CN105773976A - Fiber-stage anti-microbial product 3D printing method based on reaction extrusion - Google Patents

Abstract

The invention relates to a 3D printing method of fiber-level antibacterial products based on reactive extrusion, which melts lactam monomers and/or lactone monomers with auxiliary agents and plasticizers and then performs polymerization under the action of a catalyst. Antibacterial agents are added before or during the process to obtain the target polymer; then the target polymer is 3D printed by fusion deposition, and then the final product is obtained after heat treatment. The invention adopts a high-precision and high-adaptability 3D printer, which has high molding precision, high efficiency, good mechanical properties of products, and good dispersion of functional components; the process of directly producing products from polymerized monomers improves production flexibility and avoids It eliminates the warping of semi-crystalline polymers such as nylon and polyester due to crystallization and large temperature differences, and even fails to print. The invention broadens the types of fused deposition 3D printing materials, improves product quality, and is widely used in the fields of automobile materials, medical device materials and the like.

Description

A 3D printing method for fiber-level reactive extrusion-based antimicrobial products

technical field

The invention belongs to the technical field of 3D printing, and relates to a 3D printing method of fiber-level antibacterial products based on reaction extrusion, in particular to a 3D printing method from monomers directly to antibacterial products.

Background technique

3D printing technology is a rapid prototyping technology that is gradually becoming popular at present. This is a green desktop rapid prototyping technology, which has the advantages of small size, low cost, low pollution, and convenient use. The basic principle is to use polymer materials as the base material, adopt fused accumulation molding or fused deposition molding technology, complete the structure and formation of object pairs by layer-by-layer printing, and finally form products by layer-by-layer stacking, which can be built layer by layer under precise positioning. various three-dimensional objects.

Using the characteristics of 3D printing, it can be controlled by software, and through the transformation of equipment, materials with specific functions can be printed out. Polymer materials currently used for 3D printing include acrylonitrile-butadiene-styrene terpolymer (ABS), polylactic acid (PLA), nylon (PA), polycarbonate (PC) and polyvinyl alcohol (PVA). etc., mainly polymer products. At present, with the gradual development of 3D printer technology, the scope of product use is gradually expanding. The market's requirements for products not only stay in the performance of the body, but also increase the functional requirements for 3D printing products.

The patent "3D printing material with self-cleaning and antibacterial function and its preparation method and application" (CN104530668A) discloses a method for preparing a functional 3D printing material: the 3D printing material contains the following components: polylactic acid or acrylonitrile-butane 70-85 parts of high polymers such as ethylene-styrene terpolymer; 1-5 parts of pigment powders such as titanium dioxide and red powder; 1-5 parts of inorganic fillers such as superfine calcium carbonate, superfine silica and talcum powder , Nano antibacterial agent titanium dioxide 0.5-1.5 parts, isoprene rubber, thermoplastic polyester elastomer binder 10-20 parts. In this invention, the aforementioned components are uniformly mixed; then the uniformly mixed material is put into a single-screw plastic extruder, extruded, cooled and shaped, dried, pulled, and wound to obtain a 3D printing material with self-cleaning and antibacterial functions. The patent "a flame-retardant composite material for 3D printing and its preparation method" (CN104479349A) provides a flame-retardant composite material for 3D printing, including the following raw materials by weight: 60-95 parts by weight of nylon resin The lubricant of 0.3-2 weight part of the ABS resin of 5-40 weight part; The compatibilizer of 5-20 weight part; The antioxidant of 0.2-1 weight part; The amorphous red phosphorus of 5-30 weight part, the The 3D printing raw materials and their products prepared by the method have certain flame retardant properties. The patent "a conductive 3D printing plastic line and its production method" (CN103788565A) discloses a conductive 3D printing plastic line and its production method, which includes the following components according to the mass fraction ratio: 100 parts of ABS, 35-55 parts of nano conductive carbon black, 0.5-3 parts of titanate coupling agent, the invention obtains 3D printing plastic wire with conductivity.

From the perspective of existing technology, functional composite materials and products for 3D printing have been reported, but there are still some problems, mainly in the following aspects: Among the polymer raw materials, mainly pre-polymerized materials cannot be quickly regulated The bulk properties of the material; during the 3D printing process, the polymer needs to be remelted, and because the melting tube of the conventional 3D printing is short, in order to ensure the melting of the polymer, the heating temperature needs to be raised to 20-50°C above the melting point of the polymer , This secondary processing process affects the performance of the polymer itself, and it is easy to produce low molecules, and bubbles are prone to appear during the printing process, which affects the performance of the part. At the same time, the remelting process is also a waste of energy. In the process of making functionalized 3D printing raw materials, the method of blending is usually used, which is difficult to achieve uniform distribution of functional components, especially nano-scale functional powders are prone to agglomeration during the blending process, resulting in functional The effect is reduced and the product quality is not stable, and there may be clogging of the nozzle due to the accumulation of functional components. For nylon and polyester materials, they have strong water absorption, relatively poor chemical stability, inconvenient storage of materials, and are not suitable for industrialization. These are important factors that limit the development of 3D printing nylon and polyester materials.

Contents of the invention

In order to overcome the deficiencies of the prior art, the present invention provides a 3D printing method of fiber-level antibacterial products based on reaction extrusion, which is a 3D printing method from monomers directly to products. The invention adopts a 3D printer with high precision, high efficiency and high adaptability, uses polymer monomers as raw materials, adds a certain amount of functional components, and obtains 3D printed products with specific functions through 3D printer molding. This method is directly from the monomer to the product, which reduces the cooling and remelting steps in the conventional 3D printing steps, reduces the cost, and also avoids the impact of the degradation of the secondary melting process on the product quality, and also avoids the degradation of the material due to water absorption, etc. Degradation and performance degradation during processing; direct products from monomers can reduce the processing and molding temperature, avoiding the problem of dimensional changes caused by thermal shrinkage due to excessive temperature differences; at the same time, functional components and Uniform blending of monomers, or adding functional components during the polymerization process, to achieve in-situ polymerization of functional components. Compared with conventional screw blending, it improves the dispersion effect of functional components, avoids the agglomeration of functional components, and improves the product quality. High quality, avoiding nozzle clogging; and strong controllability, the production process can be adjusted according to product quality requirements to achieve single-line multi-variety production with good production continuity; at the same time, the use of high-precision, high-efficiency and high-adaptability 3D printers improves the degree of freedom of molding, Production speed and molding precision.

A fiber-level 3D printing method based on reactive extrusion antibacterial products of the present invention, after melting lactam monomers and/or lactone monomers with auxiliary agents and plasticizers, the polymerization reaction is carried out under the action of a catalyst. Adding an antibacterial agent before or during the process to obtain the target polymer; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is heat-treated to obtain the final product;

The plasticizer is more than one of dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, and rare earth; an appropriate amount of plasticizer is added to the printing raw materials, The crystallinity of the semi-crystalline polymer is reduced, and the melting point of the polymer is lowered so that it can be printed at a lower temperature. At the same time, the plasticizer can interact with multiple molecular chains in the system at the same time, so that the molecular chains Form a network structure and reduce the mobility of molecular chains. The plasticizer is the crosslinking center and plays the role of micro-crosslinking, so that the difference in fluidity of the polymer before and after melting is reduced.

The heat treatment refers to keeping at 100-180° C. for 3-60 minutes. 3D printed parts, the polymerization reaction is not completely completed; the polymerization reaction system used in the present invention, at a certain temperature, the polymer described in the present invention still has polymerization activity under the action of a catalyst, which can be obtained by heat treatment at a certain temperature For a period of time, the polymerization reaction is continued to obtain a product with a specific molecular weight, and the performance of the product can be adjusted.

As a preferred technical solution:

A fiber-level 3D printing method based on reactive extrusion antibacterial products as described above, the lactam monomer is valerolactam, caprolactam, enantholactam, capryllactam, caprolactam, decanolactam, decaprolactam More than one of monolactam and laurolactam; the lactone monomer is valerolactone, caprolactone, enantholactone, capryllactone, decanolactone, dedecalactone, undecalactone, More than one of laurolactone; the catalyst is more than one of sodium hydroxide, potassium hydroxide, and organometallic compounds; the organometallic compound is methyl, ethyl, propyl, butyl, benzene A stable compound formed by combining one of the bases with one of the sodium, potassium, calcium, and magnesium; the auxiliary agent is more than one of the acetyl caprolactam, isocyanate, carbamate, carbonate, and sulfonate .

As mentioned above, a fiber-level 3D printing method based on reactive extrusion antibacterial products can add antibacterial agents before or during polymerization to endow products with antibacterial functions. The antibacterial agent is nano-titanium dioxide, zinc oxide, iron oxide, chitosan, nano-silver, nano-copper or quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Wherein, R ₁ , R ₂ =C8-C20, R ₁ , R ₂ are the same or different, and X ^- is Cl ^- , Br ^- , I ^- .

A fiber-level 3D printing method based on reactive extrusion antibacterial products as described above, the temperature of the polymerization reaction is 150-300°C, the amount of catalyst added is 0.01-1wt%, and the amount of additives added is 0.1-5wt% , the added amount of the plasticizer is 10-40wt%, the added amount of the antibacterial agent is 0.01-10wt% of the monomer, and the number average molecular weight of the target polymer is 1000-20000.

A fiber-level 3D printing method based on reaction-extruded antibacterial products as described above, the polymerization reaction is completed in a screw extruder, and the number-average molecular weight of the polymer is precisely regulated by controlling the screw temperature and catalyst content; The screw extruder includes a screw, an extrusion motor connected to the screw, a heating ring, a temperature sensor and a metering pump; the screw is one of single screw, twin screw, and triple screw, and the aspect ratio is 12-48, etc. The screw pitch, the helix angle is 14-18°, the screw groove depth is 1.5-3.5mm, and the surface roughness is Ra0.4-0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, supported by a vertical shaft fixed; the heating ring and the temperature sensor are installed outside the screw rod.

A fiber-level 3D printing method based on reaction-extruded antibacterial products as described above, the steps of the 3D printing include:

(1) Use CAD or CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately and quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system, and the forming platform moves in the X-Y plane under the control of the computer system; when the temperature of the extruded polymer is low After the curing temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part. The deposited material at the end of one layer is quickly solidified and bonded with the surrounding materials. The deposition, so layer by layer to form a three-dimensional workpiece.

As mentioned above, a fiber-level 3D printing method based on reactive extrusion antibacterial products, the moving speed of the forming platform is 10-10000mm/s; the melt flow rate of the metering pump is 0.1-3000L/h, and the precision It is ±0.1%, so as to ensure the precise control of the extrusion volume during the molding process, ensure the stability of the entire mechanism in continuous work, and at the same time play the role of pressurization to ensure the smooth extrusion of high-viscosity thermoplastic materials.

A fiber-level 3D printing method based on reaction-extruded antibacterial products as described above, the 3D printing adopts a three-dimensional printer device, including a screw extrusion mechanism, a three-dimensional motion mechanism, a working platform mechanism and a computer control and drive arranged in sequence system, the screw extrusion mechanism is fixed relative to the working platform and the molded parts; the working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and driving system is used for the automatic control and driving of the whole machine .

A kind of 3D printing method of the antibacterial product based on reaction extruding of a kind of fiber level as above, described three-dimensional kinematic mechanism is made up of X-axis kinematic mechanism, Y-axis kinematic mechanism and Z-axis kinematic mechanism; Said X-axis kinematic mechanism comprises X Axis motor and lead screw guide; the Y-axis movement mechanism consists of a Y-axis motor and a lead screw guide; the Z-axis movement mechanism consists of a Z-axis motor and a lead screw guide; the X-axis support is fixed on the Y-axis wire On the bar nut, the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base.

As mentioned above, a fiber-level 3D printing method based on reactive extrusion antibacterial products, the working platform mechanism is composed of a forming working platform, a forming working platform support frame and a leveling nut; the forming working platform is installed on the The X-axis motion mechanism has a suitable friction coefficient, which can well fix the first layer of printing materials; the forming work platform support frame is fixedly connected with the Y-axis motion mechanism, and is fixed with the Z-axis motion slider at the same time. Connected, it can move up and down linearly with the Z axis; the leveling nut can adjust the height of the forming work platform to ensure the verticality requirement of the forming work platform plane to the discharge port of the nozzle.

As mentioned above, a fiber-level 3D printing method based on reactive extrusion of antibacterial products, the screw extrusion mechanism is vertical or horizontal, and it includes a feeding cylinder, a screw extrusion device, and a screw extrusion device. The nozzle system; the feeding cylinder includes a feeding cylinder connected to the screw extruder, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a delivery pipeline, a nozzle, a turntable, a cut-off Composed of a valve and a cooling device; the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes at least one, and its shape is one or more of circular, rectangular, triangular, rhombus, and the nozzle contains 1-1000 spray holes , the shape of the nozzle hole is one or more of circular, rectangular, triangular, rhombus, cross-shaped, in-line, Y-shaped, the diameter of the nozzle outlet is 10-500μm, and a cooling device is installed above the nozzle, and the cooling device is a ring Blowing or side blowing, the wind temperature is 15-25°C, and the wind speed is 0.01-0.1m/s; the cut-off valve is installed above the cooling device of the nozzles, and is used to control the working state of the multiple nozzles.

Beneficial effect:

Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

(1) By adopting the combination of screw and metering pump, the present invention realizes the precise control of the amount of wire output from the nozzle and the stability of the wire output during the molding process, and improves the molding accuracy; at the same time, through the pressurization of the metering pump, it realizes molding of high-viscosity thermoplastic Polymers, thereby broadening the range of options for molding materials and making them highly adaptable.

(2) The present invention can effectively improve the extrusion speed of the material from the nozzle through the boosting effect of the metering pump, and accumulate the molded parts faster, thereby improving the molding efficiency; in addition, the booster can use a nozzle with a smaller diameter, reducing The cross-sectional area of the extruded material is small, and better molding accuracy is achieved. At the same time, due to the large increase in the specific surface area of the extruded wire, its cooling rate increases, which can further increase the molding speed, and the increase in the molding speed can greatly increase extrusion. The degree of orientation of the filaments can be improved, thereby improving the mechanical properties of the molded parts.

(3) By adopting multiple nozzles and multiple nozzles in the present invention, multiple molded parts can be molded at the same time, thereby effectively improving the molding efficiency and meeting the requirements of batch molding.

(4) Since the fused deposition 3D printing heating tube is relatively short, in order to completely melt the polymer, the melting temperature must be increased, while the present invention reduces the steps of cooling and remelting in the conventional 3D printing steps from the monomer directly to the product, reducing the The cost is reduced; the secondary melting process is easy to produce small molecules and cause degradation. Small molecules will form stress concentration points in the workpiece, which greatly reduces the mechanical properties of the workpiece, and degradation will reduce the molecular weight of the polymer. The reduction of molecular weight means that the material The reduction of the mechanical properties of itself brings about the reduction of the mechanical properties of the product. The present invention eliminates the secondary melting process, thereby avoiding the influence of small molecules produced in the secondary melting process and other degradation processes on product quality.

(5) From the monomer to the product, the present invention reduces the steps of cooling and remelting in the conventional 3D printing steps, avoids the remelting process of the slices, can reduce the processing and molding temperature, and also avoids the printing materials due to water absorption during storage. The decline of the material quality and the degradation caused by it; the present invention can precisely control the polymerization temperature, control the molecular weight of the polymer during printing, and then obtain the finished product through post-processing, which can reduce the printing temperature and avoid thermal damage due to excessive temperature difference. The problem of dimensional changes caused by shrinkage; the invention can also obtain products with different properties by adjusting the post-treatment process, and at the same time eliminate thermal history, heat setting, and further improve the performance of the product.

(6) In conventional fused deposition 3D printing, usually one raw material can only print products with one performance. In this invention, from the monomer directly to the product, different products can be obtained by adjusting the polymerization process and formula, which greatly improves the flexibility of product production. , reducing the dependence of product performance on raw materials.

(7) The present invention introduces an appropriate amount of plasticizer in the printing raw material, which reduces the crystallinity of the semi-crystalline polymer, reduces the melting point of the polymer, enables printing at a lower temperature, and reduces the printing temperature and The difference between ambient temperatures avoids the shrinkage and performance degradation of parts caused by crystallization and temperature differences; at the same time, the plasticizer can interact with multiple molecular chains in the system at the same time, so that the molecular chains form a network Structure, reducing the mobility of molecular chains, plasticizers are cross-linking centers, which play the role of micro-cross-linking, so that the difference in fluidity of the polymer before and after melting is reduced, which is conducive to the shape retention of the filaments extruded from the nozzle . At the same time, the plasticizer can play a lubricating role, so that the nozzle will not be blocked during the FDM forming process, and the 3D printed product is easy to separate the support material or the forming platform, and the forming is more stable.

(8) The present invention realizes the uniform blending of functional components and monomer beating, or adds functional components during the polymerization process to realize in-situ polymerization of functional components, and improves the dispersion effect of functional components compared with conventional screw blending , to avoid the agglomeration of functional components, improve product quality, and avoid nozzle clogging.

(9) Compared with conventional fused deposition 3D printing, the diameter of the nozzle hole outlet used in the present invention can be as small as 10 μm, reaching the fiber-level standard. This design can greatly improve the accuracy of 3D printing, make 3D printing more delicate, and improve 3D printing. The quality and fineness of printed products have also improved the scope of application of 3D printing.

detailed description

The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer valerolactam and the lactone monomer valerolactone with the addition of 0.1wt% of the auxiliary agent acetyl caprolactam and the addition of 10wt% % plasticizer dibutyl phthalate; after melting, under the action of 0.01wt% catalyst sodium hydroxide, the polymerization reaction is carried out at a temperature of 150°C, and 0.01wt% antibacterial agent nanometer is added before polymerization Titanium dioxide, the target polymer that obtains number-average molecular weight is 1000, and polymerization reaction is finished in screw extruder, and screw extruder comprises screw, the extruding motor that connects screw, heating ring, temperature sensor and metering pump; Screw is a single screw. , the aspect ratio is 12, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.4; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, supported by a vertical shaft Fixed; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 100°C for 3 minutes to obtain the final product, and the 3D printing adopts a three-dimensional printer device, including The screw extrusion mechanism, the three-dimensional motion mechanism, the working platform mechanism and the computer control and drive system are arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded parts; the working platform mechanism is installed on the three-dimensional movement mechanism; the computer control and The driving system is used for the automatic control and driving of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; the X-axis motion mechanism is composed of X-axis motor and screw guide rail; the Y-axis motion The mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis movement mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut, and the Y-axis support is fixed on the support frame of the forming work platform. The shaft is fixed vertically on the base; the working platform mechanism is composed of a forming working platform, a forming working platform support frame and a leveling nut; the forming working platform is installed on the X-axis movement mechanism, which has a suitable friction coefficient and can be well fixed The first layer of printing materials; the supporting frame of the forming work platform is fixedly connected with the Y-axis motion mechanism, and is also fixedly connected with the Z-axis movement slider, which can move up and down linearly with the Z-axis; the leveling nut can adjust the position of the forming work platform Height, to ensure the verticality requirements of the forming working platform plane to the nozzle outlet; the screw extrusion mechanism is vertical, which includes the feeding cylinder, the screw extrusion device and the nozzle system connected with the screw extrusion device; the feeding cylinder includes The feeding cylinder connected with the screw extrusion device is in the shape of a round funnel, and a drying heater is installed outside; the nozzle system is composed of a conveying pipeline, a nozzle, a turntable, a shut-off valve and a cooling device; the nozzle is installed at the end of the conveying pipeline, The number of nozzles is one, and its shape is circular. The nozzle contains 1 spray hole, the shape of the spray hole is circular, and the diameter of the spray hole outlet is 10 μm. 15°C, the wind speed is 0.01m/s; the shut-off valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 10mm/s. The melt flow rate of the pump is 0.1L/h, and the precision is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The deposited material at the end of one layer solidifies rapidly and Bonded with the surrounding materials, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 2

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer caprolactam and the lactone monomer caprolactone are added with an additive of 5wt% isocyanate and an added amount of 40wt% plasticizer Citric acid ester; After melting, under the action of 1wt% catalyst potassium hydroxide, the temperature is 300°C to carry out polymerization reaction. During the polymerization reaction, add 10wt% antibacterial agent zinc oxide to obtain a number average molecular weight of 20000 The target polymer, the polymerization reaction is completed in the screw extruder, the screw extruder includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a metering pump; the screw is a twin screw, and the aspect ratio is 48, etc. The screw pitch, the helix angle is 18°, the depth of the screw groove is 3.5mm, and the surface roughness is Ra0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw and fixed by the vertical support shaft; the heating ring and the temperature sensor are installed On the outside of the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 180°C for 60 minutes to obtain the final product. Three-dimensional motion mechanism, working platform mechanism and computer control and drive system, the screw extrusion mechanism is fixed relative to the working platform and molding parts; the working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the whole machine Automatic control and drive; three-dimensional motion mechanism consists of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion mechanism includes X-axis motor and screw guide rail; Y-axis motion mechanism includes Y-axis motor and lead screw Composed of guide rails; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut, the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base The working platform mechanism is composed of forming working platform, forming working platform support frame and leveling nut; forming working platform is installed on the X-axis motion mechanism, which has a suitable friction coefficient and can well fix the first layer of printing materials; forming work The platform support frame is fixedly connected with the Y-axis motion mechanism, and is also fixedly connected with the Z-axis motion slider, which can move up and down linearly with the Z-axis; the leveling nut can adjust the height of the forming work platform to ensure that the plane of the forming work platform is discharged to the nozzle The verticality requirements of the mouth; the screw extrusion mechanism is horizontal, which includes the feeding cylinder, the screw extrusion device and the nozzle system connected with the screw extrusion device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, The feeding cylinder is in the shape of a round funnel, and a drying heater is installed outside; the nozzle system is composed of a conveying pipe, nozzle, turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipe, the number of nozzles includes 2, and its shape is rectangular , the nozzle contains 1000 nozzle holes, the shape of the nozzle holes is rectangular, and the diameter of the nozzle outlet is 500μm. At the same time, a cooling device is installed above the nozzle. Installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 10000mm/s. The melt flow rate of the pump is 3000L/h, and the accuracy is -0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The deposited material at the end of one layer solidifies rapidly and Bonded with the surrounding materials, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 3

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer enantholactam and the lactone monomer enantholactone with an additive amount of 0.5wt% carbamate and an additive amount of 15wt% plasticizer gallium chloride; after melting, under the action of a stable compound formed by adding 0.08wt% of the catalyst methyl group and sodium, the temperature is 250°C to carry out the polymerization reaction. During the polymerization reaction, add The antimicrobial iron oxide of 0.9wt% obtains the target polymer that the number average molecular weight is 10000, and polymerization reaction is finished in screw extruder, and screw extruder comprises screw, the extruding motor that connects screw, heating ring, temperature sensor and Metering pump; the screw is three-screw, the length-to-diameter ratio is 45, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.8mm, and the surface roughness is Ra0.6; the extrusion motor connected to the screw is fixedly installed on the right side of the screw The side is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 120°C for 10 minutes to obtain the final product, 3D The printing adopts a three-dimensional printer device, including a screw extrusion mechanism, a three-dimensional movement mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part; the working platform mechanism is installed on the three-dimensional On the motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of the X-axis motion mechanism, the Y-axis motion mechanism and the Z-axis motion mechanism; the X-axis motion mechanism includes the X-axis motor and the wire The Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut, and the Y-axis support is fixed on the molding On the support frame of the working platform, the Z-axis is vertically fixed on the base; the working platform mechanism is composed of the forming working platform, the forming working platform support frame and the leveling nut; the forming working platform is installed on the X-axis movement mechanism, with suitable friction coefficient, which can fix the first layer of printing material very well; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move up and down linearly with the Z-axis; the leveling nut can be adjusted The height of the forming work platform ensures that the plane of the forming work platform is perpendicular to the outlet of the nozzle; the screw extrusion mechanism is vertical, which includes a feeding cylinder, a screw extrusion device and a nozzle system connected to the screw extrusion device; The feeding cylinder includes the feeding cylinder connected with the screw extrusion device. The feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system is composed of a conveying pipeline, a nozzle, a turntable, a shut-off valve and a cooling device; the nozzle is installed on the At the end of the pipeline, the number of nozzles includes 3, which are triangular in shape. The nozzles contain 800 nozzle holes. The wind temperature is 20°C and the wind speed is 0.05m/s; the shut-off valve is installed in the cooling above the device;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is transported forward, and is accurately and quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 100mm/s , the melt flow rate of the metering pump is 1000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part, and the deposition material of the end layer solidifies rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 4

A fiber-level 3D printing method for antibacterial products based on reactive extrusion, the lactam monomer capryllactam and the lactone monomer capryllactone are added with 2wt% additive carbonate and 20wt% Plasticizer Lithium Chloride; After melting, under the action of a stable compound formed by the combination of 0.07wt% ethyl and potassium, the polymerization reaction is carried out at a temperature of 200°C. During the polymerization reaction, 2.5wt% antibacterial Chitosan is used to obtain the target polymer with a number average molecular weight of 1000. The polymerization reaction is completed in a screw extruder. The screw extruder includes a screw, an extrusion motor connected to the screw, a heating ring, a temperature sensor and a metering pump; It is a single screw with a length-to-diameter ratio of 15, equal pitch, a helix angle of 16°, a screw groove depth of 1.8mm, and a surface roughness of Ra0.6; the extrusion motor connected to the screw is fixedly installed on the right side of the screw. The straight support shaft is fixed; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 100°C for 60 minutes to obtain the final product, and the 3D printing uses a three-dimensional printer The device includes a screw extruding mechanism, a three-dimensional motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence, the screw extruding mechanism is fixed relative to the working platform and the molded part; the working platform mechanism is installed on the three-dimensional moving mechanism; The computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; the X-axis motion mechanism is composed of X-axis motor and screw guide rail; The Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut, and the Y-axis support is fixed on the support frame of the forming work platform Above, the Z axis is vertically fixed on the base; the working platform mechanism is composed of a forming working platform, a forming working platform support frame and a leveling nut; The first layer of printing material is well fixed; the supporting frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and at the same time, it is fixedly connected with the Z-axis movement slider, which can move up and down linearly with the Z-axis; the leveling nut can adjust the forming The height of the working platform ensures that the plane of the forming working platform is perpendicular to the discharge port of the nozzle; the screw extrusion mechanism is horizontal, which includes a feeding cylinder, a screw extrusion device and a nozzle system connected to the screw extrusion device; The barrel includes a feed barrel connected to the screw extrusion device. The feed barrel is in the shape of a round funnel, and a drying heater is installed outside; the nozzle system is composed of a conveying pipeline, a nozzle, a turntable, a stop valve and a cooling device; the nozzle is installed on the conveyor At the end of the pipeline, the number of nozzles includes one, which is diamond-shaped. The nozzle contains 500 nozzle holes. The shape of the nozzle holes is diamond-shaped, and the diameter of the nozzle outlet is 50 μm. The temperature is 19°C, and the wind speed is 0.02m/s; the shut-off valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 6000mm/s , the melt flow rate of the metering pump is 1500L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 5

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer caprolactam and the lactone monomer caprolactone are added with an additive sulfonate of 3.5wt% and an added amount of 25wt % plasticizer calcium chloride; after melting, under the action of a stable compound formed by the combination of 0.3wt% propyl and calcium, the polymerization reaction is carried out at a temperature of 160°C. During the polymerization reaction, 3wt% antibacterial Agent nano-silver, the target polymer that obtains number-average molecular weight is 1000, polyreaction is finished in screw extruder, and screw extruder comprises screw, the extruding motor that connects screw, heating ring, temperature sensor and metering pump; Screw is Single screw, length-to-diameter ratio is 32, equal pitch, helix angle is 16°, screw groove depth is 1.5mm, surface roughness is Ra0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, and is driven by a vertical The support shaft is fixed; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 110°C for 12 minutes to obtain the final product, and the 3D printing adopts a three-dimensional printer device , including a screw extrusion mechanism, a three-dimensional motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part; the working platform mechanism is installed on the three-dimensional movement mechanism; the computer The control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; the X-axis motion mechanism is composed of X-axis motor and screw guide rail; Axis motion mechanism consists of Y-axis motor and screw guide rail; Z-axis motion mechanism consists of Z-axis motor and screw guide rail; X-axis support is fixed on the Y-axis screw nut, and Y-axis support is fixed on the support frame of the forming work platform , the Z axis is vertically fixed on the base; the working platform mechanism is composed of a forming working platform, a forming working platform support frame and a leveling nut; The first layer of printing material is fixed; the supporting frame of the forming working platform is fixedly connected with the Y-axis movement mechanism, and at the same time, it is fixedly connected with the Z-axis moving slider, which can move up and down linearly with the Z-axis; the leveling nut can adjust the height of the forming working platform , to ensure the verticality requirements of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is vertical, which includes the feeding cylinder, the screw extrusion device and the nozzle system connected with the screw extrusion device; the feeding cylinder includes The feeding cylinder connected to the screw extrusion device is in the shape of a round funnel, and a drying heater is installed outside; the nozzle system is composed of a conveying pipeline, a nozzle, a turntable, a shut-off valve and a cooling device; the nozzle is installed at the end of the conveying pipeline, and the nozzle The number includes 10, the shape of which is rhombus, the nozzle contains 600 nozzle holes, the shape of the nozzle hole is cross-shaped, the diameter of the nozzle outlet is 80 μm, and a cooling device is installed above the nozzle, the cooling device is side blowing, and the air temperature is 22 ℃, the wind speed is 0.09m/s; the shut-off valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD or CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 6000mm/s. The melt flow rate of the pump is 100L/h, and the accuracy is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The surrounding materials are bonded and formed, and the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 6

A 3D printing method for fiber-grade antibacterial products based on reactive extrusion, the lactam monomer decanolactam and the lactone monomer dedecalactone with the additive acetyl caprolactam with an additive amount of 4wt% and an additive amount of 23wt% plasticizer clay; after melting, under the action of a stable compound formed by adding 0.2wt% catalyst butyl and magnesium, the polymerization reaction is carried out at a temperature of 160°C. During the polymerization reaction, 5wt% antibacterial agent is added Nano-copper, the target polymer that obtains number-average molecular weight is 1200, and polymerization reaction is finished in screw extruder, and screw extruder comprises screw, the extruding motor that connects screw, heating ring, temperature sensor and metering pump; Screw is single The screw has an aspect ratio of 30, equal pitch, a helix angle of 14°, a screw groove depth of 1.8mm, and a surface roughness of Ra0.5; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, supported by a vertical The shaft is fixed; the heating ring and temperature sensor are installed on the outside of the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 130°C for 30 minutes to obtain the final product, and the 3D printing adopts a three-dimensional printer device. It includes screw extrusion mechanism, three-dimensional motion mechanism, working platform mechanism and computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded parts; the working platform mechanism is installed on the three-dimensional movement mechanism; computer control The driving system is used for the automatic control and driving of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; the X-axis motion mechanism is composed of X-axis motor and screw guide rail; The motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut, and the Y-axis support is fixed on the support frame of the forming work platform. The Z axis is vertically fixed on the base; the working platform mechanism is composed of the forming working platform, the forming working platform support frame and the leveling nut; the forming working platform is installed on the X axis movement mechanism, which has a suitable friction coefficient and can be well The first layer of printing material is fixed; the supporting frame of the forming working platform is fixedly connected with the Y-axis movement mechanism, and at the same time, it is fixedly connected with the Z-axis moving slider, which can move up and down linearly with the Z-axis; the leveling nut can adjust the height of the forming working platform, Guarantee the verticality requirements of the plane of the forming work platform to the outlet of the nozzle; the screw extrusion mechanism is horizontal, which includes the feeding cylinder, the screw extrusion device and the nozzle system connected with the screw extrusion device; The feeding cylinder connected to the extrusion device is in the shape of a round funnel, and a drying heater is installed outside; the nozzle system is composed of a conveying pipeline, a nozzle, a turntable, a shut-off valve and a cooling device; the nozzle is installed at the end of the conveying pipeline, and each nozzle The number includes 8, the shape of which is round or rectangular. The nozzle contains 650 nozzle holes. The shape of the nozzle hole is round or rectangular. The diameter of the nozzle outlet is 35 μm. The wind temperature is 15°C, and the wind speed is 0.1m/s; the shut-off valve is installed above the cooling device of the nozzle ;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 30mm/s , the melt flow rate of the metering pump is 120L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 7

A 3D printing method for fiber-level antibacterial products based on reactive extrusion, the lactam monomer undecalactam and the lactone monomer undecalactone are added with 0.1wt% additives acetyl caprolactam and isocyanate and Adding 30wt% plasticizer rare earth; the mass ratio of acetylcaprolactam to isocyanate is 1:1; after melting, under the action of a stable compound formed by adding 1wt% catalyst phenyl and sodium, the temperature is 300°C Polymerization reaction is carried out under, in polymerization reaction process, add the antibacterial agent quaternary ammonium salt compound of 6wt%; Described quaternary ammonium salt compound molecular formula is Among them, R ₁ , R ₂ = C8, X ^- is Cl ^- , and the target polymer with a number average molecular weight of 1000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw and an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is three-screw, the length-to-diameter ratio is 48, the pitch is equal, the helix angle is 18°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 160°C The final product is obtained after 40 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism, and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move along the Z-axis Make up and down linear motion; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is vertical or horizontal, which includes a feeding cylinder, a screw extrusion The output device and the nozzle system connected with the screw extrusion device; the supply cylinder includes the supply cylinder connected with the screw extrusion device, the supply cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipe, a nozzle , turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes 10, and its shape is triangular or rhombus, and the nozzle contains 800 spray holes, which are cross-shaped or straight. The diameter of the hole outlet is 25 μm, and a cooling device is installed above the nozzle. The cooling device is ring blowing or side blowing, the air temperature is 25 ° C, and the wind speed is 0.1 m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is transported forward, and is accurately and quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 8

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer laurolactam and the lactone monomer laurolactone with the addition of 5wt% additives carbamate and carbonate The mixture, wherein the mass ratio of carbamate and carbonate is 1:2, and the plasticizer added in an amount of 36wt% is a mixture of dibutyl phthalate and citrate, wherein phthalate di The mass ratio of butyl ester and citrate is 1:3; the mixture of catalyst sodium hydroxide and potassium hydroxide in an amount of 0.9wt% after melting (wherein the mass ratio of sodium hydroxide and potassium hydroxide is 2:1) Carry out the polymerization reaction at a temperature of 160°C under the action, and add 7wt% antibacterial agent quaternary ammonium salt compounds before the polymerization reaction; the molecular formula of the quaternary ammonium salt compounds is Among them, R ₁ , R ₂ = C9, X ^- is Br ^- , the target polymer with a number average molecular weight of 10000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 30, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 3.5mm, and the surface roughness is Ra0.4; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 150°C The final product is obtained after 10 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move along the Z-axis Make up and down linear motion; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is vertical or horizontal, which includes a feeding cylinder, a screw extrusion The output device and the nozzle system connected with the screw extrusion device; the supply cylinder includes the supply cylinder connected with the screw extrusion device, the supply cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipe, a nozzle , turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes 6, and its shape is rhombus, the nozzle contains 600 nozzle holes, the shape of the nozzle holes is Y-shaped, and the diameter of the nozzle outlet is 300μm At the same time, a cooling device is installed above the nozzle, the cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10000mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, ending a layer of deposited material Rapidly solidified and bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 9

A 3D printing method for fiber-level antibacterial products based on reactive extrusion, using valerolactam and caprolactam with a mass ratio of 1:1 and additives acetyl caprolactam in an amount of 5wt% and plasticizers in an amount of 35wt% The agent is a mixture of clay and rare earth, wherein the mass ratio of clay and rare earth is 4:3; after melting, the polymerization reaction is carried out under the action of 0.01wt% catalyst sodium hydroxide at a temperature of 300 ° C. During the polymerization reaction Add 8wt% antibacterial agent quaternary ammonium compound; The molecular formula of the quaternary ammonium compound is Among them, R ₁ , R ₂ = C10, X ^- is I ^- , and the target polymer with a number average molecular weight of 20,000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw and an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw and fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 100 °C The final product is obtained after 60 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move along the Z-axis Make up and down linear motion; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is vertical or horizontal, which includes a feeding cylinder, a screw extrusion The output device and the nozzle system connected with the screw extrusion device; the supply cylinder includes the supply cylinder connected with the screw extrusion device, the supply cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipe, a nozzle , turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes one, its shape is circular, and the nozzle contains 1 nozzle hole, the shape of the nozzle hole is circular, and the diameter of the nozzle outlet is 500μm. At the same time, a cooling device is installed above the nozzle, the cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is transported forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 500mm/s , the melt flow rate of the metering pump is 3000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposition material of one layer is solidified rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 10

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer valerolactam and the lactone monomer valerolactone with the addition of 0.1wt% of the auxiliary agent acetyl caprolactam and the addition of 10wt% % of plasticizer dibutyl phthalate; after melting, under the action of 0.01wt% catalyst sodium hydroxide, the polymerization reaction is carried out at a temperature of 150°C. During the polymerization reaction, 1wt% of antibacterial Agent quaternary ammonium salt compound; The molecular formula of the quaternary ammonium salt compound is Among them, R ₁ , R ₂ = C11, X ^- is Cl ^- , and the target polymer with a number average molecular weight of 1000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw and an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.4; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw and fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 100 °C The final product is obtained after 3 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move along the Z-axis Make up and down linear motion; the leveling nut can adjust the height of the forming work platform to ensure the verticality requirement of the forming work platform plane to the discharge port of the nozzle; the screw extrusion mechanism is vertical, which includes a feeding cylinder, a screw extrusion device and The nozzle system connected with the screw extrusion device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; The shut-off valve and the cooling device are composed; the nozzle is installed at the end of the conveying pipeline. A cooling device is installed on the top, the cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 10mm/s. The melt flow rate of the pump is 0.1L/h, and the precision is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The deposited material at the end of one layer solidifies rapidly and Bonded with the surrounding materials, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 11

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer caprolactam and the lactone monomer caprolactone are added with an additive of 5wt% isocyanate and an added amount of 40wt% plasticizer Citric acid ester; After melting, under the action of 1wt% catalyst potassium hydroxide, the polymerization reaction is carried out at a temperature of 300°C, and 5wt% antibacterial agent quaternary ammonium salt compounds are added during the polymerization process; the quaternary ammonium salt The molecular formula of the compound is Among them, R ₁ , R ₂ = C12, X ^- is Br ^- , and the target polymer with a number average molecular weight of 20,000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw and an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is twin-screw, the length-to-diameter ratio is 48, the pitch is equal, the helix angle is 18°, the depth of the screw groove is 3.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 180°C The final product is obtained after 60 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable coefficient of friction, which can well fix the first layer of printing materials; the supporting frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and at the same time fixedly connected with the Z-axis movement slider, which can make a straight line up and down along the Z-axis The leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is horizontal, which includes a feeding cylinder, a screw extrusion device and a screw extrusion The nozzle system connected with the output device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipeline, a nozzle, a turntable, a shut-off valve and The cooling device is composed of: the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes 2, the shape is rectangular, the nozzle contains 1000 nozzle holes, the shape of the nozzle holes is rectangular, and the diameter of the nozzle outlet is 500 μm, and a cooling device is installed above the nozzle , the cooling device is side blowing, the air temperature is 25°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 10000mm/s. The melt flow rate of the pump is 3000L/h, and the accuracy is -0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The deposited material at the end of one layer solidifies rapidly and Bonded with the surrounding materials, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 12

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer enantholactam and the lactone monomer enantholactone with an additive amount of 0.5wt% carbamate and an additive amount of 15wt% plasticizer gallium chloride; after melting, the polymerization reaction is carried out at a temperature of 250°C under the action of a stable compound formed by the addition of 0.08wt% catalyst methyl group and sodium, and 8wt% is added during the polymerization reaction % of the antibacterial agent quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Among them, R ₁ , R ₂ = C13, X ^- is Br ^- , the target polymer with a number average molecular weight of 10000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is three-screw, the length-to-diameter ratio is 45, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.8mm, and the surface roughness is Ra0.6; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is maintained at 120°C The final product is obtained after 10 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient, which can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and at the same time, it is fixed with the Z-axis movement slider, which can make a straight line up and down along the Z-axis movement; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is vertical, which includes a feeding cylinder, a screw extrusion device and a screw extrusion The nozzle system connected with the output device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipeline, a nozzle, a turntable, a shut-off valve and The cooling device is composed of: the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes 3, and its shape is triangular. , the cooling device is a circular blower, the air temperature is 20°C, and the wind speed is 0.05m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is transported forward, and is accurately and quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 100mm/s , the melt flow rate of the metering pump is 1000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part, and the deposition material of the end layer solidifies rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 13

A fiber-level 3D printing method for antibacterial products based on reactive extrusion, the lactam monomer capryllactam and the lactone monomer capryllactone are added with 2wt% additive carbonate and 20wt% Plasticizer Lithium Chloride; After melting, under the action of a stable compound formed by the combination of 0.07wt% ethyl and potassium, the polymerization reaction is carried out at a temperature of 200 ° C, and 1.7wt% antibacterial agent is added during the polymerization process. Ammonium salt compounds; the molecular formula of the quaternary ammonium salt compounds is Among them, R ₁ , R ₂ = C14, X ^- is I ^- , the target polymer with a number average molecular weight of 1000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 15, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.8mm, and the surface roughness is Ra0.6; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw and fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 100 °C The final product is obtained after 60 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable friction coefficient and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and is also fixedly connected with the Z-axis movement slider, which can move along the Z-axis Make up and down linear motion; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is horizontal, which includes a feeding cylinder, a screw extrusion device and The nozzle system connected with the screw extrusion device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; The shut-off valve and the cooling device are composed of a stop valve and a cooling device; the nozzle is installed at the end of the conveying pipeline. Cooling device, the cooling device is a circular air blower, the air temperature is 19°C, and the wind speed is 0.02m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 6000mm/s , the melt flow rate of the metering pump is 1500L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 14

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer caprolactam and the lactone monomer caprolactone are added with an additive sulfonate of 3.5wt% and an added amount of 25wt % plasticizer calcium chloride; after melting, the polymerization reaction is carried out under the action of the stable compound formed by the combination of 0.3wt% propyl group and calcium at a temperature of 160°C, and 2wt% antibacterial is added during the polymerization reaction Agent quaternary ammonium salt compound; The molecular formula of the quaternary ammonium salt compound is Wherein, R ₁ , R ₂ = C15, X ^- is I ^- , the target polymer with a number average molecular weight of 1000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 32, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 110°C The final product is obtained after 12 minutes. The 3D printing adopts a 3D printer device, including a screw extrusion mechanism, a 3D motion mechanism, a working platform mechanism, and a computer control and drive system arranged in sequence. The screw extrusion mechanism is fixed relative to the working platform and the molded part. ;The working platform mechanism is installed on the three-dimensional motion mechanism; the computer control and drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion The mechanism consists of an X-axis motor and a screw guide rail; the Y-axis motion mechanism consists of a Y-axis motor and a screw guide rail; the Z-axis motion mechanism consists of a Z-axis motor and a screw guide rail; the X-axis support is fixed on the Y-axis screw nut , the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base; the work platform mechanism is composed of the forming work platform, the support frame of the forming work platform and the leveling nut; In terms of mechanism, it has a suitable coefficient of friction, which can well fix the first layer of printing materials; the supporting frame of the forming work platform is fixedly connected with the Y-axis movement mechanism, and at the same time fixedly connected with the Z-axis movement slider, which can make a straight line up and down along the Z-axis movement; the leveling nut can adjust the height of the forming work platform to ensure the verticality of the forming work platform plane to the discharge port of the nozzle; the screw extrusion mechanism is vertical, which includes a feeding cylinder, a screw extrusion device and a screw extrusion The nozzle system connected with the output device; the feeding cylinder includes the feeding cylinder connected with the screw extrusion device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system consists of a conveying pipeline, a nozzle, a turntable, a shut-off valve and The cooling device is composed of: the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes 10, and its shape is rhombus. The cooling device is side blowing, the air temperature is 22°C, and the wind speed is 0.09m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD or CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system. The moving speed of the forming platform is 6000mm/s. The melt flow rate of the pump is 100L/h, and the accuracy is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part. The surrounding materials are bonded and formed, and the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 15

A 3D printing method for fiber-grade antibacterial products based on reactive extrusion, the lactam monomer decanolactam and the lactone monomer dedecalactone with the additive acetyl caprolactam with an additive amount of 4wt% and an additive amount of 23wt% plasticizer clay; after melting, under the action of a stable compound formed by adding 0.2wt% catalyst butyl and magnesium, the temperature is 160 ° C, and 1.2wt% antibacterial agent is added during the polymerization process Quaternary ammonium compound; The molecular formula of the quaternary ammonium compound is Among them, R ₁ , R ₂ = C16, X ^- is Br ^- , the target polymer with a number average molecular weight of 1200 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 30, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 1.8mm, and the surface roughness is Ra0.5; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 130°C The final product was obtained after 30 minutes. The three-dimensional printer device of Example 15 was used for 3D printing. The number of nozzles included 8, and its shape was rectangular. The nozzles contained 650 nozzle holes. The shape of the nozzle holes was circular, and the diameter of the nozzle outlet was 35 μm. At the same time, a cooling device is installed above the nozzle, the cooling device is side blowing, the air temperature is 15°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 30mm/s , the melt flow rate of the metering pump is 120L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 16

A 3D printing method for fiber-level antibacterial products based on reactive extrusion, the lactam monomer undecalactam and the lactone monomer undecalactone are added with 0.1wt% additives acetyl caprolactam and isocyanate and Adding 30wt% plasticizer rare earth; the mass ratio of acetylcaprolactam to isocyanate is 1:1; after melting, under the action of a stable compound formed by adding 1wt% catalyst phenyl and sodium, the temperature is 300°C Polymerization reaction is carried out under, add the antibacterial agent quaternary ammonium salt compound of 4wt% in the polymerization reaction process; Described quaternary ammonium salt compound molecular formula is Wherein, R ₁ , R ₂ = C17, X ^- is I ^- , the target polymer with a number average molecular weight of 1000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is three-screw, the length-to-diameter ratio is 48, the pitch is equal, the helix angle is 18°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 160°C After 40 minutes, the final product was obtained. The 3D printing adopts the three-dimensional printer device of Embodiment 15. The number of nozzles includes 10 nozzles in a rhombus shape. The nozzles include 800 nozzle holes. 25μm, and a cooling device is installed above the nozzle, the cooling device is ring blowing or side blowing, the air temperature is 25°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is transported forward, and is accurately and quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 17

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer laurolactam and the lactone monomer laurolactone with the addition of 5wt% additives carbamate and carbonate The mixture, wherein the mass ratio of carbamate and carbonate is 1:2, and the plasticizer added in an amount of 36wt% is a mixture of dibutyl phthalate and citrate, wherein phthalate di The mass ratio of butyl ester and citrate is 1:3; the mixture of catalyst sodium hydroxide and potassium hydroxide in an amount of 0.9wt% after melting (wherein the mass ratio of sodium hydroxide and potassium hydroxide is 2:1) Under the action, the polymerization reaction is carried out at a temperature of 160°C, and 0.5wt% of antibacterial agent quaternary ammonium salt compounds are added during the polymerization reaction process; the molecular formula of the quaternary ammonium salt compounds is Wherein, R ₁ , R ₂ = C18, X ^- is I ^- , the target polymer with a number average molecular weight of 10000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 30, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 3.5mm, and the surface roughness is Ra0.4; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 150°C The final product was obtained after 10 minutes, and the 3D printing adopts the three-dimensional printer device of Embodiment 15. The number of nozzles includes 6, and its shape is rhombus. The nozzles include 600 nozzle holes, the shape of the nozzle holes is Y-shaped, and the diameter of the nozzle outlet is 300μm, and a cooling device is installed above the nozzle, the cooling device is a circular blower, the air temperature is 15°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10000mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, ending a layer of deposited material Rapidly solidified and bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 18

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the mass ratio of 1:1 valerolactam, caprolactam and the additive acetyl caprolactam of 5wt% and the plasticizer of 35wt% It is a mixture of clay and rare earth, wherein the mass ratio of clay and rare earth is 4:3; after melting, the polymerization reaction is carried out under the action of 0.01wt% catalyst sodium hydroxide at a temperature of 300°C, and 1.4wt% is added before polymerization % antibacterial agent quaternary ammonium compound; the quaternary ammonium compound molecule Among them, R ₁ , R ₂ = C19, X ^- is Cl ^-1 , the target polymer with a number average molecular weight of 20000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, an extruder connecting the screw Motor, heating coil, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The output motor is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is heated at 100 ° C Obtain the final product after keeping for 60 minutes. The 3D printing adopts the three-dimensional printer device of Embodiment 15. The number of nozzles is 1, and its shape is circular. The nozzle contains 1 nozzle hole. The shape of the nozzle hole is circular, and the diameter of the nozzle outlet is At the same time, a cooling device is installed above the nozzle. The cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is transported forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 500mm/s , the melt flow rate of the metering pump is 3000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposition material of one layer is solidified rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 19

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the mass ratio of 1:1 valerolactam, caprolactam and the additive acetyl caprolactam of 5wt% and the plasticizer of 36wt% It is a mixture of clay and rare earth, wherein the mass ratio of clay and rare earth is 4:3; after melting, the polymerization reaction is carried out under the action of 0.01wt% catalyst sodium hydroxide at a temperature of 300 °C, and 1.8wt% is added before polymerization % of the antibacterial agent is a quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Among them, R ₁ , R ₂ = C20, X ^- is Br ^- , and the target polymer with a number average molecular weight of 20,000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw and an extrusion motor connected to the screw , heating ring, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the extrusion of the connecting screw The motor is fixedly installed on the right side of the screw and fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is maintained at 100 °C The final product was obtained after 60 minutes. The 3D printing adopts the three-dimensional printer device of Embodiment 15. The nozzle contains 1 nozzle hole, the shape of the nozzle hole is circular, and the diameter of the nozzle outlet is 500 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is Ring blowing, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is transported forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 500mm/s , the melt flow rate of the metering pump is 3000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposition material of one layer is solidified rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 20

A 3D printing method for fiber-level antibacterial products based on reactive extrusion, the lactam monomer undecalactam and the lactone monomer undecalactone are added with 0.1wt% additives acetyl caprolactam and isocyanate and Adding 30wt% plasticizer rare earth; the mass ratio of acetylcaprolactam to isocyanate is 1:1; after melting, under the action of a stable compound formed by adding 1wt% catalyst phenyl and sodium, the temperature is 300°C Polymerization reaction is carried out under, add the antibacterial agent quaternary ammonium salt compound of 3.4wt% in the polymerization reaction process; Described quaternary ammonium salt compound molecular formula is Wherein, R ₁ =C11, R2 = 14, X ^- is I ^- , wherein the mass ratio of titanium dioxide and zinc oxide is 3:4, the target polymer with a number average molecular weight of 1000 is obtained, and the polymerization reaction is completed in a screw extruder , The screw extruder includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a metering pump; the screw is three-screw, the length-to-diameter ratio is 48, the pitch is equal, the helix angle is 18°, and the screw groove depth is 1.5mm , the surface roughness is Ra0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition , stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece was kept at 160° C. for 40 minutes to obtain the final product. The 3D printing adopts the three-dimensional printer device of Example 15. The number of nozzles includes 10, which are triangular in shape, and 800 nozzles are included on the nozzle. The shape of the nozzle hole is cross-shaped, and the diameter of the outlet of the nozzle hole is 25 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is ring blowing or side blowing. above the cooling device;

The specific steps of 3D printing include:

(1) Use CAD software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding;

(2) The target polymer is transported forward, and is accurately and quantitatively controlled by the metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is 0.1%. When the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part, and the deposited material of one layer ends quickly After solidification and bonding with the surrounding materials, the molding platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 21

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the lactam monomer laurolactam and the lactone monomer laurolactone with the addition of 5wt% additives carbamate and carbonate The mixture, wherein the mass ratio of carbamate and carbonate is 1:2, and the plasticizer added in an amount of 36wt% is a mixture of dibutyl phthalate and citrate, wherein phthalate di The mass ratio of butyl ester and citrate is 1:3; the mixture of catalyst sodium hydroxide and potassium hydroxide in an amount of 0.9wt% after melting (wherein the mass ratio of sodium hydroxide and potassium hydroxide is 2:1) Under the action, the temperature is 160°C to carry out the polymerization reaction, and 0.3wt% antibacterial agent quaternary ammonium salt compound is added during the polymerization reaction process; the molecular formula of the quaternary ammonium salt compound is Wherein, R1 ₌ C18, R2=14, X- is I- ^, the target polymer with number average molecular weight ^of 10000 is obtained, the polymerization reaction is completed in the screw extruder, and the screw extruder includes a screw, an extruder connecting the screw Motor, heating coil, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 30, the pitch is equal, the helix angle is 14°, the depth of the screw groove is 3.5mm, and the surface roughness is Ra0.4; the extrusion of the connecting screw The output motor is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is heated at 150 ° C After keeping for 10 minutes, the final product was obtained. The 3D printing adopts the three-dimensional printer device of Embodiment 15. The number of nozzles includes 6, which are rhombus-shaped, and each nozzle contains 600 nozzle holes. The shape of the nozzle holes is Y-shaped, and the nozzle holes The diameter of the outlet is 300 μm, and a cooling device is installed above the nozzle. The cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.1m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is conveyed forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 10000mm/s , the melt flow rate of the metering pump is 0.1L/h, and the accuracy is -0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, ending a layer of deposited material Rapidly solidified and bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 22

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the mass ratio of 1:1 valerolactam, caprolactam and the additive acetyl caprolactam of 5wt% and the plasticizer of 35wt% It is a mixture of clay and rare earth, wherein the mass ratio of clay and rare earth is 4:3; after melting, the polymerization reaction is carried out under the action of 0.01wt% catalyst sodium hydroxide at a temperature of 300°C, and 1.4wt% is added before polymerization % of the antibacterial agent quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Wherein, R ₁ =C19, R ₂ =8, X ^- is Cl ^-1 , the target polymer with a number average molecular weight of 20000 is obtained, the polymerization reaction is completed in a screw extruder, and the screw extruder includes a screw, a connecting screw Extrusion motor, heating coil, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the connecting screw The extrusion motor is fixedly installed on the right side of the screw, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is in The final product was obtained after keeping at 100°C for 60 minutes. The 3D printing adopts the three-dimensional printer device of Example 15. The nozzle contains 1 nozzle hole, the shape of the nozzle hole is circular, and the diameter of the nozzle outlet is 500 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is circular blowing, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is transported forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 500mm/s , the melt flow rate of the metering pump is 3000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposition material of one layer is solidified rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Example 23

A fiber-level 3D printing method based on reactive extrusion antibacterial products, the mass ratio of 1:1 valerolactam, caprolactam and the additive acetyl caprolactam of 5wt% and the plasticizer of 36wt% It is a mixture of clay and rare earth, wherein the mass ratio of clay and rare earth is 4:3; after melting, the polymerization reaction is carried out under the action of 0.01wt% catalyst sodium hydroxide at a temperature of 300 °C, and 1.8wt% is added before polymerization % of the antibacterial agent is a quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Wherein, R ₁ =C20, R ₂ =12, X ^- is Br ^- , and the target polymer with a number average molecular weight of 20,000 is obtained, and the polymerization reaction is completed in a screw extruder, which includes a screw, an extruder connected to the screw Outlet motor, heating coil, temperature sensor and metering pump; the screw is a single screw, the length-to-diameter ratio is 12, the pitch is equal, the helix angle is 16°, the depth of the screw groove is 1.5mm, and the surface roughness is Ra0.8; the connection screw The extrusion motor is fixedly installed on the right side of the screw, and is fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer is 3D printed by fusion deposition, and the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is in 100 After keeping at ℃ for 60 minutes to obtain the final product, the 3D printing adopts the three-dimensional printer device of Example 15, the number of nozzles includes one, and its shape is circular, and the nozzle contains 1 nozzle hole, the shape of the nozzle hole is circular, and the diameter of the nozzle outlet is At the same time, a cooling device is installed above the nozzle. The cooling device is a ring blower, the air temperature is 15°C, and the wind speed is 0.01m/s; the stop valve is installed above the cooling device of the nozzle;

The specific steps of 3D printing include:

(1) Use CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the formed coordinate G code;

(2) The target polymer is transported forward, and is accurately quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system. The forming platform moves in the X-Y plane under the control of the computer system, and the moving speed of the forming platform is 500mm/s , the melt flow rate of the metering pump is 3000L/h, and the accuracy is 0.1%; when the temperature of the extruded polymer is lower than the solidification temperature, it starts to solidify and form, and becomes a section with a thickness of one layer of the molded part, and the deposition material of one layer is solidified rapidly And bonded with the surrounding materials to form, the forming platform moves the height of one layer in the Z-axis direction to deposit the next layer, so that the three-dimensional workpiece is formed layer by layer.

Claims (10)

1. A fiber-level 3D printing method based on reactive extrusion antibacterial products, characterized in that: after the lactam monomer and/or lactone monomer are melted with auxiliary agents and plasticizers, polymerization is carried out under the action of a catalyst , adding an antibacterial agent before or during the polymerization to obtain the target polymer; then the target polymer is 3D printed by fusion deposition, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is heat-treated to obtain the final product; The plasticizer is more than one of dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, and rare earth; The heat treatment refers to keeping at 100-180° C. for 3-60 minutes. 2. a kind of fiber grade according to claim 1 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described lactam monomer is valerolactam, caprolactam, enantholactam, capryllactam, More than one of decanolactam, decalactam, undecylactam, and laurolactam; the lactone monomer is valerolactone, caprolactone, enantholactone, capryllactone, decanolactone, More than one of dedecalactone, undecalactone, and laurolactone; the catalyst is more than one of sodium hydroxide, potassium hydroxide, and an organic metal compound; the organic metal compound is methyl, ethyl A stable compound formed by combining one of base, propyl, butyl, and phenyl with one of sodium, potassium, calcium, and magnesium; the auxiliary agent is acetyl caprolactam, isocyanate, carbamate, carbonate and more than one of sulfonate; the antibacterial agent is nano-titanium dioxide, zinc oxide, iron oxide, chitosan, nano-silver, nano-copper or quaternary ammonium compound; the molecular formula of the quaternary ammonium compound is Wherein, R ₁ , R ₂ =C8-C20, R ₁ , R ₂ are the same or different, and X ^- is Cl ^- , Br ^- , I ^- . 3. The 3D printing method of a fiber-level antibacterial product based on reactive extrusion according to claim 1, wherein the temperature of the polymerization reaction is 150-300°C, and the amount of catalyst added is 0.01-1wt%. The addition amount of auxiliary agent is 0.1-5wt%, the addition amount of the plasticizer is 10-40wt%, the addition amount of the antibacterial agent is 0.01-10wt% of the monomer, and the number average molecular weight of the target polymer is 1000- 20000. 4. a kind of fiber grade according to claim 1 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described polymerization reaction is finished in screw extruder, and described screw extruder comprises screw rod, Extrusion motor, heating coil, temperature sensor and metering pump connected to the screw; the screw is one of single screw, twin screw and triple screw, with an aspect ratio of 12-48, equal pitch, and a helix angle of 14-18 °, the screw groove depth is 1.5-3.5mm, and the surface roughness is Ra0.4-0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw and fixed by a vertical support shaft; the heating ring and temperature The sensor is mounted outside the screw. 5. a kind of fiber grade according to claim 1 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, the step of described 3D printing comprises: (1) Use CAD or CAM software to design product graphics on the computer, and then perform automatic layering and slicing of the model to obtain the plane data information of each processing level, and convert it into the coordinate G code of the molding; (2) The target polymer is conveyed forward, and is accurately and quantitatively controlled by a metering pump and extruded to the forming platform by the nozzle system, and the forming platform moves in the X-Y plane under the control of the computer system; when the temperature of the extruded polymer is low After the curing temperature, it starts to solidify and form, and becomes a cross-section of one layer thickness of the molded part. The deposited material at the end of one layer is quickly solidified and bonded with the surrounding materials. The deposition, so layer by layer to form a three-dimensional workpiece. 6. a kind of fiber grade according to claim 5 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, the moving speed of described forming platform is 10-10000mm/s; The flow rate is 0.1-3000L/h, and the accuracy is ±0.1%. 7. a kind of fiber grade according to claim 1 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described 3D printing adopts three-dimensional printer device, comprises screw extruding mechanism, three-dimensional motion mechanism arranged in sequence , a working platform mechanism and a computer control and drive system, the screw extrusion mechanism is fixed relative to the working platform and the molding; the working platform mechanism is installed on a three-dimensional motion mechanism; the computer control and drive system is It is used for the automatic control and drive of the whole machine. 8. a kind of fiber grade according to claim 7 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described three-dimensional kinematic mechanism is made up of X-axis kinematic mechanism, Y-axis kinematic mechanism and Z-axis kinematic mechanism The X-axis motion mechanism includes an X-axis motor and a screw guide rail; the Y-axis motion mechanism includes a Y-axis motor and a screw guide rail; the Z-axis motion mechanism includes a Z-axis motor and a screw guide rail; The X-axis support is fixed on the Y-axis lead screw nut, the Y-axis support is fixed on the support frame of the forming work platform, and the Z-axis is vertically fixed on the base. 9. a kind of fiber grade according to claim 7 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described working platform mechanism is made up of forming working platform, forming working platform support frame and leveling nut; The forming work platform is installed on the X-axis motion mechanism, has a suitable friction coefficient, and can well fix the first layer of printing materials; the support frame of the forming work platform is fixedly connected with the Y-axis motion mechanism , and is fixedly connected with the Z-axis moving slider at the same time, and can move up and down linearly with the Z-axis; the leveling nut can adjust the height of the forming work platform to ensure the verticality requirement of the forming work platform plane to the discharge port of the nozzle. 10. A kind of fiber level according to claim 7 is based on the 3D printing method of the antibacterial product of reaction extrusion, it is characterized in that, described screw extrusion mechanism is vertical or horizontal, and it comprises feeding cylinder, screw extruder Outlet device and the nozzle system that is connected with the screw extruder; The described feeding cylinder includes the feeding cylinder connected with the screw extruding device, the feeding cylinder is in the shape of a circular funnel, and a drying heater is arranged outside; the nozzle system Consists of conveying pipeline, nozzle, turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipeline, the number of nozzles includes at least one, and its shape is one or more of circular, rectangular, triangular, rhombus, The nozzle contains 1-1000 nozzle holes, and the shape of the nozzle hole is one or more of circular, rectangular, triangular, rhombus, cross-shaped, straight, Y-shaped, and the diameter of the nozzle outlet is 10-500μm. A cooling device is installed above, the cooling device is ring blowing or side blowing, the wind temperature is 15-25°C, and the wind speed is 0.01-0.1m/s; the stop valve is installed above the cooling device of the nozzle.