CN113150503B - 3D printing composite material suitable for medical treatment and aviation and preparation method thereof - Google Patents

3D printing composite material suitable for medical treatment and aviation and preparation method thereof Download PDF

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CN113150503B
CN113150503B CN202110638473.4A CN202110638473A CN113150503B CN 113150503 B CN113150503 B CN 113150503B CN 202110638473 A CN202110638473 A CN 202110638473A CN 113150503 B CN113150503 B CN 113150503B
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parts
composite material
material suitable
aviation
medical treatment
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CN113150503A (en
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司涛
孟建新
兰晓虎
门建永
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Mingdan Medical Technology Co ltd
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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
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention relates to the technical field of 3D printing, and provides a 3D printing composite material suitable for medical treatment and aviation, which comprises the following components in parts by weight: 60-70 parts of TPEE, 1-5 parts of TPU, 20-30 parts of PLA, 0.5-1 part of genipin and 1-3 parts of modified nano titanium dioxide. Through above-mentioned technical scheme, the problem that 3D printing material mechanical properties and biological skin nature do not have simultaneously among the prior art has been solved.

Description

3D printing composite material suitable for medical treatment and aviation and preparation method thereof
Technical Field
The invention relates to the technical field of 3D printing, in particular to a 3D printing composite material suitable for medical treatment and aviation and a preparation method thereof.
Background
The 3D printing is mainly composed of software, materials and equipment, wherein a computer three-dimensional design model is used as a bluebook, special materials such as metal powder, ceramic powder, plastic and cell tissues are stacked layer by layer and bonded through a software layering dispersion and numerical control forming system in modes of laser beams, hot melting nozzles and the like, and finally, the materials are stacked and formed to manufacture a solid product. In recent years, 3D printing technology has been a research focus in various fields, but the development time is still short, and there are some imperfect areas in various aspects, and the type of consumables is limited, and the performance is insufficient, which is an important problem facing 3D printing.
At present, few 3D printing materials which can be applied to medical treatment and aviation fields exist in the market, and the requirements for high mechanical property and biological skin adhesion performance cannot be met.
Disclosure of Invention
The invention provides a 3D printing composite material suitable for medical treatment and aviation and a preparation method thereof, and solves the problem that the mechanical property and the biological skin adhesion property of a 3D printing material in the prior art are not compatible.
The technical scheme of the invention is as follows:
A3D printing composite material suitable for medical treatment and aviation comprises the following components in parts by weight: 60-70 parts of TPEE, 1-5 parts of TPU, 20-30 parts of PLA, 0.5-1 part of genipin and 1-3 parts of modified nano titanium dioxide.
As a further technical scheme, the 3D printing composite material suitable for medical treatment and aviation comprises the following components in parts by weight: 65 parts of TPEE, 3 parts of TPU, 25 parts of PLA, 0.8 part of genipin and 2 parts of modified nano titanium dioxide.
As a further technical scheme, the modified nano titanium dioxide comprises the following components: the ratio of the diphenyl siloxy phenyl trimethicone to the nano titanium dioxide is 1 (40-50).
The invention also provides a preparation method of the 3D printing composite material suitable for medical treatment and aviation, which comprises the following steps:
s1, preparing materials according to the raw materials;
s2, drying TPEE;
s3, extruding the raw materials in an extruder and then drawing wires to obtain the product.
As a further technical scheme, in the step S2, the drying temperature is 80-120 ℃, and the drying time is 6-8 h.
As a further technical proposal, the step S2 is dried until the moisture content of the TPEE is less than 0.1%.
In the step S3, a gradual change screw is adopted as the extruder, and the length-diameter ratio is (24-28): 1, the compression ratio is (2.7-4): 1.
as a further technical scheme, the temperature of the extruder barrel is 160-220 ℃, the temperature of the nozzle is 175-220 ℃, and the temperature of the die is 25-55 ℃.
According to a further technical scheme, the injection pressure of the extruder is 45-65 MPa, and the screw back pressure is 4-10 MPa.
As a further technical scheme, the rotating speed of a screw of the extruder is 20-100 r/pm, and the molding period is 10-30 s.
The beneficial effects of the invention are as follows:
1. the thermoplastic polyester elastomer (TPEE) is a block copolymer, which contains a crystalline polyester hard segment with high melting point and high hardness and an amorphous polyether or polyester soft segment with lower glass transition temperature, and has a two-phase association structure, wherein the hard segment crystallization plays a role in physical crosslinking to stabilize the size of a product, and the soft segment amorphousness endows the polymer with high resilience. In the invention, genipin is added, can be crosslinked with a hard chain segment in TPEE, improves the mechanical property, and meets the requirements of aviation materials. TPEE has excellent melt stability and sufficient thermoplasticity, and thus has good processability, and is prepared by an extrusion molding method. At low shear rates, the TPEE melt viscosity is insensitive to shear rate, whereas at high shear rates, the melt viscosity decreases with increasing shear rate. Since TPEE melt is very sensitive to temperature, its melt viscosity varies several times to several tens times within a 10 ℃ variation range, and thus the temperature should be strictly controlled during molding.
2. Polylactic Acid (PLA) is a polyester polymer obtained by polymerizing lactic Acid serving as a main raw material, is a novel biodegradable material and can be biodegraded into active compost. The melt viscosity of PLA is high, the melt fluidity of the thermal shrinkage elastomer can be reduced, the melt flow rate of the composite material is 42-68 g/10min, and the processability is excellent.
3. TPU (thermoplastic polyurethanes) is named as thermoplastic polyurethane elastomer rubber, and is a high molecular material formed by jointly reacting diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), etc., with macromolecular polyol and low molecular polyol (chain extender) and polymerizing. The TPU is added into the material, so that the toughness of 3D printing forming can be improved. This characteristic is applicable to fixed wing unmanned aerial vehicle's 3D printing material.
4. According to the invention, the titanium dioxide is added, so that the ageing resistance of the material can be improved, and the strength of the material can also be improved. On the other hand, because the compatibility of the titanium dioxide and the matrix high polymer material is poor, the diphenyl siloxy phenyl trimethyl siloxane is utilized, on one hand, a flexible group is introduced, the flexibility of the composite material is improved, on the other hand, the compatibility of the inorganic filler and the organic resin can be improved, and the titanium dioxide is attached to the composite material in a good mechanical property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall relate to the scope of protection of the present invention.
The operating parameters of the extruders in the following examples and comparative examples are shown in table 1:
TABLE 1 screw extruder Process parameters
Figure BDA0003106771460000031
Example 1
S1, preparing materials: 70 parts of TPEE, 5 parts of TPU, 30 parts of PLA, 1 part of genipin, 3 parts of nano titanium dioxide and 0.06 part of diphenyl siloxy phenyl trimethyl polysiloxane;
s2, drying the TPEE for 6h at 120 ℃ until the water content is less than 0.1 percent;
s3, mixing diphenylsiloxy phenyl trimethicone with glycerol according to the mass ratio of 1:5, putting nano titanium dioxide into a high-speed mixer, pumping the fine-mist mixed solution under stirring, treating for 20min, and drying for later use;
s4, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Example 2
S1, preparing materials: 60 parts of TPEE, 1 part of TPU, 20 parts of PLA, 0.5 part of genipin, 1 part of nano titanium dioxide and 0.025 part of diphenyl siloxy phenyl trimethyl polysiloxane;
s2, drying the TPEE for 8h at the temperature of 80 ℃ until the water content is less than 0.1 percent;
s3, mixing diphenylsiloxy phenyl trimethicone with glycerol according to the mass ratio of 1:5, putting nano titanium dioxide into a high-speed mixer, pumping the fine-mist mixed solution under stirring, treating for 20min, and drying for later use;
s4, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Example 3
S1, preparing materials: TPEE 65 parts, TPU 3 parts, PLA 25 parts, genipin 0.75 part, nano titanium dioxide 2 parts, diphenyl siloxy phenyl trimethyl polysiloxane 0.04 part;
s2, drying the TPEE for 7h at 100 ℃ until the water content is less than 0.1 percent;
s3, mixing diphenylsiloxy phenyl trimethicone with glycerol according to the mass ratio of 1:5, putting nano titanium dioxide into a high-speed mixer, pumping the fine-mist mixed solution under stirring, treating for 20min, and drying for later use;
s4, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Example 4
S1, preparing materials: 65 parts of TPEE, 6 parts of hydroxyapatite, 3 parts of TPU, 25 parts of PLA, 0.75 part of genipin, 2 parts of nano titanium dioxide and 0.04 part of diphenyl siloxy phenyl trimethyl polysiloxane;
s2, drying the TPEE for 8 hours at the temperature of 80 ℃ until the water content is less than 0.1 percent;
s3, mixing diphenylsiloxy phenyl trimethicone with glycerol according to the mass ratio of 1:5, putting nano titanium dioxide into a high-speed mixer, pumping the fine-mist mixed solution under stirring, treating for 20min, and drying for later use;
s4, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Comparative example 1
S1, preparing materials: TPEE 65 parts, TPU 3 parts, PLA 25 parts, genipin 0.75 parts;
s2, drying the TPEE for 7h at 100 ℃ until the water content is less than 0.1 percent;
s3, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Comparative example 2
S1, preparing materials: 65 parts of TPEE, 3 parts of TPU, 25 parts of PLA, 0.75 part of genipin and 2 parts of nano titanium dioxide;
s2, drying the TPEE for 7h at 100 ℃ until the water content is less than 0.1 percent;
s3, extruding the raw materials in an extruder and then drawing wires to obtain the product.
Comparative example 3
S1, preparing materials: 65 parts of TPEE, 3 parts of TPU, 25 parts of PLA, 2 parts of nano titanium dioxide and 0.04 part of diphenyl siloxy phenyl trimethyl polysiloxane;
s2, drying the TPEE for 7h at 100 ℃ until the water content is less than 0.1 percent;
s3, mixing diphenylsiloxy phenyl trimethicone with glycerol according to the mass ratio of 1:5, putting nano titanium dioxide into a high-speed mixer, pumping the fine-mist mixed solution under stirring, treating for 20min, and drying for later use;
s4, extruding the raw materials in an extruder, and then pulling to obtain the product.
TABLE 2 summary of the raw materials of inventive examples and comparative examples
Figure BDA0003106771460000041
Figure BDA0003106771460000051
The Melt Flow Rate (MFR) test is carried out according to GB/T3682-2000 test, the test conditions are that the temperature is 220 ℃, and the load is 10 kg; the tensile strength is tested according to GB/T1040-2018, and the volume shrinkage is tested by GB/T1033.1-2008 dipping method. The test data of the examples and comparative examples are shown in table 3.
Table 3 test data for examples and comparative examples
Figure BDA0003106771460000052
The composite material obtained by the embodiment of the invention can meet the requirements of a 3D printer, and the nontoxic, environment-friendly and naturally degradable material is suitable for manufacturing the liner of a medical rehabilitation instrument and is suitable for a buffer material in the field of 3D printing of an aerial unmanned aerial vehicle. The clamp plate and the lining are printed and formed at one time through the double-extruder 3D printer, so that the manufacturing period and the working procedure of the clamp plate are greatly reduced, and the comfort level of a patient is improved.
The hydroxyapatite with 10% of PLA content is added in the embodiment 4 of the invention, which shows that the HA addition can improve the strength of the composite material, the movement of PLA molecular chains is inhibited and the flexibility is reduced due to the addition of the rigid particles, but the melt flow speed in the embodiment 4 is in a moderate state, and the forming precision and the dimensional stability of the material are ensured.
In the comparative example 1, the nano titanium dioxide is not added, the melt flow rate is increased, but the tensile strength is reduced, in the comparative example 2, the nano titanium dioxide is not modified, compared with the comparative example 1, the tensile strength is increased by only 2MPa, the increase amplitude is small, and in the modified nano titanium dioxide in the application example 3, the tensile strength of the composite material is greatly improved, the elongation at break is relatively moderate, and the toughness can meet the production requirement. Compared with the prior art, genipin is not added in the comparative example 3, so that the obtained composite material has large volume shrinkage, poor dimensional stability and reduced mechanical property, because genipin can be crosslinked with a hard chain segment in TPEE, and the mechanical property is improved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The 3D printing composite material suitable for medical treatment and aviation is characterized by comprising the following components in parts by weight: 60-70 parts of TPEE, 1-5 parts of TPU, 20-30 parts of PLA, 0.5-1 part of genipin and 1-3 parts of modified nano titanium dioxide; the modified nano titanium dioxide comprises the following components: the ratio of the diphenyl siloxy phenyl trimethyl siloxane to the nano titanium dioxide is 1 (40-50).
2. The 3D printed composite material suitable for medical and aerospace according to claim 1, comprising the following components in parts by weight: 65 parts of TPEE, 3 parts of TPU, 25 parts of PLA, 0.8 part of genipin and 2 parts of modified nano titanium dioxide.
3. A preparation method of a 3D printing composite material suitable for medical treatment and aviation is characterized by comprising the following steps:
s1, preparing the raw material according to any one of claims 1-2;
s2, drying TPEE;
s3, extruding the raw materials in an extruder and then drawing wires to obtain the product.
4. The preparation method of the 3D printing composite material suitable for medical treatment and aviation according to claim 3, wherein in the step S2, the drying temperature is 80-120 ℃, and the drying time is 6-8 h.
5. The method for preparing 3D printed composite material suitable for medical and aeronautics according to claim 4, wherein the step S2 is drying until TPEE moisture content is less than 0.1%.
6. The preparation method of the 3D printing composite material suitable for medical treatment and aviation as claimed in claim 3, wherein in the step S3, the extruder is a tapered screw, and the length-diameter ratio is (24-28): 1, the compression ratio is (2.7-4): 1.
7. the preparation method of the 3D printing composite material suitable for medical treatment and aviation according to claim 6, wherein the temperature of the extruder barrel is 160-220 ℃, the temperature of the nozzle is 175-220 ℃, and the temperature of the die is 25-55 ℃.
8. The preparation method of the 3D printing composite material suitable for medical treatment and aviation according to claim 6, wherein the extrusion pressure of the extruder is 45-65 MPa, and the screw back pressure is 4-10 MPa.
9. The preparation method of the 3D printing composite material suitable for medical treatment and aviation is characterized in that the rotation speed of a screw of an extruder is 20-100 r/pm, and the molding period is 10-30 s.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530668A (en) * 2014-12-17 2015-04-22 广州飞胜高分子材料有限公司 3D printing material having self-cleaning antibacterial function as well as preparation method and application of 3D printing material
CN106633723A (en) * 2016-11-22 2017-05-10 福建师范大学 3D printing wire rod with pearl effect and preparation method thereof
CN107987497A (en) * 2017-12-22 2018-05-04 衢州听语信息科技有限公司 A kind of 3D printing material
AU2019100615A4 (en) * 2019-05-28 2019-07-18 Kingfa Sci Tech Co Ltd Polylactic acid 3D printing material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530668A (en) * 2014-12-17 2015-04-22 广州飞胜高分子材料有限公司 3D printing material having self-cleaning antibacterial function as well as preparation method and application of 3D printing material
CN106633723A (en) * 2016-11-22 2017-05-10 福建师范大学 3D printing wire rod with pearl effect and preparation method thereof
CN107987497A (en) * 2017-12-22 2018-05-04 衢州听语信息科技有限公司 A kind of 3D printing material
AU2019100615A4 (en) * 2019-05-28 2019-07-18 Kingfa Sci Tech Co Ltd Polylactic acid 3D printing material and preparation method thereof

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