CN103073739B - Microsphere tissue engineering scaffold used in beauty filling, and preparation method of microsphere tissue engineering scaffold - Google Patents
Microsphere tissue engineering scaffold used in beauty filling, and preparation method of microsphere tissue engineering scaffold Download PDFInfo
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- CN103073739B CN103073739B CN201310008187.5A CN201310008187A CN103073739B CN 103073739 B CN103073739 B CN 103073739B CN 201310008187 A CN201310008187 A CN 201310008187A CN 103073739 B CN103073739 B CN 103073739B
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
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- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- 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
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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/34—Materials or treatment for tissue regeneration for soft tissue reconstruction
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
Abstract
The invention relates to a microsphere tissue engineering scaffold used in beauty filling, and a preparation method of the microsphere tissue engineering scaffold, and belongs to the field of tissue engineering scaffold materials. The method comprises the following processing steps: (1) preparing polyurethane microspheres: feeding isocyanate monomers and oligomer divalent alcohol into a reaction vessel, carrying out 1.5 to 3.5 h's reaction under 70 to 90 DEG C, feeding hydrophilic chain extender, viscosity modifier and catalyst, heating till the temperature is 45 to 55 DEG C, and carrying out reaction for 3 to 4 h; feeding the reaction liquid into salt forming agent solution in a high-speed stirring manner, shearing and emulsifying for 1 to 3.5 h, cleaning the microspheres with deionized water, and carrying out vacuum freeze drying; (2) preparing a polyurethane microsphere scaffold: dispersing the polyurethane microspheres in NaCl solution to form uniform emulsion, pouring the emulsion into a die, and carrying out freeze drying under -50 to -20 DEG C; and (3), conducting mineralization treatment on the surface of the scaffold: fixing the polyurethane microsphere scaffold in calcium-phosphorus supersaturated solution containing urease in a slowly stirring manner, carrying out mineralization treatment for 2 to 24 h, cleaning the scaffold for 2 to 24 h with deionized water, and carrying out freeze drying.
Description
Technical field
The invention belongs to tissue engineering bracket material field, particularly a kind of for the microsphere tissue engineering scaffold of filling and preparation method thereof of improving looks.
Background technology
In recent years, micro-sphere material is more for the injection packing material of improving looks, and during due to operation, without otch, simple to operate, patient suffering is little, meets modern and require the demand of Wicresoft's shaping, so micro-sphere material is just extensively welcome by patient once application.But the mobility of micro-sphere material is larger, can not according to preoperative expectation be confined to like that the position that needs, and may and body between there is mutually parcel, form granulation tissue; While developing complications after surgery, take out prosthese very difficult, thereby its application is restricted.At present for the micro-sphere material of beauty and shaping, comprise silica gel microball, agar dextran microspheres, polyvinyl alcohol porous microsphere etc., but there is short-term or long-term inflammatory reaction in these materials, as local low grade inflammation reaction (postoperative 2 weeks), wound repair reaction (postoperative 4 weeks) and chronic foreign body reaction (postoperative 8 months), and mobility is larger, fixing effect need to improve, and therefore in the urgent need to the performance to micro-sphere material, improves.
Polyurethane material is since nineteen thirty-seven comes out, and because it has good anticoagulation function, hypotoxicity has good biocompatibility in clinical application, undistorted effect, and without anaphylaxis, thereby increasingly extensive in application medically.At present aspect medical science, to apply more be polyurethane elastomer to polyurethane material, mainly for the preparation of medical treatment and healthcare product, the good microporous polyurethane foams of elasticity are widely used aspect beauty and shaping, as urethane artificial skin, urethane prosthese, jaw face repair materials etc.; The directions such as the domestic and international immobilization that mainly concentrates on fractionation by adsorption, pharmaceutical carrier and enzyme and cell about polyaminoester microball in the research aspect biology at present.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of microsphere tissue engineering scaffold and preparation method thereof for improving looks and filling is provided, support biocompatibility prepared by described method is good, and fixed effect improves, and technological operation is simple.
Microsphere tissue engineering scaffold preparation method for improving looks and filling of the present invention, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
Take isocyanate-monomer and oligopolymer dibasic alcohol as raw material, by the mol ratio of the hydroxyl in the isocyanate groups in isocyanate-monomer and oligopolymer dibasic alcohol, be 1.3 ~ 2.2:1 metering isocyanate-monomer and oligopolymer dibasic alcohol, isocyanate-monomer and oligopolymer dibasic alcohol are added in reaction vessel, under agitation in normal pressure, 70 ℃ ~ 90 ℃, react, the reaction times is 1.5h ~ 3.5h;
2. chain extending reaction
Under agitation hydrophilic chain extender is added in the reaction solution that 1. step form, and its temperature is down to room temperature, then add viscosity modifier and catalyzer, after stirring, be warming up to 45 ℃ ~ 55 ℃, keep aforementioned stirring velocity under this temperature and normal pressure, to react 3h ~ 4 h
The add-on of described hydrophilic chain extender is 1. in described isocyanate-monomer 0.1 ~ 0.3 times of isocyanate groups molar weight of step, the add-on of described viscosity modifier is 1. 0.5 ~ 5 times of described isocyanate-monomer molar weight of step, the add-on of described catalyzer be step 1. described isocyanate-monomer quality 0.01% ~ 1%;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in the salt forming agent solution of room temperature that the reaction solution under high-speed stirring, 2. step being formed adds temperature, and keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 1h ~ 3.5h, continue after by the centrifugation of described microballoon emulsion, and remove remaining viscosity modifier and the lyophilize of small particle size microballoon final vacuum with washed with de-ionized water centrifugation thus obtained microsphere, obtain polyaminoester microball;
Described stirring velocity is 1500rpm ~ 3000rpm, and the concentration of described salt forming agent solution is 0.35 ~ 0.8mol/L, in described salt forming agent solution the molar weight of salt forming agent at least with step 2. the molar weight of described hydrophilic chain extender equate;
(2) preparation of polyaminoester microball support
Polyaminoester microball prepared by step (1) is scattered in the NaCl aqueous solution that concentration is 0.1mol/L ~ 0.5mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL ~ 5mL, described emulsion is injected in mould, in-50 ℃ ~-20 ℃ lyophilizes, form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated aqueous solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated aqueous solution of urease, the described calcium phosphorus supersaturated aqueous solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then during the polyaminoester microball support of being prepared by step (2) under slow stirring is fixed on containing the calcium phosphorus supersaturated aqueous solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 2h ~ 24h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 12h ~ 24h lyophilize,
In described calcium phosphorus supersaturated aqueous solution, the concentration of urea is 0.1mol/L, the concentration of Sodium phosphate dibasic is 5mmol/L, the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 5 ~ 6, described stirring velocity is 50rpm ~ 100rpm, and the amount of the described calcium phosphorus supersaturated aqueous solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
In aforesaid method, the shape of polyaminoester microball support needs design according to beauty treatment, and described mould is made according to designed support shape.
In aforesaid method, the mineralising treatment time is selected the requirement of polyaminoester microball support mineralized layer thickness according to beauty treatment position, and required mineralized layer is thicker, and the mineralising treatment time is longer.
In aforesaid method, also can add small molecule chain extender during chain extending reaction, the add-on of described small molecule chain extender is to be not more than 1/4 of isocyanate groups molar weight in isocyanate-monomer.
In aforesaid method, small molecule chain extender is ethylene glycol, BDO, glycol ether, the one in methyl propanediol.
In aforesaid method, described oligopolymer dibasic alcohol is polyester type dibasic alcohol or polyether-type dibasic alcohol.
In aforesaid method, polyester type dibasic alcohol is that hexanodioic acid is the one in polyester glycol, aliphatic polyester binary alcohol, polycaprolactone glycol, polycarbonate diol, and polyether-type dibasic alcohol is the one in polyoxypropyleneglycol, PTMG, quadrol polyether Glycols.
In aforesaid method, isocyanate-monomer is the one in tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate polycondensation derivative.
In aforesaid method, described viscosity modifier is acetone or ethyl acetate.
In aforesaid method, described hydrophilic chain extender is 2,2-dimethylol propionic acid, the one in dihydroxyl half ester, trolamine, diethanolamine; Described catalyzer is tertiary amine catalyst or organo-metallic catalyst; Described tertiary amine catalyst is the one in triethylenediamine, two (dimethylamino ethyl) ether, ring ethyl-methyl tertiary amine, dimethylethanolamine, triethylamine; Described organo-metallic catalyst is the one in stannous octoate, dibutyltin diacetate, dibutyl tin laurate, tetrabutyl titanate.
In aforesaid method, salt forming agent solution is the one in triethylamine aqueous solution, aqueous hydrochloric acid, aqueous acetic acid, ammoniacal liquor, the propylene oxide aqueous solution.
The present invention has following beneficial effect:
1, the microsphere tissue engineering scaffold for improving looks and filling of the present invention, mineralising processing has been passed through on its surface, has deposited mineralising hydroxyapatite coating layer, has improved biological activity and the cellular affinity of this material.
2, the microsphere tissue engineering scaffold for improving looks and filling of the present invention, the mineralising hydroxyapatite coating layer of its surface deposition can effectively prevent the loss of microballoon, after implanting, microsphere support can be limited in to specific position, thereby reach good fixed effect, avoid the formation of granulation tissue and serious inflammatory reaction.
3, the microsphere tissue engineering scaffold for improving looks and filling of the present invention, the thickness of shape, size and the mineralized layer of support etc. can design according to different application demands, applied widely.
4, the microsphere tissue engineering scaffold for improving looks and filling of the present invention, the wide material sources of its raw materials, and can, by regulating wherein as material composition and/or the ratio of the urethane of matrix and select different hydroxyl donor compositions, reach the object that regulates timbering material degradation property.
5, the microsphere tissue engineering scaffold for improving looks and filling of the present invention, its mechanical property can change by polyethers and/or polyester in adjusting timbering material soft section and the ratio of the hard section of isocyanate prepolymer composition, thereby makes its mechanical property adapt to the filling needs of different tissues.
6, of the present invention have larger specific surface area for the microsphere tissue engineering scaffold of filling of improving looks, and have slow-release function, can directly to inflammation, ulcer etc., carry out personalized treatment by discharging different medicines.
7, in the method for the invention in and emulsifying step adopt self-emulsifying technical scheme, thereby greatly reduced the bio-toxicity of microballoon, the extremely low even nontoxicity of prepared polyaminoester microball toxicity.
8, the production technique of the method for the invention is simple, and starting material wide material sources are easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of microsphere tissue engineering scaffold surface mineralising processing of filling for improving looks of the present invention;
Fig. 2 is a kind of photomacrograph of microsphere tissue engineering scaffold for improving looks and filling prepared by the method for the invention;
Fig. 3 be the method for the invention prepare for improve looks fill microsphere tissue engineering scaffold mineralising before and after infrared spectrum, wherein a is mineralising infrared spectrum before treatment, b is mineralising infrared spectrum after treatment;
Fig. 4 is the stereoscan photograph for improving looks after the microsphere tissue engineering scaffold mineralising of filling prepared by the method for the invention, and magnification is 400 times.
Embodiment
Below by embodiment, the microsphere tissue engineering scaffold preparation method who fills for improving looks of the present invention and prepared microsphere tissue engineering scaffold are described further.
In following embodiment, the principle of the microsphere tissue engineering scaffold surface mineralising processing of filling for improving looks as shown in Figure 1, prepared is truncated cone-shaped for the microsphere tissue engineering scaffold of filling of improving looks, as shown in Figure 2, as shown in Figure 4, the infrared spectrum before and after mineralising as shown in Figure 3 for stereoscan photograph after microsphere tissue engineering scaffold mineralising.
Embodiment 1
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.27mol isoflurane chalcone diisocyanate and 0.15mol poly-epsilon-caprolactone glycol 2000 are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 1000r/min, under normal pressure, 75 ℃ and nitrogen protection, react 2.5h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 1000r/min, 0.07mol hydrophilic chain extender trolamine is added in the reaction solution that 1. step form, and its temperature is down to room temperature, then add 0.01% catalyzer dibutyltin diacetate of the acetone of 4 times of isoflurane chalcone diisocyanate molar weight and isoflurane chalcone diisocyanate quality, after stirring, be warming up to 50 ℃, under this temperature and normal pressure, react 3.5h, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration aqueous acetic acid that is 0.8mol/L that the reaction solution under the stirring velocity of 2000 r/min, 2. step being formed adds 100mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 2h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining acetone and small particle size microballoon lyophilize at 130Pa ,-50 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution that concentration is 0.1mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 5mL, described emulsion is injected in mould, in 130pa ,-40 ℃ of lyophilizes, can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 50rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 6h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 12h lyophilize,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 6, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.26mol diphenylmethanediisocyanate and 0.19mol poly-epsilon-caprolactone glycol 1000 are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 1000r/min, under normal pressure, 75 ℃ and nitrogen protection, react 3.5h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 1000r/min, by 0.02mol small molecule chain extender ethylene glycol and 0.03mol hydrophilic chain extender 2,2-dimethylol propionic acid adds in the reaction solution that 1. step form, and its temperature is down to room temperature, then add 1% catalyzer dimethylethanolamine of the ethyl acetate of 1.1 times of diphenylmethanediisocyanate molar weight and diphenylmethanediisocyanate quality, after stirring, be warming up to 50 ℃, keep aforementioned stirring speed to react 4h under this temperature and normal pressure, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration triethylamine aqueous solution that is 0.35mol/L that the reaction solution under the stirring velocity of 3000r/min, 2. step being formed adds 100mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 2.5h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining ethyl acetate and small particle size microballoon lyophilize at 130Pa ,-50 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution that concentration is 0.2mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 5mL, described emulsion is injected in mould, and at 130Pa ,-20 ℃, lyophilize can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 50rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 24h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 16h lyophilize,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 6, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.27mol isoflurane chalcone diisocyanate and 0.15mol poly-epsilon-caprolactone glycol 2000 are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 900r/min, under normal pressure, 70 ℃ and nitrogen protection, react 3h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 900r/min, by 0.07mol hydrophilic chain extender 2,2-dimethylol propionic acid adds in the reaction solution that 1. step form, and its temperature is down to room temperature, then 0.02% the catalyzer dibutyltin diacetate that adds the acetone of 3 times of isoflurane chalcone diisocyanate molar weight and isoflurane chalcone diisocyanate quality, after stirring, is warming up to 50 ℃, keep aforementioned stirring speed to react 3.5h under this temperature and normal pressure, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration ammonia soln that is 0.8mol/L that the reaction solution under the stirring velocity of 3000r/min, 2. step being formed adds 100mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 3.5h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining acetone and small particle size microballoon lyophilize at 130Pa ,-50 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution that concentration is 0.15mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL, described emulsion is injected in mould, in 130Pa ,-40 ℃ of lyophilizes, can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 100rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 24h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 24h lyophilize,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 5, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
Embodiment 4
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.33mol hexamethylene diisocyanate and 0.15mol polycarbonate diol are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 1000r/min, under normal pressure, 90 ℃ and nitrogen protection, react 1.5h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 1000r/min, by 0.05mol small molecule chain extender ethylene glycol and 0.1mol hydrophilic chain extender 2,2-dimethylol propionic acid adds in the reaction solution that 1. step form, and its temperature is down to room temperature, then add 0.01% catalyzer dibutyl tin laurate of the acetone of 5 times of hexamethylene diisocyanate molar weight and hexamethylene diisocyanate quality, after stirring, be warming up to 45 ℃, keep aforementioned stirring speed to react 4h under this temperature and normal pressure, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration ammonia soln that is 0.6mol/L that the reaction solution under the stirring velocity of 2000r/min, 2. step being formed adds 200mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 1h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining acetone and small particle size microballoon lyophilize at 130Pa ,-20 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution of 0.5mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL, described emulsion is injected in mould, in 130Pa ,-20 ℃ of lyophilizes, can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 50rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 2h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 12h lyophilize,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 6, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
Embodiment 5
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.27mol isoflurane chalcone diisocyanate, 0.15mol PTMG 1000 are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 800r/min, under normal pressure, 75 ℃ and nitrogen protection, react 2h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 800r/min, by 0.04mol small molecule chain extender 1,4-butyleneglycol and 0.05mol hydrophilic chain extender 2,2-dimethylol propionic acid adds in the reaction solution that 1. step form, and its temperature is down to room temperature, then add 0.01% the sub-tin of octoate catalyst of the acetone of 0.5 times of isoflurane chalcone diisocyanate molar weight and isoflurane chalcone diisocyanate quality, after stirring, be warming up to 55 ℃, keep aforementioned stirring velocity to react 3h under this temperature and normal pressure, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration triethylamine aqueous solution that is 0.6mol/L that the reaction solution under the stirring velocity of 1500r/min, 2. step being formed adds 100mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 2h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining acetone and small particle size microballoon lyophilize at 130Pa ,-50 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution that concentration is 0.1mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL, described emulsion is injected in mould, and at 130Pa ,-50 ℃, lyophilize can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 100rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 2h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 24h and at 130Pa, lyophilize at-50 ℃,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 5, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
Embodiment 6
The microsphere tissue engineering scaffold that the present embodiment adopts the method for the invention to fill for the preparation of beauty treatment, processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
0.27mol isoflurane chalcone diisocyanate, 0.15mol PTMG 1000 are added in the four-hole three-necked bottle that is provided with agitator, thermometer, prolong, nitrogen discrepancy pipe; under the stirring velocity of 800r/min, under normal pressure, 75 ℃ and nitrogen protection, react 2h, in reaction process to logical water of condensation in prolong;
2. chain extending reaction
Under the stirring velocity of 800r/min, by 0.04mol small molecule chain extender 1,4-butyleneglycol and 0.05mol hydrophilic chain extender trolamine add in the reaction solution that 1. step form, and its temperature is down to room temperature, then add 0.01% the sub-tin of octoate catalyst of the acetone of 0.5 times of isoflurane chalcone diisocyanate molar weight and isoflurane chalcone diisocyanate quality, after stirring, be warming up to 55 ℃, keep aforementioned stirring velocity to react 3h under this temperature and normal pressure, in reaction process, in prolong, lead to water of condensation;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in room temperature, the concentration aqueous acetic acid that is 0.6mol/L that the reaction solution under the stirring velocity of 1500r/min, 2. step being formed adds 100mL temperature, keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 2h, continue after by the centrifugation of described microballoon emulsion, and remove after remaining acetone and small particle size microballoon lyophilize at 130Pa ,-50 ℃ with deionized water centrifuge washing microballoon, obtain polyaminoester microball;
(2) preparation of polyaminoester microball support
The polyaminoester microball of preparation in step (1) is scattered in the NaCl aqueous solution that concentration is 0.1mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL, described emulsion is injected in mould, and at 130Pa ,-50 ℃, lyophilize can form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated solution of urease, the described calcium phosphorus supersaturated solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then the polyaminoester microball support of being prepared by step (2) under the stirring velocity of 100rpm be fixed on containing in the calcium phosphorus supersaturated solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 2h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 24h and at 130Pa, lyophilize at-50 ℃,
In described calcium phosphorus supersaturated solution, the concentration of urea is 0.1mol/L, and the concentration of Sodium phosphate dibasic is 5mmol/L, and the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 5, and the amount of the described calcium phosphorus supersaturated solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
Claims (10)
1. the microsphere tissue engineering scaffold preparation method for improving looks and filling, is characterized in that processing step is as follows successively:
(1) preparation of polyaminoester microball
1. prepolymerization reaction
Take isocyanate-monomer and oligopolymer dibasic alcohol as raw material, by the mol ratio of the hydroxyl in the isocyanate groups in isocyanate-monomer and oligopolymer dibasic alcohol, be 1.3～2.2:1 metering isocyanate-monomer and oligopolymer dibasic alcohol, isocyanate-monomer and oligopolymer dibasic alcohol are added in reaction vessel, under agitation in normal pressure, 70 ℃～90 ℃, react, the reaction times is 1.5h～3.5h;
2. chain extending reaction
Under agitation hydrophilic chain extender is added in the reaction solution that 1. step form, and its temperature is down to room temperature, then add viscosity modifier and catalyzer, after stirring, be warming up to 45 ℃～55 ℃, keep aforementioned stirring velocity to react 3h～4h under this temperature and normal pressure
The add-on of described hydrophilic chain extender is 1. in described isocyanate-monomer 0.1～0.3 times of isocyanate groups molar weight of step, the add-on of described viscosity modifier is 1. 0.5～5 times of described isocyanate-monomer molar weight of step, the add-on of described catalyzer be step 1. described isocyanate-monomer quality 0.01%～1%;
3. in and emulsion reaction
The temperature of the reaction solution that 2. step is formed is down to room temperature, then it is in the salt forming agent solution of room temperature that the reaction solution under high-speed stirring, 2. step being formed adds temperature, and keep aforementioned stirring velocity to carry out emulsification pretreatment to obtain microballoon emulsion, the time of emulsification pretreatment is 1h～3.5h, continue after by the centrifugation of described microballoon emulsion, and remove remaining viscosity modifier and the lyophilize of small particle size microballoon final vacuum with washed with de-ionized water centrifugation thus obtained microsphere, obtain polyaminoester microball;
Described stirring velocity is 1500rpm～3000rpm, and the concentration of described salt forming agent solution is 0.35～0.8mol/L, in described salt forming agent solution the molar weight of salt forming agent at least with step 2. the molar weight of described hydrophilic chain extender equate;
(2) preparation of polyaminoester microball support
Polyaminoester microball prepared by step (1) is scattered in the NaCl aqueous solution that concentration is 0.1mol/L～0.5mol/L, form the emulsion of homogeneous, the amount of the NaCl aqueous solution is every milligram of polyaminoester microball 1mL～5mL, described emulsion is injected in mould, in-50 ℃～-20 ℃ lyophilizes, form polyaminoester microball support;
(3) the mineralising processing of polyaminoester microball rack surface
In 1mL calcium phosphorus supersaturated aqueous solution, add the ratio preparation of 0.1 unit urease containing the calcium phosphorus supersaturated aqueous solution of urease, the described calcium phosphorus supersaturated aqueous solution containing urease is added in container and by its temperature and is controlled at 37 ℃, then during the polyaminoester microball support of being prepared by step (2) under slow stirring is fixed on containing the calcium phosphorus supersaturated aqueous solution of urease and the temperature that maintains solution at 37 ℃, carry out mineralising processing, the mineralising treatment time is 2h～24h, after the mineralising treatment time expires, taking-up is through the polyaminoester microball support of mineralising processing, with deionized water rinsing 12h～24h lyophilize,
In described calcium phosphorus supersaturated aqueous solution, the concentration of urea is 0.1mol/L, the concentration of Sodium phosphate dibasic is 5mmol/L, the concentration of calcium chloride is 12.5mmol/L, pH value is controlled at 5～6, described stirring velocity is 50rpm～100rpm, and the amount of the described calcium phosphorus supersaturated aqueous solution containing urease is can keep its liquid level to be limited higher than polyaminoester microball rack surface.
According to claim 1 for improve looks fill microsphere tissue engineering scaffold preparation method, while it is characterized in that chain extending reaction, also can add small molecule chain extender, the add-on of described small molecule chain extender is to be not more than step 1. in described isocyanate-monomer 1/4 of isocyanate groups molar weight.
3. according to claim 2 for the microsphere tissue engineering scaffold preparation method of the filling of improving looks, it is characterized in that small molecule chain extender is ethylene glycol, BDO, glycol ether, the one in methyl propanediol.
4. according to the microsphere tissue engineering scaffold preparation method for improving looks and filling described in arbitrary claim in claims 1 to 3, it is characterized in that described oligopolymer dibasic alcohol is polyester type dibasic alcohol or polyether-type dibasic alcohol.
According to claim 4 for improve looks fill microsphere tissue engineering scaffold preparation method, it is characterized in that polyester type dibasic alcohol is that hexanodioic acid is the one in polyester glycol, aliphatic polyester binary alcohol, polycaprolactone glycol, polycarbonate diol, polyether-type dibasic alcohol is the one in polyoxypropyleneglycol, PTMG.
6. according to the microsphere tissue engineering scaffold preparation method for improving looks and filling described in arbitrary claim in claims 1 to 3, it is characterized in that isocyanate-monomer is the one in tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate polycondensation derivative.
7. according to the microsphere tissue engineering scaffold preparation method for improving looks and filling described in arbitrary claim in claims 1 to 3, it is characterized in that described viscosity modifier is acetone or ethyl acetate.
8. according to the microsphere tissue engineering scaffold preparation method for improving looks and filling described in arbitrary claim in claims 1 to 3, it is characterized in that described hydrophilic chain extender is 2,2-dimethylol propionic acid, the one in dihydroxyl half ester, trolamine, diethanolamine; Described catalyzer is tertiary amine catalyst or organo-metallic catalyst; Described tertiary amine catalyst is the one in triethylenediamine, two (dimethylamino ethyl) ether, dimethylethanolamine, triethylamine; Described organo-metallic catalyst is the one in stannous octoate, dibutyltin diacetate, dibutyl tin laurate, tetrabutyl titanate.
9. according to the microsphere tissue engineering scaffold preparation method for improving looks and filling described in arbitrary claim in claims 1 to 3, it is characterized in that salt forming agent solution is the one in triethylamine aqueous solution, aqueous hydrochloric acid, aqueous acetic acid, ammoniacal liquor, the propylene oxide aqueous solution.
10. the microsphere tissue engineering scaffold for improving looks and filling that in claim 1 to 9, described in arbitrary claim prepared by method.
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| CN201310008187.5A CN103073739B (en) | 2013-01-09 | 2013-01-09 | Microsphere tissue engineering scaffold used in beauty filling, and preparation method of microsphere tissue engineering scaffold |
| PCT/CN2013/079119 WO2014107948A1 (en) | 2013-01-09 | 2013-07-10 | Microsphere tissue engineering scaffold for beauty filling and preparation method thereof |
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| CN103073739B (en) * | 2013-01-09 | 2014-05-07 | 四川大学 | Microsphere tissue engineering scaffold used in beauty filling, and preparation method of microsphere tissue engineering scaffold |
| CN108148172B (en) * | 2017-01-06 | 2019-05-03 | 四川大学华西医院 | A kind of polyurethane microcarrier and its preparation method and application |
| CN107661538A (en) * | 2017-11-09 | 2018-02-06 | 四川大学 | Biomaterial for medical purpose and preparation method with bionical surface structure |
| CN108250384B (en) * | 2018-02-09 | 2020-09-01 | 济南大学 | Simple method for preparing fluorine-containing polyurethane monodisperse microspheres with high yield |
| KR102172140B1 (en) * | 2019-05-03 | 2020-11-02 | 가톨릭대학교 산학협력단 | Biodegradable polyurethane microparticles |
| CN110240691B (en) * | 2019-05-20 | 2021-09-24 | 齐鲁工业大学 | Preparation method of waterborne polyurethane/collagen/hydroxyapatite composite material |
| CN115197390A (en) * | 2022-08-02 | 2022-10-18 | 明新梅诺卡(江苏)新材料有限公司 | Method for preparing waterborne polyurethane by one-step method |
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| CN1948358A (en) * | 2006-11-14 | 2007-04-18 | 赵强 | Biodegradable polymer material polyurethane and its preparation method |
| CN101391113B (en) * | 2008-11-07 | 2012-09-19 | 四川大学 | Polyurethane medical compound film and preparation method thereof |
| CN102557716B (en) * | 2012-02-14 | 2013-07-03 | 西南交通大学 | Direct interface method for preparing porous calcium phosphate nano ceramics with three-dimensional hierarchical surface morphologies |
| CN102600506B (en) * | 2012-03-07 | 2013-12-04 | 中国人民解放军第四军医大学 | NGF (nerve growth factor) chitosan microsphere and high-bionic stent slow releasing system and preparation method thereof |
| CN103073739B (en) * | 2013-01-09 | 2014-05-07 | 四川大学 | Microsphere tissue engineering scaffold used in beauty filling, and preparation method of microsphere tissue engineering scaffold |
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