CN109251280A - A kind of preparation method with anticoagulant property biology 3D printing material - Google Patents

A kind of preparation method with anticoagulant property biology 3D printing material Download PDF

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CN109251280A
CN109251280A CN201810784599.0A CN201810784599A CN109251280A CN 109251280 A CN109251280 A CN 109251280A CN 201810784599 A CN201810784599 A CN 201810784599A CN 109251280 A CN109251280 A CN 109251280A
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printing material
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赵延延
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium

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Abstract

The invention discloses a kind of preparation method with anticoagulant property biology 3D printing material, which passes through high speed ball milling for raw materials such as polycarbonate, ethylene carbonate, kaolin, aluminium oxide, chlorinated paraffin, butyl stearate, sulfonation glucan, hyaluronic acid, ethylene glycol diglycidylether, lauric acid zinc soaps respectively, sieving sorts, vacuum nitrogen is catalyzed reaction, vacuum filtration, wash repeatedly, drying, sonic oscillation disperses, cryospray drying and other steps are prepared with anticoagulant property biology 3D printing material.What is be prepared has anticoagulant property biology 3D printing material, and cost of material is low, light hardness is big, has significant anticoagulant functions, is suitable for the application of a variety of surgical instrument consumptive materials, hemostatic device etc..

Description

A kind of preparation method with anticoagulant property biology 3D printing material
Technical field
The present invention relates to this technical fields of 3D printing material, are related specifically to a kind of with the 3D printing of anticoagulant property biology The preparation method of material.
Background technique
3D printing (3D printing) is one kind based on digital model file, with flow-like, powdered, silk (stick) shape etc. is curable, bonds, alloying material, and the technology of object is constructed by way of successively solidifying, bonding, fuse.Often Be used for modeling in fields such as mold manufacture, industrial designs, after be gradually available for the direct manufactures of some products, having had makes The components made of the printing of this technology.The technology is in jewelry, footwear, industrial design, building, engineering and construction (AEC), vapour Vehicle, aerospace, dentistry and medical industries, education, GIS-Geographic Information System, civil engineering, gun and other field are all Using.3D printing technique appears in mid-term the 1990s, actually utilizes the newest of the technologies such as photocuring and paper layer be folded Rapid molding device.It is essentially identical with common print working principle, and printer is provided with liquid or powder etc. " printed material ", After being connect with computer, is controlled by computer and " printed material " is stacked up from level to level, finally the blueprint on computer is become It is in kind.This printing technique is known as 3D three-dimensional printing technology.Traditional manufacture, which generally requires, to be cut raw material or is drilled, i.e., Subtract material manufacture, can be mass-produced;3D printing is that material is stacked to bonding, fusion, i.e. increasing material manufacturing from level to level;It can be achieved quick Individual character manufacturing can produce the impossible shape of traditional manufacture.Based on biologic applications be directed toward 3D printing technique, Printed material composition has more particular/special requirements compared with other field 3D printing material.Such as high temperature sintering, organic solvent, The conditions such as ultraviolet irradiation and crosslinking agent must often avoid as far as possible during biological 3D printing.Specifically, according to application purpose Must consider claimed below: a. printability, what the performances such as viscosity, rheology and the gelation of material directly influenced 3D printing can Operability, it is resolved that print the room and time resolution ratio of product.B. biocompatibility includes biological safety and biological function Property material does not require nothing more than very low toxicity and does not cause any adverse reaction of body, and material is required specifically to answer With the corresponding function of middle excitation body.C. degradability includes the degradation speed controllability of material, with regeneration speed With property, catabolite safety, the swelling of material and shrinkage character etc..D. structure and mechanical performance, the material of 3D printing is often Have the function of supporting cell and tissue three-dimensional structure.For specific organization type, from skin, muscle, cartilage to os osseum, Must have different mechanical strength and micro-structure, the especially hole of material after file printing.E. bionics characteristic, material are imitative Raw characteristic of learning is conducive to stimulate cellular response.Biological active component is mixed in biomaterial to glue endogenous or foreign cell Attached, migration, proliferation and functional expression generate positive effect.In addition, the modification of material surface property such as chemical group, roughness, What hydrophilic and hydrophobic, micro nano structure etc. directly influenced cell sprawls shape, atomization, movement, orientation, the group of cytoskeleton Dress, the even associated signal paths of cell interior.
Summary of the invention
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparations with anticoagulant property biology 3D printing material Method, the technique gather polycarbonate, ethylene carbonate, kaolin, aluminium oxide, chlorinated paraffin, butyl stearate, sulfonation Portugal The raw materials such as sugar, hyaluronic acid, ethylene glycol diglycidylether, lauric acid zinc soap pass through high speed ball milling, sieving sorting, vacuum respectively Nitrogen catalysis reaction, vacuum filtration, tool is prepared in washing, dry, sonic oscillation dispersion, cryospray drying and other steps repeatedly There is anticoagulant property biology 3D printing material.What is be prepared has anticoagulant property biology 3D printing material, and cost of material is low, matter Light hardness is big, has significant anticoagulant functions, is suitable for the application of a variety of surgical instrument consumptive materials, hemostatic device etc..
Technical solution: to solve the above-mentioned problems, the invention discloses one kind to have anticoagulant property biology 3D printing material Preparation method, comprising the following steps:
(1) by 12-15 parts of polycarbonate, 15-20 parts of ethylene carbonate, 2-7 parts of kaolin, 1-4 parts of aluminium oxide, chlorinated paraffin 2- 6 parts, 2-4 parts of butyl stearate are added in high speed ball mill, and ratio of grinding media to material 99:4 carries out ball milling, obtained mixture of powders sieving Sorting, it is spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 2-5 parts of sulfonation glucan, hyaluronic acid 1-3 is added Part, 2-5 parts of ethylene glycol diglycidylether, 1-4 parts of lauric acid zinc soap, 1-3 parts of initiator, 2-3 parts of auxiliary agent, are heated to 70-75 It is passed through nitrogen after DEG C and excludes oxygen, then temperature rises to 80-85 DEG C again, continues insulation reaction 6-10h, after reaction in furnace Air pressure returns back to normal pressure, and reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), with sterile water washing 3 times, it is dry that suction filtration product is placed in 65 DEG C of vacuum Dry 40-60min in dry case;
(4) it by 3-5 parts of the dried object of step (3), dispersing agent, is added in ultrasonator, carries out ultrasonic disperse;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, carries out powdered material, drying, collection, packet It fills, get product.
Preferably, the rotational speed of ball-mill in the step (1) is 3000r/min, Ball-milling Time 30-50min.
Preferably, the mesh size of crossing in the step (1) is 5000 mesh.
Preferably, the initiator in the step (2) is selected from azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide first One or more of acyl, lauroyl peroxide.
Preferably, the auxiliary agent in the step (2) is in stearoylketene amine, oleamide, erucyl amide, zinc stearate It is one or more of.
Preferably, the nitrogen pressure in the step (2) is 5MPa.
Preferably, the vacuum filtration pressure in the step (3) is 5*10-8Pa。
Preferably, the dispersing agent in the step (4) is in sodium pyrophosphate, more sodium metaphosphates, potassium citrate, sodium metasilicate One or more.
Preferably, the sonic oscillation power in the step (4) is 500W, ultrasonic time 90min.
Preferably, it is -25 DEG C that the cryospray drying parameter in the step (5), which is cryogenic temperature, and condenser temperature is -75 DEG C, atomisation pressure 5BAR.
Compared with prior art, the present invention has the advantages that:
(1) a kind of preparation method with anticoagulant property biology 3D printing material of the invention by polycarbonate, ethylene carbonate, Kaolin, aluminium oxide, chlorinated paraffin, butyl stearate, sulfonation glucan, hyaluronic acid, ethylene glycol diglycidylether, laurel The raw materials such as sour zinc soap pass through high speed ball milling respectively, sieving sorting, vacuum nitrogen catalysis reaction, vacuum filtration, wash repeatedly, is dry Dry, sonic oscillation dispersion, cryospray drying and other steps are prepared with anticoagulant property biology 3D printing material.It is prepared Have anticoagulant property biology 3D printing material, cost of material is low, light hardness is big, have significant anticoagulant functions, fit Together in the application of a variety of surgical instrument consumptive materials, hemostatic device etc..
(2) of the invention there is anticoagulant property biology 3D printing material feedstock to be easy to get, simple process, be suitable for large-scale industry Change and uses, it is practical.
Specific embodiment
Embodiment 1
(1) by 12 parts of polycarbonate, 15 parts of ethylene carbonate, 2 parts of kaolin, 1 part of aluminium oxide, 2 parts of chlorinated paraffin, stearic acid fourth It 2 parts of ester, is added in high speed ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 30min, ratio of grinding media to material 99:4 carries out ball Mill, obtained mixture of powders sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 2 parts of sulfonation glucan, 1 part of hyaluronic acid, second is added 2 parts of Hexanediol diglycidyl ether, 1 part of lauric acid zinc soap, 1 part of azodiisobutyronitrile, 2 parts of stearoylketene amine, after being heated to 70-75 DEG C It is passed through nitrogen and excludes oxygen, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 6h, reaction knot Air pressure returns back to normal pressure in Shu Houlu, and reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), vacuum filtration pressure is 5*10-8Pa, with sterile water washing 3 It is secondary, it filters product and is placed in 65 DEG C of vacuum ovens dry 40min;
(4) it by 3 parts of the dried object of step (3), sodium pyrophosphate, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation function Rate is 500W, ultrasonic time 90min;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Embodiment 2
(1) by 13 parts of polycarbonate, 17 parts of ethylene carbonate, 3 parts of kaolin, 2 parts of aluminium oxide, 4 parts of chlorinated paraffin, stearic acid fourth It 3 parts of ester, is added in high speed ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 40min, ratio of grinding media to material 99:4 carries out ball Mill, obtained mixture of powders sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 3 parts of sulfonation glucan, 2 parts of hyaluronic acid, second is added 3 parts of Hexanediol diglycidyl ether, 2 parts of lauric acid zinc soap, 2 parts of azobisisoheptonitrile, 2 parts of oleamide, after being heated to 70-75 DEG C It is passed through nitrogen and excludes oxygen, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 7h, reaction knot Air pressure returns back to normal pressure in Shu Houlu, and reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), vacuum filtration pressure is 5*10-8Pa, with sterile water washing 3 It is secondary, it filters product and is placed in 65 DEG C of vacuum ovens dry 50min;
(4) it by 4 parts of the dried object of step (3), more sodium metaphosphates, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation Power is 500W, ultrasonic time 90min;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Embodiment 3
(1) by 14 parts of polycarbonate, 19 parts of ethylene carbonate, 6 parts of kaolin, 3 parts of aluminium oxide, 5 parts of chlorinated paraffin, stearic acid fourth It 3 parts of ester, is added in high speed ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 45min, ratio of grinding media to material 99:4 carries out ball Mill, obtained mixture of powders sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, sulfonation bextran 45 part, 3 parts of hyaluronic acid, second is added 4 parts of Hexanediol diglycidyl ether, 3 parts of lauric acid zinc soap, 2 parts of benzoyl peroxide, 3 parts of erucyl amide, after being heated to 70-75 DEG C It is passed through nitrogen and excludes oxygen, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 9h, reaction knot Air pressure returns back to normal pressure in Shu Houlu, and reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), vacuum filtration pressure is 5*10-8Pa, with sterile water washing 3 It is secondary, it filters product and is placed in 65 DEG C of vacuum ovens dry 45min;
(4) it by 4 parts of the dried object of step (3), potassium citrate, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation function Rate is 500W, ultrasonic time 90min;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Embodiment 4
(1) by 15 parts of polycarbonate, 20 parts of ethylene carbonate, 7 parts of kaolin, 4 parts of aluminium oxide, 6 parts of chlorinated paraffin, stearic acid fourth It 4 parts of ester, is added in high speed ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 50min, ratio of grinding media to material 99:4 carries out ball Mill, obtained mixture of powders sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 5 parts of sulfonation glucan, 3 parts of hyaluronic acid, second is added 5 parts of Hexanediol diglycidyl ether, 4 parts of lauric acid zinc soap, 3 parts of lauroyl peroxide, 3 parts of zinc stearate, after being heated to 70-75 DEG C It is passed through nitrogen and excludes oxygen, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 10h, reaction After in furnace air pressure return back to normal pressure, reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), vacuum filtration pressure is 5*10-8Pa, with sterile water washing 3 It is secondary, it filters product and is placed in 65 DEG C of vacuum ovens dry 60min;
(4) it by 5 parts of the dried object of step (3), sodium metasilicate, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation power For 500W, ultrasonic time 90min;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Comparative example 1
(1) it by 12 parts of polycarbonate, 15 parts of ethylene carbonate, 2 parts of kaolin, 1 part of aluminium oxide, 2 parts of butyl stearate, is added high In fast ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 30min, ratio of grinding media to material 99:4 carry out ball milling, obtained powder Mixture sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 1 part of hyaluronic acid, ethylene glycol diglycidyl is added 2 parts of ether, 1 part of lauric acid zinc soap, 1 part of azodiisobutyronitrile, 2 parts of stearoylketene amine are passed through nitrogen and exclude oxygen after being heated to 70-75 DEG C Gas, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 6h, and air pressure is returned in furnace after reaction Again to normal pressure, reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), vacuum filtration pressure is 5*10-8Pa, with sterile water washing 3 It is secondary, it filters product and is placed in 65 DEG C of vacuum ovens dry 40min;
(4) it by 3 parts of the dried object of step (3), sodium pyrophosphate, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation function Rate is 500W, ultrasonic time 90min;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Comparative example 2
(1) by 15 parts of polycarbonate, 20 parts of ethylene carbonate, 7 parts of kaolin, 4 parts of aluminium oxide, 6 parts of chlorinated paraffin, stearic acid fourth It 4 parts of ester, is added in high speed ball mill, rotational speed of ball-mill 3000r/min, Ball-milling Time 50min, ratio of grinding media to material 99:4 carries out ball Mill, obtained mixture of powders sieving sorting, crossing mesh size is 5000 mesh, spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 5 parts of sulfonation glucan, 3 parts of hyaluronic acid, second is added 5 parts of Hexanediol diglycidyl ether, 4 parts of lauric acid zinc soap, 3 parts of lauroyl peroxide, 3 parts of zinc stearate, after being heated to 70-75 DEG C It is passed through nitrogen and excludes oxygen, nitrogen pressure 5Mpa, then temperature rises to 80-85 DEG C again, continues insulation reaction 10h, reaction After in furnace air pressure return back to normal pressure, reactant cooling is spare;
(3) it by 5 parts of the dried object of step (2), sodium metasilicate, is added in ultrasonator, carries out ultrasonic disperse, sonic oscillation power For 500W, ultrasonic time 90min;
(4) the ultrasonic disperse product of step (3) is injected into cryospray drying machine, cryospray drying parameter is cryogenic temperature Be -25 DEG C, condenser temperature be -75 DEG C, atomisation pressure 5BAR, carry out powdered material, drying, collection, packaging, up at Product.
Will made from embodiment 1-4 and comparative example 1-2 have anticoagulant property biology 3D printing material carry out respectively density, This several blood coagulation test, compression strength performance tests, test result are shown in Table 1.
Table 1
  Density/g.cm-1 30min is tested in blood coagulation Compression strength/Mpa
Embodiment 1 1.253 Without blood coagulation 625
Embodiment 2 1.312 Without blood coagulation 620
Embodiment 3 1.273 Without blood coagulation 630
Embodiment 4 1.280 Without blood coagulation 635
Comparative example 1 1.783 Without blood coagulation 265
Comparative example 2 1.906 Without blood coagulation 315
A kind of preparation method with anticoagulant property biology 3D printing material of the invention is by polycarbonate, ethylene carbonate, height Ridge soil, aluminium oxide, chlorinated paraffin, butyl stearate, sulfonation glucan, hyaluronic acid, ethylene glycol diglycidylether, lauric acid The raw materials such as zinc soap pass through respectively high speed ball milling, sieving sorting, vacuum nitrogen catalysis reaction, vacuum filtration, wash repeatedly, be dry, Sonic oscillation dispersion, cryospray drying and other steps are prepared with anticoagulant property biology 3D printing material.It is prepared With anticoagulant property biology 3D printing material, cost of material is low, light hardness is big, has significant anticoagulant functions, is suitble to In the application of a variety of surgical instrument consumptive materials, hemostatic device etc..Of the invention has anticoagulant property biology 3D printing material former Material be easy to get, simple process, be suitable for heavy industrialization use, it is practical.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (10)

1. a kind of preparation method with anticoagulant property biology 3D printing material, which comprises the following steps:
(1) by 12-15 parts of polycarbonate, 15-20 parts of ethylene carbonate, 2-7 parts of kaolin, 1-4 parts of aluminium oxide, chlorinated paraffin 2- 6 parts, 2-4 parts of butyl stearate are added in high speed ball mill, and ratio of grinding media to material 99:4 carries out ball milling, obtained mixture of powders sieving Sorting, it is spare;
(2) the sieving powder of step (1) is added in vacuum reaction kettle, 2-5 parts of sulfonation glucan, hyaluronic acid 1-3 is added Part, 2-5 parts of ethylene glycol diglycidylether, 1-4 parts of lauric acid zinc soap, 1-3 parts of initiator, 2-3 parts of auxiliary agent, are heated to 70-75 It is passed through nitrogen after DEG C and excludes oxygen, then temperature rises to 80-85 DEG C again, continues insulation reaction 6-10h, after reaction in furnace Air pressure returns back to normal pressure, and reactant cooling is spare;
(3) vacuum filtration machine is added in the reactant of step (2), with sterile water washing 3 times, it is dry that suction filtration product is placed in 65 DEG C of vacuum Dry 40-60min in dry case;
(4) it by 3-5 parts of the dried object of step (3), dispersing agent, is added in ultrasonator, carries out ultrasonic disperse;
(5) the ultrasonic disperse product of step (4) is injected into cryospray drying machine, carries out powdered material, drying, collection, packet It fills, get product.
2. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Rotational speed of ball-mill in step (1) is 3000r/min, Ball-milling Time 30-50min.
3. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Mesh size of crossing in step (1) is 5000 mesh.
4. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Initiator in step (2) is in azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide It is one or more of.
5. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Auxiliary agent in step (2) is selected from one or more of stearoylketene amine, oleamide, erucyl amide, zinc stearate.
6. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Nitrogen pressure in step (2) is 5MPa.
7. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Vacuum filtration pressure in step (3) is 5*10-8Pa。
8. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Dispersing agent in step (4) is selected from one or more of sodium pyrophosphate, more sodium metaphosphates, potassium citrate, sodium metasilicate.
9. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that described Sonic oscillation power in step (4) is 500W, ultrasonic time 90min.
10. the preparation method according to claim 1 with anticoagulant property biology 3D printing material, which is characterized in that institute It is -25 DEG C that state the cryospray drying parameter in step (5), which be cryogenic temperature, and condenser temperature is -75 DEG C, and atomisation pressure is 5BAR。
CN201810784599.0A 2018-07-17 2018-07-17 A kind of preparation method with anticoagulant property biology 3D printing material Pending CN109251280A (en)

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CN108136496A (en) * 2015-10-09 2018-06-08 赛丹思科大学 3d printing raw material and its application

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CN108136496A (en) * 2015-10-09 2018-06-08 赛丹思科大学 3d printing raw material and its application

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* Cited by examiner, † Cited by third party
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CN109771701A (en) * 2019-02-11 2019-05-21 赵延延 A kind of preparation method of soft biological 3D printing material

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