CN113372658A

CN113372658A - 3D printing TPX composite material suitable for medical treatment and aviation and preparation method thereof

Info

Publication number: CN113372658A
Application number: CN202110638483.8A
Authority: CN
Inventors: 司涛; 孟建新; 兰晓虎; 门建永
Original assignee: Mingdan Medical Technology Co ltd
Current assignee: Mingdan Medical Technology Co ltd
Priority date: 2021-06-08
Filing date: 2021-06-08
Publication date: 2021-09-10
Anticipated expiration: 2041-06-08
Also published as: CN113372658B

Abstract

The invention relates to 3D printing, and provides a 3D printing TPX composite material suitable for medical treatment and aviation, which comprises the following components in parts by weight: 70-90 parts of TPX, 10-20 parts of PLA, 1-5 parts of TPU and 0.1-2 parts of Sumilizer GM. Through above-mentioned technical scheme, solved among the prior art 3D printing material and can't realize light, high strength, the problem of close skin simultaneously.

Description

3D printing TPX 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 TPX composite material suitable for medical treatment and aviation and a preparation method thereof.

Background

Compared with the traditional manufacturing technology, the 3D printing technology greatly reduces the links of processing procedures, shortens the processing period, and has more remarkable manufacturing efficiency when being used for products with complex structures. 3D printing technology will revolutionize not only in the development and manufacturing stage, but also in the logistics and marketing areas.

However, 3D printing materials are an important material basis for the development of 3D printing technology, and to some extent, the development of materials determines whether 3D printing can be applied more widely. At present, 3D printing materials mainly include engineering plastics, photosensitive resins, rubber-like materials, metal materials, ceramic materials, and the like.

Among the present 3D printing material, the 3D printing new material that can be applicable to medical rehabilitation can not be applicable to the 3D printing new material in the aviation field, can not realize light, excel in, close skin simultaneously.

Disclosure of Invention

The invention provides a 3D printing TPX composite material suitable for medical treatment and aviation and a preparation method thereof, and solves the problem that the 3D printing material in the prior art cannot realize light weight, high strength and skin friendliness at the same time.

The technical scheme of the invention is as follows:

A3D printing TPX composite material suitable for medical treatment and aviation comprises the following components in parts by weight: 70-90 parts of TPX, 10-20 parts of PLA, 1-5 parts of TPU and 0.1-2 parts of Sumilizer GM.

As a further technical scheme, the 3D printing TPX composite material suitable for medical treatment and aviation comprises the following components in parts by weight: TPX 80 parts, PLA 15 parts, TPU 3 parts and Sumilizer GM 1 part.

The invention also provides a preparation method of the 3D printing TPX composite material suitable for medical treatment and aviation, which comprises the following steps:

s1, drying the TPX;

s2, preheating TPX;

s3, feeding TPU, Sumilizer GM and the preheated TPX into an extruder for extrusion at a first stage;

and S4, adding PLA to the second stage, extruding and granulating the PLA and the mixture obtained in the S3, and drawing the yarns to obtain the product.

As a further technical scheme, in the step S1, the drying temperature of TPX is 90-120 ℃.

As a further technical proposal, in the step S1, TPX is dried to a water content of 0.025% or less.

As a further technical scheme, the preheating temperature in the step S2 is 210-230 ℃.

As a further technical scheme, in the step S3, the temperature is controlled to be 240-280 ℃, the rotating speed is 80-100 r/pm, and the injection pressure is 50-60 MPa.

As a further technical scheme, in the step S4, the temperature is controlled to be 240-280 ℃, the rotating speed is 120-140 r/pm, and the injection pressure is 45-55 MPa.

As a further technical solution, the injection pressure in the step S4 is smaller than the injection pressure in the step S3.

The invention has the beneficial effects that:

1. the yield strength of the 3D printing TPX composite material suitable for medical treatment and aviation can reach 200-220 kg/cm²After PLA and TPU are added as modifiers, the melt flow rate is 15-55 g/10min, and the composite material is very suitable for being used as a printing material for a 3D printer. No deformation at 150 deg.C or higher under no load, and the density after molding is 0.55-0.95 g/cc. TPX still has good air permeability after being added with the composite material, and the material has no suffocation and good skin affinity and is suitable for manufacturing a wearable covering piece for medical rehabilitation through a 3D printing rehabilitation splint use test. The composite material base material is compounded with the food contact safety certification of the United states Food and Drug Administration (FDA) and conforms to the European EN13432 standard, the European 2002/72/EC food contact safety certification and the Japanese JHOOSPA food contact safety certification.

2. Poly-4-methylpentene-1, referred to herein simply as TPX. TPX has a specific gravity of 0.83 and is the lightest of all plastics, so that TPX is selected as a main material of a new 3D printing material. However, TPX has a melting point of 240 ℃ and is the highest among polyolefins and has a large specific heat, so that a large amount of heat is supplied in the plasticizing step. TPX has a high melting point of about 240 ℃ and thus has excellent temperature resistance. TPX has a low melt viscosity and a large temperature change. The specific gravity is only 0.83, and is the smallest plastic. When the screw is extruded, the extrusion amount is less than that of PE and PP, and if the rotating speed of the screw is increased, the extrusion corrugation is increased rapidly, so that the safety production is difficult. Under the condition, the inventor sets a specific extrusion process, preheats the raw materials, and then extrudes the raw materials and other auxiliary materials to enhance the plasticizing capacity and improve the extrusion amount. Through the improvement of extrusion conditions, the extrusion amount can reach 70-80% of PP at most. On the other hand, the inventor extrudes PLA as an auxiliary material in sections with other raw materials, and the pressure of the second stage is controlled to be slightly smaller than that of the first stage, so that the processing performance of TPX can be improved, the heat required to be supplied in the plasticizing stage is reduced, the safe production is facilitated, the high screw rotating speed can be adapted, the extrusion amount can reach the same level as PP and PE through the process improvement of the two aspects, and a uniform wire rod with the diameter of 1.75mm can be obtained.

3. 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. However, PLA is weak against temperature changes and deforms at temperatures exceeding 50 ℃, thereby limiting its application in 3D printing materials. The temperature change resistance of the PLA can be improved by mixing the PLA and the TPX, the PLA has higher melt viscosity, the heat required by the TPX plasticizing stage can be reduced, and the PLA and the TPX are mutually cooperated to improve the processing performance of the composite material.

4. The chemical name of Sumilizer GM described in the present invention is 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, abbreviated as GM. The traditional antioxidant has poor effect of enhancing heat resistance, and GM can enhance the super heat resistance of the material, so that the melting point of the composite material is 190-240 ℃. The GM contains two active groups of phenolic hydroxyl and acrylate group, can effectively prevent the thermal aging of the polymer, can capture alkyl free radicals in TPX, PLA and TPU, and effectively prevent the thermal aging of TPX, PLA and TPU.

5. 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 has the characteristics of excellent high tension, high tensile force, toughness and aging resistance, and can improve the toughness of the composite material. The TPU WHT-1195 is adopted in the invention.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a graph showing the effect of temperature on the tensile yield strength of TPX composite and other polymeric materials in example 1 of the present invention.

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 inventive step, are intended to be within the scope of the present invention.

Example 1

S1, preparing materials: 80 parts of TPX, 15 parts of PLA, 3 parts of TPU and 1 part of Sumilizer GM;

s2, drying TPX at 110 ℃ until the water content is 0.02%;

s3, preheating TPX at 220 ℃;

s4, feeding the TPU, the Sumilizer GM and the preheated TPX into an extruder for extrusion in the first stage, controlling the temperature to be 240-280 ℃, the rotating speed to be 80-100 r/pm and the injection pressure to be 50-60 MPa;

and S5, adding PLA into the second stage, extruding and granulating the PLA and the mixture obtained in the S3, controlling the temperature to be 240-280 ℃, the rotating speed to be 120-140 r/pm, the injection pressure to be 45-55 MPa, and the retention time in the whole extrusion process to be 1-2 minutes, and drawing wires to obtain the product.

Example 2

Preparing materials: TPX 70 parts, PLA 10 parts, TPU 1 part, and Sumilizer GM 0.1 part, the preparation method is the same as example 1.

Example 3

Preparing materials: TPX 90 parts, PLA 20 parts, TPU 5 parts, and Sumilizer GM 2 parts, the preparation method is the same as example 1.

Example 4

Preparing materials: TPX 85 parts, PLA 18 parts, TPU 2 parts, and Sumilizer GM 0.5 parts, the preparation method is the same as example 1.

Example 5

S1, preparing materials: 80 parts of TPX, 15 parts of PLA, 3 parts of TPU, 1 part of Sumilizer GM and 0.8 part of aluminum starch octenyl succinate;

s2, drying TPX at 120 ℃ until the water content is 0.01%;

s3, preheating TPX at 220 ℃;

s4, feeding TPU, Sumilizer GM, aluminum starch octenyl succinate and preheated TPX into an extruder for first-stage extrusion, controlling the temperature to be 240-280 ℃, the rotating speed to be 80-100 r/pm and the injection pressure to be 50-60 MPa;

Comparative example 1

The same procedure as in example 1 was repeated except that Sumilizer GM was not added.

Comparative example 2

S1, preparing materials: TPX 80 parts, TPU 3 parts and Sumilizer GM 1 part;

s2, drying TPX at 110 ℃ until the water content is 0.02%;

s3, preheating TPX at 220 ℃;

s4, feeding the TPU, the Sumilizer GM and the preheated TPX into an extruder for first-stage extrusion, controlling the temperature to be 240-280 ℃, the rotating speed to be 80-100 r/pm, the injection pressure to be 50-60 MPa, the residence time in the whole extrusion process to be 1-2 minutes, and drawing wires to obtain the product.

Comparative example 3

The feed was the same as in example 1, but TPX was not preheated.

Comparative example 4

s2, drying TPX at 110 ℃ until the water content is 0.02%;

s3, preheating TPX at 220 ℃;

s4, feeding the TPU, the Sumilizer GM, the PLA and the preheated TPX into an extruder for extrusion, controlling the temperature to be 240-280 ℃, the rotating speed to be 80-100 r/pm, the injection pressure to be 50-60 MPa, the residence time in the whole extrusion process to be 1-2 minutes, and pulling wires to obtain the product.

The Melt Flow Rate (MFR) test was carried out according to GB/T3682-2000 under the test conditions of 240 ℃ at a load of 10 kg. Other test data for examples and comparative examples are shown in table 1.

TABLE 1 test results of examples and comparative examples

The effect of temperature on the tensile yield strength of the TPX composite material obtained in example 1 of the present invention, polycarbonate, propylene copolymer, and low density polyethylene is shown in fig. 1, and it can be seen that the example can maintain a certain strength at 150 ℃, but other high molecular materials are softened.

In the embodiment 5 of the invention, aluminum starch octenyl succinate is added, so that the melt viscosity of the high polymer material can be improved, the 3D printing composite material has proper melt fluidity, the yield strength of the composite material is improved, the heat resistance of the material is improved, and the aluminum starch octenyl succinate can be attached to the ultraviolet resistance of the composite material.

Compared with the example 1, the comparative example 1 is not added with the Sumilizer GM, and the obtained composite material has poor heat resistance and poor melt flowability, so that the jet head is difficult to extrude a wire for printing, and the printing quality is influenced. Comparative example 2, in which no PLA was added, produced a composite material that was relatively lightweight, but had a melt flow rate that was too low, resulting in poor processability, and required a higher temperature during processing. In comparative example 3, the heat resistance and the mechanical property of the final composite material are reduced without preheating the TPX, and the inventor analyzes that the heat resistance and the mechanical property of the final composite material are probably caused by that the processability of the TPX which is not preheated is poor and the plasticizing capability is poor, so that the performances of the final product are poor in all aspects. In comparative example 4, the sectional extrusion was not performed, which is the first technical solution of the present inventors, but the present inventors found that the final product obtained by this process is inferior in all properties, and finally found that the solid and the melt are separated and plasticized by the sectional extrusion, which not only increases the extrusion amount, but also improves the heat resistance and mechanical properties of the final product.

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

1. The 3D printing TPX composite material suitable for medical treatment and aviation is characterized by comprising the following components in parts by weight: 70-90 parts of TPX, 10-20 parts of PLA, 1-5 parts of TPU and 0.1-2 parts of Sumilizer GM.

2. The 3D printed TPX composite material suitable for medical and aerospace use according to claim 1, comprising the following components in parts by weight: TPX 80 parts, PLA 15 parts, TPU 3 parts and Sumilizer GM 1 part.

3. A preparation method of a 3D printing TPX composite material suitable for medical treatment and aviation is characterized by comprising the following steps:

s1, drying the TPX;

s2, preheating TPX;

4. The preparation method of 3D printing TPX composite material suitable for medical treatment and aviation according to claim 3, wherein the step S1 is to dry TPX at 90-120 ℃.

5. The method for preparing a 3D printed TPX composite material suitable for medical and aerospace use according to claim 4, wherein in step S1 TPX is dried to a moisture content of 0.025% or less.

6. The preparation method of the 3D printing TPX composite material suitable for medical treatment and aviation according to claim 3, wherein the preheating temperature in the step S2 is 210-230 ℃.

7. The preparation method of the 3D printing TPX composite material suitable for medical treatment and aviation according to claim 3, wherein in the step S3, the temperature is controlled to be 240-280 ℃, the rotating speed is 80-100 r/pm, and the injection pressure is 50-60 MPa.

8. The preparation method of the 3D printing TPX composite material suitable for medical treatment and aviation according to claim 3, wherein in the step S4, the temperature is controlled to be 240-280 ℃, the rotating speed is 120-140 r/pm, and the injection pressure is 45-55 MPa.

9. The method for preparing a 3D printed TPX composite suitable for medical and aerospace use according to claim 8, wherein the injection pressure in step S4 is less than the injection pressure in step S3.