CN112194802B - Preparation of biodegradable 3D printing gel, product and application thereof - Google Patents
Preparation of biodegradable 3D printing gel, product and application thereof Download PDFInfo
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- CN112194802B CN112194802B CN202010992206.2A CN202010992206A CN112194802B CN 112194802 B CN112194802 B CN 112194802B CN 202010992206 A CN202010992206 A CN 202010992206A CN 112194802 B CN112194802 B CN 112194802B
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- 238000010146 3D printing Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000499 gel Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 239000006188 syrup Substances 0.000 claims abstract description 12
- 235000020357 syrup Nutrition 0.000 claims abstract description 12
- 108010010803 Gelatin Proteins 0.000 claims abstract description 9
- 239000008273 gelatin Substances 0.000 claims abstract description 9
- 229920000159 gelatin Polymers 0.000 claims abstract description 9
- 235000019322 gelatine Nutrition 0.000 claims abstract description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims description 20
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 4
- 244000005700 microbiome Species 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012620 biological material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000013334 tissue model Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
- C08J3/075—Macromolecular gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
本发明提出一种可生物降解的3D打印凝胶的制备、其产物和应用，所述的制备方法包括操作：将柠檬酸和甘油和水配制为溶液，其中柠檬酸、甘油和水的质量比为1：(2～10)：(2～10)；将葡萄糖浆与(1)所得溶液混合，所述葡萄糖浆与柠檬酸的质量比为(5～9)：1；向步骤(2)所得溶液中加入明胶，所述明胶与柠檬酸的质量比为(6～12)：1。本发明提出的3D打印凝胶的制备方法，通过调节水与甘油的比例实现凝胶稳定的加工性能和加工条件即实现机械强度的调节；柠檬酸的添加可以调节凝胶的pH环境，同时也可抑制微生物的生长；所有选用的材料均为食品级，环保易降解。The present invention proposes a preparation of biodegradable 3D printing gel, its product and application. The preparation method includes operations: preparing a solution of citric acid, glycerol and water, wherein the mass ratio of citric acid, glycerol and water is is 1: (2-10): (2-10); the glucose syrup is mixed with the solution obtained from (1), the mass ratio of the glucose syrup and citric acid is (5-9): 1; to step (2) Gelatin is added to the obtained solution, and the mass ratio of the gelatin to citric acid is (6-12):1. The preparation method of the 3D printing gel proposed by the present invention realizes stable processing performance and processing conditions of the gel by adjusting the ratio of water and glycerol, that is, the adjustment of mechanical strength; the addition of citric acid can adjust the pH environment of the gel, and at the same time It can inhibit the growth of microorganisms; all selected materials are food grade, environmentally friendly and easy to degrade.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to preparation and application of a 3D printing material.
Background
3D printing techniques, also known as additive manufacturing, form three-dimensionally shaped objects by sequentially depositing materials layer by layer. The 3D printing technology reveals a completely new way of producing components, and the potential development of this technology in the field of biological tissue engineering has now developed as an important tool for the production of biological constructs with regenerative purposes or for use as tissue models. Extrusion-based 3D printing is one of the most common ways of manufacturing biological tissue models, and extrusion-based 3D printing facilities mainly include mechanical or pneumatic dispensing systems that deposit biological material onto a platform continuously, layer by layer, through a nozzle (print head) of the dispensing system. The extrusion-based 3D printing method is easy to program, the viscosity range of the printed biological material is the widest, but the technology has the limitation that the biological material needs to generate shear stress.
The 3D printed material used for biomedical tissue models also requires properties such as certain stretchability, i.e. adjustable mechanical properties and biodegradability. The following problems exist in the biological materials used in the current 3D printing: the synthetic material with higher mechanical strength has poor biodegradability, and part of biological materials from natural sources cannot meet the requirements of mechanical performance in printing and application. Synthetic materials such as polyurethane are not only time consuming and energy consuming to synthesize, but also degrade slowly, preventing their widespread use, and biologically derived hydrogels based on starch, alginate, etc. are inexpensive and degrade rapidly, but do not provide sufficient mechanical integrity under high load conditions.
Disclosure of Invention
Aiming at the defects in the field, the invention aims to provide a preparation method of a biodegradable 3D printing gel, and the preparation method can be used for adjusting the mechanical properties such as elasticity of the product.
The second purpose of the invention is to propose the preparation method of the 3D printing gel.
A third object of the invention is to propose a method for 3D printing using said 3D printing gel.
The technical scheme for realizing the aim of the invention is as follows:
a method of preparing a biodegradable 3D printing gel, comprising the operations of:
(1) preparing citric acid, glycerin and water into a solution, wherein the mass ratio of the citric acid to the glycerin to the water is 1: (2-10): (2-10);
(2) mixing glucose syrup with the solution obtained in the step (1), wherein the mass ratio of the glucose syrup to the citric acid is (5-9): 1;
(3) adding gelatin into the solution obtained in the step (2), wherein the mass ratio of the gelatin to the citric acid is (3-15): 1.
for convenience of operation, in the step (1), the raw material is preferably heated to 50-80 ℃ to prepare a solution.
More preferably, in the step (2), the glucose syrup is heated to 50-80 ℃ to reduce the viscosity of the glucose syrup, and then is mixed with the solution obtained in the step (1).
According to the preparation method, the elasticity of the printed product is adjusted by adjusting the adding ratio of the glycerol to the water, and the larger the using amount of the glycerol is, the larger the elasticity of the obtained printed object is.
When the adding proportion of the glycerol and the water is different, the elasticity of the product is different, and the restorable degree of the elastic deformation is different. When the gel is elastically deformed, the gel can be recovered to the original state within a short time, but the recovery degree is different, and the larger the addition amount of the glycerol is, the better the toughness of the gel is, and the easier the recovery is. Preferably, the mass ratio of the glycerol to the water is (8-10): (2-3). At this ratio, the printed product has elasticity to substantially completely recover the shape after deformation.
The method can adjust the elasticity of the product, compares the change degree of the glycerol addition on the elasticity of the printed product in the test, and the main mechanical property of the product is mainly determined by the material (gelatin and the like).
The 3D printing gel prepared by the preparation method is provided by the invention.
A method of 3D printing using said 3D printing gel, comprising the operations of:
s1, filling the 3D printing gel into a printing tube and removing bubbles;
s2 inputs a print pattern to print.
According to a preferable technical scheme, the 3D printing gel is heated to 50-80 ℃ and then is filled into a printing tube.
In another preferred embodiment of the present invention, the bubble removal method in step S1 is centrifugation under the following conditions: rotating at 8000-15000 rpm, and centrifuging for 5-20 min.
In step S2, the print parameters are: the printing temperature is 20-30 ℃, and the printing height is 0.1-0.7 mm.
Furthermore, the extrusion rate during printing is 20-50 mm/s, and the diameter of the nozzle is 0.3-1.0 mm.
The invention has the beneficial effects that:
according to the preparation method of the 3D printing gel, the stable processing performance and the processing condition of the gel, namely the elasticity is adjusted by adjusting the proportion of water and glycerol; the addition of citric acid can adjust the pH environment of the gel and inhibit the growth of microorganisms; all selected materials are food-grade, environment-friendly and easy to degrade.
The composite hydrogel prepared by the invention combines various bio-based materials, each material has unique functions, and simultaneously, the combination of various bio-based materials ensures that the gel printed product has adjustable elastic property and biodegradability. The used material gelatin is a main polymer forming a gel network, can be easily derived, has easy degradation and good biocompatibility, has moderate elasticity in the air, and is not easy to generate plastic deformation; the addition of glucose syrup enhances the extensibility of the gel.
Detailed Description
The following examples are intended to illustrate the invention but should not be construed as limiting the scope thereof. In the examples, all the means used are conventional in the art unless otherwise specified.
Example 1
A preparation method of 3D printing gel with adjustable mechanical property and biodegradability comprises the following steps:
(1) dissolving 1g of citric acid and 5g of glycerol in 8g of deionized water, and heating to 60 ℃ to prepare a solution;
(2) 7g of glucose syrup was heated to 60 ℃ to lower its viscosity, and mixed with the solution obtained in (1).
(3) And (3) cooling the solution prepared in the step (2) to room temperature, adding 4g of gelatin powder, and uniformly mixing.
Printing example 1
The mixture obtained in example 1 was heated in an oven at 70 ℃ for 1 hour, stirred uniformly, loaded into a printing tube, and centrifuged at 10000rpm for 10min to remove air bubbles.
Setting the printing parameters as follows: the printing temperature is 25 ℃, the printing height is 0.5mm, the extrusion rate is 30mm/s, and the diameter of a nozzle is 0.5 mm;
after the print pattern was entered in the printer, printing was started with the hydrogel.
Example 2:
substantially the same production method as in example 1 was employed except that 4g of glycerin was added in step (3) dissolved in 8g of deionized water.
Example 3
Substantially the same production method as in example 1 was employed except that 9g of glycerin was added in step (3) dissolved in 3g of deionized water.
Example 4
Substantially the same production method as in example 1 was employed except that 10g of glycerin was added in step (3) dissolved in 2g of deionized water.
Printing examples 2 to 4
The same printing method as in printing example 1 was used, and a sample having the same shape was printed, the sample specification was 1cm by 0.3cm by 3cm, and the sample was left to stand at room temperature for 20 days and then left to stand.
The specific gel component ratios are shown in table 1, the simple evaluation results of the elasticity degrees under different glycerin and water ratios are shown in table 1, and the simple evaluation method of the elasticity degrees comprises the following steps: the gel is placed on a glass slide, and can keep a vertical state and a good shape in a standing state. The gel was manually bent by 90 degrees, and after releasing the hand, the degree of recovery of the bent state of the gel was recorded after 5 seconds.
TABLE 1 gel composition ratios and properties of printed products
Although the present invention has been described in detail hereinabove, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (1)
1. A method of 3D printing using a biodegradable 3D printing gel, comprising the acts of:
(1) preparing citric acid, glycerin and water into a solution, wherein the mass ratio of the citric acid to the glycerin to the water is 1: (8-10): (2-3) adjusting the elasticity of the printed product by adjusting the adding ratio of glycerin to water, wherein the larger the using amount of the glycerin is, the larger the elasticity of the obtained printed object is;
(2) heating glucose syrup to 50-80 ℃ to reduce the viscosity of the glucose syrup, and then mixing the glucose syrup with the solution obtained in the step (1), wherein the mass ratio of the glucose syrup to the citric acid is (5-9): 1;
(3) adding gelatin into the solution obtained in the step (2), wherein the mass ratio of the gelatin to the citric acid is (3-15): 1;
s1, heating the obtained 3D printing gel to 50-80 ℃, then putting the gel into a printing tube, and removing bubbles, wherein the bubble removing method is centrifugation, and the centrifugation conditions are as follows: rotating at 8000-15000 rpm, and centrifuging for 5-20 min;
s2, inputting a print pattern for printing, the print parameters being: the printing temperature is 20-30 ℃, the printing height is 0.1-0.7 mm, the extrusion rate during printing is 20-50 mm/s, and the diameter of the nozzle is 0.3-1.0 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010992206.2A CN112194802B (en) | 2020-09-21 | 2020-09-21 | Preparation of biodegradable 3D printing gel, product and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010992206.2A CN112194802B (en) | 2020-09-21 | 2020-09-21 | Preparation of biodegradable 3D printing gel, product and application thereof |
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| Publication Number | Publication Date |
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| CN112194802A CN112194802A (en) | 2021-01-08 |
| CN112194802B true CN112194802B (en) | 2021-11-19 |
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| CN113599362A (en) * | 2021-01-15 | 2021-11-05 | 中国人民解放军军事科学院军事医学研究院 | 3D printing preparation, and preparation method and application thereof |
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2020
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| Title |
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