CN108659476B - Low-shrinkage 3D printing material and preparation method and application thereof - Google Patents
Low-shrinkage 3D printing material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2293—Oxides; Hydroxides of metals of nickel
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a low-shrinkage 3D printing material and a preparation method and application thereof, and belongs to the field of high polymer materials. The 3D printing material comprises the following substances in percentage by mass: 35 to 73.9 percent of PBAT, 2 to 5 percent of nano zinc oxide, 10 to 20 percent of inorganic whisker material, 10 to 20 percent of inorganic mineral, 2 to 10 percent of starch, 2 to 10 percent of plasticizer and 0.1 to 1 percent of antioxidant. When in preparation, the plasticizer and the starch are uniformly mixed, then other components are added for mixing, and finally a double screw or an internal mixer is adopted for carrying out melt mixing to obtain the starch-based adhesive. The invention adopts the nano zinc oxide as the bacteriostatic agent, which can improve the bacteriostatic property of the material; the shrinkage of the material is reduced by adopting the whiskers and the inorganic flaky minerals. The prepared 3D printing material has wide application prospect in the fields of tumor radiotherapy position fixators and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-shrinkage 3D printing material, and a preparation method and application thereof.
Background
Malignant tumor is a disease seriously threatening the life safety of human beings, and has been on the rise since the 70 s in the 20 th century. According to the WHO report, the number of new cancer cases worldwide in 1990 is about 807 ten thousand, which is 37.4% higher than 517 ten thousand in 1975, and according to the trend, 2000 ten thousand new cancer cases are supposed to occur globally in 2020, and about 429 ten thousand new cancer cases per year in China.
At present, the clinical treatment of tumors mainly adopts operations, radiotherapy and chemotherapy. Radiotherapy has the advantages of wide adaptation, good curative effect and the like, and has an important position in tumor treatment without doubt. According to statistics of various centers for preventing and treating large tumors in China, about 70% of patients need to receive radiotherapy, and people who receive radiotherapy in foreign countries such as the United states, Japan and the like account for about 50-60% of new cases of recent years, and the trend is still rising at present.
In recent 10 years, radiotherapy technology has been developed dramatically, and in order to reduce the side effects and adverse effects of tumor radiotherapy on normal tissues, the original two-dimensional radiotherapy is developed into three-dimensional high-precision directional radiotherapy, such as new technologies of Stereotactic Radiotherapy (SRT), three-dimensional conformal radiotherapy (3D-CRT), conformal radiotherapy with emphasis (IMRT) and image-guided radiotherapy (IGRT), and the tumor radiotherapy is stepped into the "three-essence era" of "precise positioning, precise planning and precise radiotherapy".
At present, tumor radiotherapy mainly adopts high-energy X-rays for radiotherapy, the radiotherapy dose is generally 3000-8000cGy, a radiotherapy machine adopts computer program control, the radiation dose and the radiation time of different parts can be accurately controlled, the radiation intensity and the radiation range can be adjusted as required, and the times of radiotherapy are 1-35 times and are different.
In order to meet the requirement of precise radiotherapy, various body position fixing devices are clinically used for limiting the movement of the body position, namely a radiotherapy body position fixing technology, and the aims of improving the body position fixing precision, improving the body position repeatability and achieving the purpose of precise radiotherapy are fulfilled. When a radiotherapy plan is made, the tumor position must be accurately positioned, and CT scanning is performed before radiotherapy, and each radiotherapy positioning is expected to be completely consistent with the primary tumor position positioning. The existing body position fixing technology adopts a thermoplastic film and a vacuum negative pressure pad, the thermoplastic film adopts Polycaprolactone (PCL) to shape a patient by a thermoplastic method, and the problems of large shrinkage rate and unsatisfactory positioning accuracy exist; the vacuum negative pressure pad is used for positioning the back of a patient, and the accuracy and the repeatability are not ideal. In addition, the patients need 1-35 times of radiotherapy, and the body position fixator is stored in a hospital warehouse, so that the defects of cross infection and the like exist.
Therefore, a 3D printing material with a bacteriostatic function and a low shrinkage rate is researched and prepared, and is used for preparing a position positioner for tumor radiotherapy, and the positioning accuracy and repeatability are improved by reducing the shrinkage rate of the material; the antibacterial component is added to inhibit the growth of bacteria, so that the risk of cross infection of the body position fixator during storage in a hospital is reduced, and the antibacterial body position fixator has a good application prospect in the aspect of accurate positioning of tumor radiotherapy.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provide a low-shrinkage 3D printing material. The 3D printing material is prepared by taking PBAT (a copolymer of butanediol adipate and butanediol terephthalate) as a main raw material, nano zinc oxide as a bacteriostatic component, taking whisker and a flaky mineral material as a reinforcing agent and adding starch to adjust the degradation performance of the material. The 3D printing material has an antibacterial function, can be used for the technical field of preparation of position fixators for tumor radiotherapy and the like, and has a wide application prospect.
The invention also aims to provide a preparation method of the 3D printing material.
Still another object of the present invention is to provide an application of the 3D printed material.
The purpose of the invention is realized by the following technical scheme:
a low-shrinkage 3D printing material comprises the following substances in percentage by mass: 35 to 73.9 percent of PBAT, 2 to 5 percent of nano zinc oxide, 10 to 20 percent of inorganic whisker material, 10 to 20 percent of inorganic mineral, 2 to 10 percent of starch, 2 to 10 percent of plasticizer and 0.1 to 1 percent of antioxidant.
The number average molecular weight of the PBAT is preferably 60000-200000, and the melt flow index (190 ℃/2.16KG) is 2-10 g/10 min.
The nano zinc oxide is preferably zinc oxide with the diameter of 5-100 nm.
The inorganic whisker material is preferably an inorganic whisker material with the diameter of 2-10 um and the length-diameter ratio of more than or equal to 5.
The inorganic whisker material is preferably one or a composite of at least two of silicon carbide whisker, silicon nitride whisker, aluminum oxide whisker and potassium titanate whisker.
The inorganic mineral is preferably an inorganic mineral with flaky or fibrous characteristics and a length-diameter ratio of more than or equal to 5.
The inorganic mineral is preferably talcum powder or/and wollastonite.
The starch is preferably the starch with the particle fineness of more than or equal to 200 meshes and the water content of less than or equal to 6 percent.
The starch is preferably corn starch or/and tapioca starch.
The plasticizer is epoxidized monoglyceride undecanoate, and a preparation method reference thereof (diacetyl epoxy glyceryl undecanoate, a preparation method and application thereof, Chinese patent No. 201610575474.8) has the following structure:
the antioxidant is an antioxidant for plastic processing, and is preferably a phenolic antioxidant.
The phenolic antioxidant is preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010) or/and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076).
The preparation method of the 3D printing material comprises the following steps:
mixing 2-10% of starch and 2-10% of plasticizer according to a ratio of 1:1 for 5-10 minutes to obtain plasticized starch; uniformly mixing the plasticized starch with 35-73.9% of PBAT, 2-5% of nano zinc oxide, 10-20% of inorganic whisker material, 10-20% of inorganic mineral and 0.1-1% of antioxidant, and then carrying out melt mixing and extrusion granulation by adopting a double-screw extruder at the temperature of 120-180 ℃ and the rotating speed of a main machine of 10-400 rpm to obtain the 3D printing material, wherein the percentages are mass percentages.
The double-screw extruder is preferably a double-screw extruder with the length-diameter ratio of more than or equal to 40:1(L/D of more than or equal to 40: 1).
Preferably, the preparation method of the 3D printing material includes the following steps:
mixing 2-10% of starch and 2-10% of plasticizer according to a ratio of 1:1 for 5-10 minutes to obtain plasticized starch; uniformly mixing the plasticized starch with 35-73.9% of PBAT, 2-5% of nano zinc oxide, 10-20% of inorganic whisker material, 10-20% of inorganic mineral and 0.1-1% of antioxidant, then melting and mixing for 5-20 minutes in an internal mixer at the temperature of 120-160 ℃ and the rotating speed of 10-40 rpm, granulating by adopting a single-screw extruder or a double-screw extruder after discharging, and obtaining the 3D printing material at the extrusion temperature of 120-180 ℃ and the rotating speed of a main machine of 10-300 rpm, wherein the percentages are mass percentages.
The 3D printing material can be applied to the technical field of preparation of position fixators for tumor radiotherapy and the like, and has a wide application prospect.
Compared with the prior art, the invention has the following advantages and effects:
(1) according to the invention, the nano zinc oxide is used as a bacteriostatic agent, so that the bacteriostatic property of the 3D printing material can be improved, the growth of bacteria in the storage process of the position fixator in a hospital can be inhibited, and the risk of cross infection of patients can be reduced;
(2) according to the invention, epoxidized monoglyceride undecanoate is adopted to plasticize starch, so that the compatibility of the starch and a PBAT substrate can be obviously improved;
(3) according to the invention, the 3D printing material is prepared from the whisker and the flaky inorganic mineral material, so that the shrinkage rate of the material can be remarkably reduced.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following examples, the plasticizer epoxidized monoglyceride was prepared by itself; other raw materials and reagents, etc., unless otherwise specified, are commercially available materials and reagents from conventional markets and the like.
Example 1
Accurately weighing 5kg of corn starch and 5kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then adding 74.8kg of PBAT, 2.5kg of nano zinc oxide, 2.5kg of silicon carbide whisker, 10kg of talcum powder and 0.2kg of antioxidant 1010 into plasticized starch, uniformly mixing, and then adopting a double-screw extruder to melt, mix and extrude for granulation, wherein the temperature of a heating zone of the double-screw extruder from a feed opening to a machine head is set as follows in sequence: the temperature is 130 ℃, 150 ℃, and the rotating speed is 300rpm, and the 3D printing material is obtained.
Example 2
Accurately weighing 5kg of corn starch, 2.5kg of cassava starch and 7.5kg of epoxidized monoglyceride, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then adding 67.9kg of PBAT, 2kg of nano zinc oxide, 5kg of silicon carbide whiskers, 10kg of talcum powder and 0.1kg of antioxidant 1010 into plasticized starch, uniformly mixing, and then adopting a double-screw extruder to melt and mix, extruding and granulating, wherein the temperature of a heating zone of the double-screw extruder from a feed opening to a machine head is set as follows in sequence: the temperature is 130 ℃, 150 ℃ and the rotating speed is 250rpm, and the 3D printing material is obtained.
Example 3
Accurately weighing 2kg of starch and 2kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then 60kg of PBAT, 5kg of nano zinc oxide, 20kg of silicon nitride whisker, 10kg of talcum powder and 1kg of antioxidant 1076 are added into the plasticized starch, and after uniform mixing, a double-screw extruder is adopted for melt mixing and extrusion granulation, and the temperature of a heating zone of the double-screw extruder from a feed opening to a machine head is set as follows in sequence: the temperature is 130 ℃, 150 ℃, and the rotating speed is 300rpm, and the 3D printing material is obtained.
Example 4
Accurately weighing 10kg of starch and 10kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then adding 57.8kg of PBAT, 2kg of nano zinc oxide, 5kg of silicon carbide whiskers, 5kg of silicon nitride whiskers, 10kg of talcum powder and 0.2kg of antioxidant 1010 into plasticized starch, uniformly mixing, and then adopting an internal mixer to melt and mix for 5 minutes at 140 ℃, wherein the temperatures of a heating zone of a single-screw extruder from a feed opening to a machine head are sequentially set as follows: the temperature is 130 ℃, 150 ℃ and the rotating speed is 150rpm, and the 3D printing material is obtained.
Example 5
Accurately weighing 2kg of cassava starch and 2kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then adding 53.8kg of PBAT, 2kg of nano zinc oxide, 18kg of silicon carbide whiskers, 1kg of alumina whiskers, 1kg of potassium titanate whiskers, 20kg of talcum powder and 0.2kg of antioxidant 1010 into plasticized starch, uniformly mixing, and then adopting an internal mixer to melt and mix for 10 minutes at 140 ℃, wherein the temperature of a heating zone of a single-screw extruder from a feed opening to a machine head is set as follows in sequence: the temperature is 130 ℃, 150 ℃ and the rotating speed is 150rpm, and the 3D printing material is obtained.
Comparative example 1
Accurately weighing 5kg of starch and 5kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; 77.3kg of PBAT, 2.5kg of silicon carbide whiskers, 10kg of talc and 0.2kg of antioxidant 1010 were then added to the plasticized starch, the preparation method being the same as in example 1.
Comparative example 2
84.8kg of PBAT, 2.5kg of nano zinc oxide, 2.5kg of silicon carbide whisker, 10kg of talcum powder and 0.2kg of antioxidant 1010 are accurately weighed, and the preparation method is the same as that of example 1.
Comparative example 3
Accurately weighing 5kg of starch and 5kg of epoxidized monoglyceride undecanoate, and mixing for 5 minutes by adopting a high-speed mixer to obtain plasticized starch; then 77.3kg of PBAT, 2.5kg of nano zinc oxide, 10kg of talcum powder and 0.2kg of antioxidant 1010 are added into the plasticized starch and mixed evenly, and the preparation method is the same as that of the example 1.
Effects of the embodiment
The materials prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to the following performance tests, and the test results are shown in Table 1.
The melt index is tested according to GB 3682-2000, the temperature is 190 ℃, and the load is 2.16 Kg.
The tensile strength and elongation at break were measured according to GB/T1040.3-2006, with a tensile rate of 200 mm/min.
Shrinkage was measured as described in GB/T15585-1995.
The antibacterial performance is tested according to the method described in GB/T15979-2002.
Table 1 results of performance testing of examples
TABLE 2 comparative examples Performance test results
The results show that the antibacterial performance of the material is kept above 90% by adding more than 2% of nano zinc oxide, so that the material has a better antibacterial function; the added whisker reinforced material has relatively small size shrinkage rate and improved tensile strength.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The low-shrinkage 3D printing material is characterized by comprising the following substances in percentage by mass: 35 to 73.9 percent of PBAT, 2 to 5 percent of nano zinc oxide, 10 to 20 percent of inorganic whisker material, 10 to 20 percent of inorganic mineral, 2 to 10 percent of starch, 2 to 10 percent of plasticizer and 0.1 to 1 percent of phenol antioxidant;
the plasticizer is epoxidized monoglyceride undecanoate, and the structure of the plasticizer is as follows:
the phenolic antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or/and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
2. The low-shrinkage 3D printing material according to claim 1, wherein the PBAT has a number average molecular weight of 60000-200000 and a melt flow index of 2-10 g/10min at 190 ℃/2.16 KG.
3. The low-shrinkage 3D printing material as claimed in claim 1, wherein the nano zinc oxide is zinc oxide with a diameter of 5-100 nm; the inorganic whisker material is an inorganic whisker material with the diameter of 2-10 um and the length-diameter ratio of more than or equal to 5; the inorganic mineral is characterized by having a sheet shape or a fiber shape, and the length-diameter ratio is more than or equal to 5; the starch is the starch with the particle fineness of more than or equal to 200 meshes and the water content of less than or equal to 6 percent.
4. The low-shrinkage 3D printing material as claimed in claim 3, wherein the inorganic whisker material is one or a composite of at least two of silicon carbide whisker, silicon nitride whisker, aluminum oxide whisker and potassium titanate whisker; the inorganic mineral is talcum powder or/and wollastonite; the starch is corn starch or/and cassava starch.
5. The method for preparing a 3D printed material according to any of claims 1 to 4, comprising the steps of:
mixing 2-10% of starch and 2-10% of plasticizer according to a ratio of 1:1 for 5-10 minutes to obtain plasticized starch; uniformly mixing the plasticized starch with 35-73.9% of PBAT, 2-5% of nano zinc oxide, 10-20% of inorganic whisker material, 10-20% of inorganic mineral and 0.1-1% of antioxidant, and then carrying out melt mixing and extrusion granulation by adopting a double-screw extruder at the temperature of 120-180 ℃ and the rotating speed of a main machine of 10-400 rpm to obtain the 3D printing material, wherein the percentages are mass percentages.
6. The method of preparing the 3D printed material of any of claims 1-4, comprising the steps of:
mixing 2-10% of starch and 2-10% of plasticizer according to a ratio of 1:1 for 5-10 minutes to obtain plasticized starch; uniformly mixing the plasticized starch with 35-73.9% of PBAT, 2-5% of nano zinc oxide, 10-20% of inorganic whisker material, 10-20% of inorganic mineral and 0.1-1% of antioxidant, then melting and mixing for 5-20 minutes in an internal mixer at the temperature of 120-160 ℃ and the rotating speed of 10-40 rpm, granulating by adopting a single-screw extruder or a double-screw extruder after discharging, and obtaining the 3D printing material at the extrusion temperature of 120-180 ℃ and the rotating speed of a main machine of 10-300 rpm, wherein the percentages are mass percentages.
7. The 3D printing material of any one of claims 1-4 is applied to the technical field of preparation of position fixators for tumor radiotherapy.
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| CN112724576B (en) * | 2020-12-22 | 2022-09-02 | 金发科技股份有限公司 | Whisker fiber modified ACS/PBAT alloy and preparation method and application thereof |
| CN112724577B (en) * | 2020-12-22 | 2022-08-30 | 金发科技股份有限公司 | Scratch-resistant ACS/PBAT compound and preparation method and application thereof |
| CN113150510B (en) * | 2021-04-28 | 2023-01-13 | 张晓军 | Degradable flexible 3D printing material and preparation method and application thereof |
| CN114196169B (en) * | 2021-11-30 | 2023-05-09 | 广东基烁新材料股份有限公司 | PC/PET composite material and preparation method thereof |
| CN114671696B (en) * | 2022-03-07 | 2023-04-07 | 西北工业大学 | Method for preparing aeroengine turbine rotor based on powder 3D printing and RMI process |
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