-27 | 中国农业大学 | Medium-high internal phase emulsion material for 3D printing and application thereof |
| CN114712566A (en) * | 2022-04-22 | 2022-07-08 | 华南理工大学 | PCL/GelMA biological porous scaffold based on Pickering emulsion and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539929A (en) * | 2013-10-10 | 2014-01-29 | 华东理工大学 | Method for preparing polymer porous material by using diene synthetic reaction in high internal phase emulsion |
| CN103834057A (en) * | 2014-03-05 | 2014-06-04 | 四川大学 | Gelatin porous material prepared by using high inner phase emulsion as template and preparation method of gelatin porous material |
| CN103990182A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Three-dimensional scaffold material for bone tissue repair and preparation method thereof |
| CN105968402A (en) * | 2016-06-07 | 2016-09-28 | 成都大学 | Three-dimensional porous scaffold material prepared by taking Pickering high internal phase emulsion as template |
| CN107011641A (en) * | 2017-05-11 | 2017-08-04 | 广州飞胜高分子材料有限公司 | A kind of low temperature prop composite and its processing method for 3D printing |
| CN107115570A (en) * | 2017-03-30 | 2017-09-01 | 华南理工大学 | A kind of nano combined biological support of multistage controllable through-hole structure and preparation method and application |
| CN107362392A (en) * | 2017-07-18 | 2017-11-21 | 福州大学 | A kind of Nano-hydroxyapatite/Carboxymethyl Chitosan/polylactic-co-glycolic acid micro-nano hydridization carried stent and its bionics method for preparation |
| CN109432505A (en) * | 2018-11-02 | 2019-03-08 | 华南农业大学 | A kind of porous grade composite medical gel stent and preparation method thereof of 3D printing building |
| CN109701084A (en) * | 2019-02-22 | 2019-05-03 | 华南农业大学 | A kind of compound multiple dimensioned hole biological support of shape memory type active nanoparticles/biodegradable polyesters and preparation method thereof |
-
2019
- 2019-07-10 CN CN201910621012.9A patent/CN110396205B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539929A (en) * | 2013-10-10 | 2014-01-29 | 华东理工大学 | Method for preparing polymer porous material by using diene synthetic reaction in high internal phase emulsion |
| CN103834057A (en) * | 2014-03-05 | 2014-06-04 | 四川大学 | Gelatin porous material prepared by using high inner phase emulsion as template and preparation method of gelatin porous material |
| CN103990182A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Three-dimensional scaffold material for bone tissue repair and preparation method thereof |
| CN105968402A (en) * | 2016-06-07 | 2016-09-28 | 成都大学 | Three-dimensional porous scaffold material prepared by taking Pickering high internal phase emulsion as template |
| CN107115570A (en) * | 2017-03-30 | 2017-09-01 | 华南理工大学 | A kind of nano combined biological support of multistage controllable through-hole structure and preparation method and application |
| CN107011641A (en) * | 2017-05-11 | 2017-08-04 | 广州飞胜高分子材料有限公司 | A kind of low temperature prop composite and its processing method for 3D printing |
| CN107362392A (en) * | 2017-07-18 | 2017-11-21 | 福州大学 | A kind of Nano-hydroxyapatite/Carboxymethyl Chitosan/polylactic-co-glycolic acid micro-nano hydridization carried stent and its bionics method for preparation |
| CN109432505A (en) * | 2018-11-02 | 2019-03-08 | 华南农业大学 | A kind of porous grade composite medical gel stent and preparation method thereof of 3D printing building |
| CN109701084A (en) * | 2019-02-22 | 2019-05-03 | 华南农业大学 | A kind of compound multiple dimensioned hole biological support of shape memory type active nanoparticles/biodegradable polyesters and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YANG HUA等: ""Facile preparation of bioactive nanoparticle/poly(e-caprolactone) hierarchical porous scaffolds via 3D printing of high internal phase Pickering emulsions"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| YANG HU等: ""Facile preparation of biocompatible poly(L-lactic acid)-modified halloysite nanotubes/poly(e-caprolactone) porous scaffolds by solvent evaporation of Pickering emulsion templates"", 《J. MATER. SCI.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110810537A (en) * | 2019-11-27 | 2020-02-21 | 江南大学 | Method for preparing high internal phase emulsion by using emulsified edible oil |
| CN111760074A (en) * | 2020-07-17 | 2020-10-13 | 华南农业大学 | Preparation method of lignin-chitosan porous scaffold material |
| CN113306271A (en) * | 2021-06-22 | 2021-08-27 | 中国农业大学 | Medium-high internal phase emulsion material for 3D printing and application thereof |
| CN114712566A (en) * | 2022-04-22 | 2022-07-08 | 华南理工大学 | PCL/GelMA biological porous scaffold based on Pickering emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110396205B (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110396205A (en) | A kind of Pickering High Internal Phase Emulsion, 3D printing porous support materials and preparation method thereof | |
| Wei et al. | A 3D-printable TEMPO-oxidized bacterial cellulose/alginate hydrogel with enhanced stability via nanoclay incorporation | |
| Lu et al. | Techniques for fabrication and construction of three-dimensional scaffolds for tissue engineering | |
| Bhattacharyya et al. | Nano-biomaterials for designing functional bioinks towards complex tissue and organ regeneration in 3D bioprinting | |
| Piras et al. | Nanocellulosic materials as bioinks for 3D bioprinting | |
| Kim et al. | Mechanically-reinforced electrospun composite silk fibroin nanofibers containing hydroxyapatite nanoparticles | |
| CN104623737B (en) | A kind of personalized tissue recovery support of achievable pulsed sustained release and preparation method thereof | |
| Mostafavi et al. | Colloidal multiscale porous adhesive (bio) inks facilitate scaffold integration | |
| WO2019139381A1 (en) | Collagen peptide-containing polycaprolactone microsphere filler and preparation method therefor | |
| CN104611783B (en) | A kind of method of electrospun nanofibers and the nanofiber obtained thereof and the application of nanofiber | |
| Taneja et al. | Hydrogel based 3D printing: Bio ink for tissue engineering | |
| Zhang et al. | Porous nanofibrous scaffold incorporated with S1P loaded mesoporous silica nanoparticles and BMP-2 encapsulated PLGA microspheres for enhancing angiogenesis and osteogenesis | |
| CN108144127B (en) | Fibrin gel/polylactic acid-glycolic acid microsphere scaffold and preparation method and application thereof | |
| Wang et al. | Electrosprayed soft capsules of millimeter size for specifically delivering fish oil/nutrients to the stomach and intestines | |
| CN107115570A (en) | A kind of nano combined biological support of multistage controllable through-hole structure and preparation method and application | |
| CN109701461A (en) | A kind of preparation and its application of the calcium carbonate based on PEG/Dex aqueous two-phase/calcium alginate compounded micro-capsule | |
| Tian et al. | Fabrication of nanocomposite bioelastomer porous scaffold based on chitin nanocrystal supported emulsion-freeze-casting | |
| Abere et al. | Derivation of composites of chitosan-nanoparticles from crustaceans source for nanomedicine: A mini review | |
| Liu et al. | Pickering multiphase materials using plant‐based cellulosic micro/nanoparticles | |
| CN103834057A (en) | Gelatin porous material prepared by using high inner phase emulsion as template and preparation method of gelatin porous material | |
| AU2003245185A1 (en) | Porous gelatin material, gelatin structures, methods for preparation of the same and uses thereof | |
| Rogers et al. | The effects of fabrication strategies on 3D scaffold morphology, porosity, and vascular smooth muscle cell response | |
| CN111249524B (en) | High-porosity polycaprolactone porous microsphere scaffold for bone tissue regeneration and preparation method thereof | |
| CN105412984A (en) | Albumen-carrying 3D tissue engineering scaffold and preparation method thereof | |
| Xuan et al. | Microgels for Cell Delivery in Tissue Engineering and Regenerative Medicine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |