CN105690778A - Fiber-grade 3D (three-dimensional) printing method on basis of reactive extrusion - Google Patents

Abstract

The invention relates to a fiber-level 3D printing method based on reactive extrusion, which melts lactam monomers and/or lactone monomers with auxiliary agents and plasticizers, and performs polymerization reactions under the action of catalysts to obtain target polymers; Then, the target polymer is subjected to fused deposition 3D printing, and then a final product is obtained after heat treatment; the heat treatment refers to keeping at 100-180° C. for 3-60 minutes. The invention adopts a high-precision and high-adaptability 3D printer, which has high molding precision, high efficiency, and good mechanical properties of the product; it adopts a process from the polymerization monomer directly to the product, which improves the production flexibility and avoids semi-finished products such as nylon and polyester. Crystalline polymers are warped due to crystallization and large temperature differences, and even cannot be printed, which avoids the degradation of the performance of the part due to the degradation of the polymer. The invention broadens the types of fused deposition 3D printing materials, improves the quality of products, and has wide applications in the fields of handicrafts, machinery, chemical industry, instruments, automobiles and the like.

Description

A fiber-level 3D printing method based on reactive extrusion

technical field

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

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. 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 fiber-level 3D printing method based on reactive 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. The degradation and performance degradation in the processing process caused by it; the direct product from the monomer can reduce the processing and molding temperature, and avoid the problem of dimensional change caused by thermal shrinkage due to excessive temperature difference; and it is highly adjustable, and can be adjusted according to Product quality requires the regulation of the production process to achieve single-line multi-variety production with good production continuity; at the same time, use a 3D printer with high precision, high efficiency and high adaptability to improve the degree of freedom of molding, production speed and precision of molded parts.

A fiber-grade 3D printing method based on reactive extrusion of the present invention, after melting the lactam monomer and/or lactone monomer, auxiliary agent and plasticizer, polymerizes under the action of a catalyst 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 a 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, It reduces the crystallinity of semi-crystalline polymers, lowers the melting point of polymers, and enables printing at lower temperatures. At the same time, plasticizers can interact with multiple molecular chains in the system at the same time, thereby micro-crosslinking The effect of reducing the difference in fluidity of the polymer before and after melting, and reducing the difference in fluidity of the polymer before and after melting.

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 as described above, the lactam monomer is valerolactam, caprolactam, enantholactam, capryllactam, caprolactam, decanolactam, undecalactam , more than one of laurolactam; the lactone monomer is valerolactone, caprolactone, enantholactone, capryllactone, decanolactone, dedecalactone, undecalactone, laurolactone More than one of esters; the catalyst is more than one of sodium hydroxide, potassium hydroxide, and organometallic compounds; the organometallic compound is one or more of methyl, ethyl, propyl, butyl, and phenyl A stable compound formed by combining with one of sodium, potassium, calcium and magnesium; the auxiliary agent is more than one of acetyl caprolactam, isocyanate, carbamate, carbonate and sulfonate.

A fiber-level 3D printing method based on reactive extrusion 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%, and the number average molecular weight of the target polymer is 1000-20000.

A fiber-level 3D printing method based on reactive extrusion 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 The extruder includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a metering pump; The 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 and fixed by a vertical support shaft; The above-mentioned heating ring and temperature sensor are installed outside the screw rod.

As mentioned above, a fiber-level 3D printing method based on reactive extrusion, 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.

A fiber-level 3D printing method based on reactive extrusion as described above, 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 accuracy 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 molding of high-viscosity thermoplastic materials.

A fiber-level 3D printing method based on reactive extrusion 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 system arranged in sequence. The screw extruding 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 automatic control and driving of the whole machine.

A fiber-level 3D printing method based on reactive extrusion as described above, the three-dimensional motion mechanism is composed of an X-axis motion mechanism, a Y-axis motion mechanism and a Z-axis motion mechanism; the X-axis motion mechanism includes an X-axis motor and The Y-axis motion mechanism consists of 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 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.

A fiber-level 3D printing method based on reactive extrusion as described above, 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 The 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 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 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, the screw extrusion mechanism is vertical or horizontal, which includes a feeding cylinder, a screw extrusion device and a nozzle system connected to the screw extrusion device ; The feed cylinder includes a feed cylinder connected to a screw extruder, the feed 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 stop valve and a cooling Device composition; 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 nozzle holes, the nozzle holes The shape is one or more of circle, rectangle, triangle, rhombus, cross, inline, and Y shape. The diameter of the nozzle outlet is 10-500 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is a ring blower or a side blower. For blowing, the air 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 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, thus playing the role of micro-crosslinking , to reduce the difference in fluidity of the polymer before and after melting, and to reduce the difference in fluidity of the polymer before and after melting, which is beneficial to achieve shape retention of the filament 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) 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, the lactam monomer valerolactam and the lactone monomer valerolactone are added with 0.1wt% of additives acetyl caprolactam and 10wt% of additives Plasticizer dibutyl phthalate; After melting, under the action of 0.01wt% catalyst sodium hydroxide, the temperature is 150°C for polymerization to obtain a target polymer with a number-average molecular weight of 1000. 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 a single screw, the length-to-diameter ratio is 12, the pitch is equal, and 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, and is fixed by a vertical support shaft; the heating ring and the temperature sensor are installed outside the screw; then the target polymerization The object is 3D printed by fused 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. Computer control and drive 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 drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism It 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 screw guide rail; Z-axis motion mechanism includes Z-axis motor and screw guide rail; X-axis support is fixed on the Y-axis screw nut, Y-axis support is fixed on the support frame of the forming work platform, and Z-axis is vertically fixed on the base; the working platform mechanism is formed by the forming work platform 1. Forming working platform support frame and leveling nut; forming working platform is installed on the X-axis motion mechanism, has a suitable friction coefficient, and can well fix the first layer of printing materials; forming working platform supporting frame and the Y The axis movement mechanism is fixedly connected, 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 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 feed cylinder, a screw extrusion device and a nozzle system connected with the screw extrusion device; the feed cylinder includes a feed cylinder connected with the screw extrusion device, and the feed cylinder is round It is funnel-shaped, with a drying heater outside; the nozzle system consists of a conveying pipe, nozzle, turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipe, and the number of nozzle is one, and its shape is circular, and the nozzle contains 1 The shape of the nozzle hole is circular, and the outlet diameter of the nozzle hole is 10 μm. At the same time, a cooling device is installed above the nozzle. above the cooling unit;

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, the lactam monomer caprolactam and the lactone monomer caprolactone are added with 5wt% of auxiliary agent isocyanate and 40wt% of plasticizer citrate After melting, under the action of the catalyst potassium hydroxide in an addition amount of 1wt%, the polymerization reaction is carried out at a temperature of 300° C. to obtain a target polymer with a number average molecular weight of 20,000. The polymerization reaction is completed in a screw extruder, and the screw extrusion The machine includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a 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 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 and accumulated layer by layer Form a three-dimensional workpiece; the three-dimensional workpiece is kept at 180°C for 60 minutes to obtain the final product. The 3D printing adopts a three-dimensional printer device, including a screw extrusion mechanism, a three-dimensional movement mechanism, a working platform mechanism, a computer control and drive system, and a screw extrusion mechanism. Relative to the working platform and the molded parts are fixed; 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 consists of an X-axis motion mechanism and a Y-axis motion mechanism Composed of Z-axis motion mechanism; X-axis motion mechanism consists of X-axis motor and screw guide rail; Y-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 The shaft 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 consists of the forming work platform, the support frame of the forming work platform and the leveling nut Composition; the forming work platform is installed on the X-axis movement mechanism, which 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 at the same time it is connected with the Z-axis movement slider It is fixed 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 of the forming work platform to the discharge port of the nozzle; the screw extrusion mechanism is horizontal, including the feeding cylinder, screw extrusion device and nozzle system connected with the screw extrusion device; the feeding cylinder includes a 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 Composed 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 2, and its shape is rectangular, and the nozzle contains 1000 nozzle holes, the shape of the nozzle hole is rectangular, and the outlet of the nozzle hole The diameter is 500μm, 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 precisely 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, the lactam monomer enantholactam and the lactone monomer enantholactone with the addition of 0.5wt% additive carbamate and the addition of 15wt% Plasticizer gallium chloride; after melting, under the action of a stable compound formed by the combination of catalyst methyl and sodium in an amount of 0.08wt%, the polymerization reaction is carried out at a temperature of 250°C to obtain the target polymer with a number average molecular weight of 10,000 , 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 groove depth is 16°, the screw groove depth 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, 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 120°C for 10 minutes to obtain the final product. The 3D printing adopts a three-dimensional printer device, including a screw extrusion mechanism, a three-dimensional motion mechanism, The working platform mechanism and computer control and drive 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 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 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, 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 It is composed of forming work platform, support frame of forming work platform and leveling nut; the forming work 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; the support frame of forming work platform and The Y-axis motion mechanism is 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 the verticality of the forming work platform plane to the nozzle outlet. Requirements; 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 a feeding cylinder connected to the screw extrusion device, and the feeding cylinder is Round funnel-shaped, with a drying heater on the outside; the nozzle system consists of a conveying pipe, nozzle, turntable, shut-off valve and cooling device; the nozzle is installed at the end of the conveying pipe, and the number of nozzles includes 3, which are triangular in shape. 800 spray holes, the shape of the spray holes is triangular, and the diameter of the spray hole outlet is 100 μm. At the same time, a cooling device is installed above the nozzle. above the cooling unit;

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 based on reactive extrusion, the lactam monomer capryllactam and the lactone monomer capryllactone are added with an additive carbonate of 2wt% and a plasticizer of 20wt% Lithium chloride; After melting, under the action of a stable compound formed by the addition of 0.07wt% ethyl and potassium, the temperature is 200°C for polymerization to obtain a target polymer with a number-average molecular weight of 1000. The polymerization is carried out in the screw Completed in the extruder, the screw extruder includes the screw, the extrusion motor connected to the screw, the heating coil, the temperature sensor and the metering pump; The groove depth 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, fixed by a vertical support shaft; the heating ring and temperature sensor are installed outside the screw; then the target polymer After fused deposition 3D printing, the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is kept at 100°C for 60 minutes to obtain the final product. 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. The control and drive 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 drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of Composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion mechanism consists of X-axis motor and screw guide rail; Y-axis motion mechanism consists of Y-axis motor and screw guide rail; Z-axis motion mechanism includes Z Axis motor and lead screw guide rail; X-axis support is fixed on the Y-axis screw nut, Y-axis support is fixed on the support frame of the forming work platform, and Z-axis is vertically fixed on the base; the work platform mechanism consists of the forming work platform, Forming work platform support frame and leveling nuts; forming work platform is installed on the X-axis motion mechanism, has a suitable friction coefficient, can well fix the first layer of printing materials; forming work platform support frame and the Y-axis The movement mechanism is fixedly connected, and at the same time, it is 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 the verticality requirement of the forming work platform plane 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 with the screw extrusion device; the feeding cylinder includes a feeding cylinder connected with the screw extrusion device, and the feeding cylinder is circular Funnel-shaped, with a drying heater outside; the nozzle system is composed of a conveying pipe, nozzle, turntable, stop valve and cooling device; The shape of the nozzle hole is rhombus, and the diameter of the outlet of the nozzle hole is 50 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is a ring blower, the wind 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 5

A fiber-level 3D printing method based on reactive extrusion, the lactam monomer caprolactam and the lactone monomer caprolactone with the addition of 3.5wt% additive sulfonate and the addition of 25wt% Plasticizer calcium chloride; after melting, under the action of a stable compound formed by the combination of propyl and calcium in an amount of 0.3wt%, polymerization is carried out at a temperature of 160°C to obtain a target polymer with a number average molecular weight of 1000, and the polymerization reaction It is completed in a screw extruder, which includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a metering pump; the screw is a single screw with a length-to-diameter ratio of 32, equal pitch, and a helix angle of 16° , the depth of the screw groove is 1.5mm, 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 is fixed by a vertical support shaft; the heating ring and the temperature sensor are installed outside the screw; then the target The polymer is 3D printed by fused 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. The 3D printing adopts a three-dimensional printer device, including a screw extrusion mechanism, a three-dimensional motion mechanism, and a working platform mechanism. And the 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 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 movement The mechanism is composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion mechanism is composed of X-axis motor and screw guide rail; Y-axis motion mechanism is composed of Y-axis motor and screw guide rail; Z-axis motion mechanism It 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 formed by the forming work The platform, forming work platform support frame and leveling nut are composed; the forming work 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; the forming work platform support frame and the Y-axis movement The mechanism is fixedly connected, 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 work platform to ensure the verticality of the forming work platform plane to the discharge port of the nozzle; the screw The extrusion mechanism is vertical, which includes a feeding cylinder, a screw extrusion device and a nozzle system connected with the screw extrusion device; the feeding cylinder includes a feeding cylinder connected with the screw extrusion device, and the feeding cylinder is a circular funnel shape, with a drying heater on the outside; the nozzle system is composed of a conveying pipe, nozzle, turntable, shut-off valve and cooling device; The shape of the nozzle hole is cross-shaped, and the diameter of the outlet of the nozzle hole is 80 μm. At the same time, a cooling device is installed above the nozzle. The cooling device is side blowing, the wind temperature is 22 ° C, and the wind speed is 0.09 m/s; the stop valve is installed on the cooling device of the nozzle above;

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 fiber-level 3D printing method based on reactive extrusion, the lactam monomer decanolactam and the lactone monomer dedecalactone are added with 4wt% of additives acetyl caprolactam and 23wt% of plasticizer Agent clay; After melting, under the action of a stable compound formed by the addition of 0.2wt% catalyst butyl and magnesium, the temperature is 160°C for polymerization to obtain a target polymer with a number average molecular weight of 1200. Completed in the extruder, the screw extruder includes the screw, the extrusion motor connected to the screw, the heating coil, the temperature sensor and the metering pump; The groove depth is 1.8mm, and the surface roughness is Ra0.5; 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 After fused deposition 3D printing, the three-dimensional workpiece is formed layer by layer; the three-dimensional workpiece is kept at 130°C for 30 minutes to obtain the final product. 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. The control and drive 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 drive system is used for the automatic control and drive of the whole machine; the three-dimensional motion mechanism is composed of Composed of X-axis motion mechanism, Y-axis motion mechanism and Z-axis motion mechanism; X-axis motion mechanism consists of X-axis motor and screw guide rail; Y-axis motion mechanism consists of Y-axis motor and screw guide rail; Z-axis motion mechanism includes Z Axis motor and lead screw guide rail; X-axis support is fixed on the Y-axis screw nut, Y-axis support is fixed on the support frame of the forming work platform, and Z-axis is vertically fixed on the base; the work platform mechanism consists of the forming work platform, Forming work platform support frame and leveling nuts; forming work platform is installed on the X-axis motion mechanism, has a suitable friction coefficient, can well fix the first layer of printing materials; forming work platform support frame and Y-axis motion mechanism are fixed It is 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 of the forming work platform plane to the discharge port of the nozzle; screw extrusion The mechanism is horizontal, which includes a feeding cylinder, a screw extrusion device and a nozzle system connected with the screw extrusion device; the feeding cylinder includes a feeding cylinder connected with the screw extrusion device, and the feeding cylinder is in the shape of a circular funnel. A drying heater is set 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 8, and its shape is round or rectangular, and the nozzle contains 650 Nozzle hole, the shape of the nozzle hole is circular or rectangular, and the diameter of the nozzle hole outlet is 35 μm. At the same time, a cooling device is installed above the nozzle. above the cooling device;

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 fiber-level 3D printing method based on reactive extrusion, the lactam monomer undecalactam and the lactone monomer undecalactone and the additives acetyl caprolactam and isocyanate in an amount of 0.1wt% and the addition amount of 30wt% plasticizer rare earth; the mass ratio of acetyl caprolactam to isocyanate is 1:1; after melting, under the action of a stable compound formed by the combination of 1wt% catalyst phenyl and sodium, polymerize at a temperature of 300°C Reaction, the target polymer that obtains number-average molecular weight is 1000, polyreaction finishes in screw extruder, and screw extruder comprises screw, the extruding motor that connects screw, heating ring, temperature sensor and metering pump; Screw is a three-screw , the length-to-diameter ratio is 48, the pitch is equal, the helix angle is 18°, the groove depth is 1.5mm, and the surface roughness is Ra0.8; the extrusion motor connected to the screw is fixedly installed on the right side of the screw, supported by a vertical 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 160°C for 40 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 discharge port of the nozzle; the screw extrusion mechanism is vertical or horizontal, which includes the feeding cylinder, the screw extrusion device and the nozzle system connected with 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 10, which are triangular or rhombus-shaped. The nozzles contain 800 nozzle holes. The device is circular blowing or side blowing, the wind temperature is 25°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 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, a mixture of lactam monomer laurolactam and lactone monomer laurolactone with additives carbamate and carbonate in an amount of 5wt%, Wherein the mass ratio of carbamate and carbonate is 1:2, and the mixture of plasticizer dibutyl phthalate and citrate in an amount of 36wt%, wherein dibutyl phthalate and lemon The mass ratio of acid ester is 1:3; After melting, under the effect of the mixture of catalyst sodium hydroxide and potassium hydroxide (wherein the mass ratio of sodium hydroxide and potassium hydroxide is 2:1) in an added amount of 0.9wt%, at temperature The polymerization reaction is carried out at 160°C to obtain the target polymer with a number average molecular weight of 10,000. The polymerization reaction is completed in a screw extruder, which includes a screw, an extrusion motor connected to the screw, a heating coil, a temperature sensor and a 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 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, and stacked layer by layer to form a three-dimensional workpiece; the three-dimensional workpiece is kept at 150°C for 10 minutes to obtain the final product, 3D printing A three-dimensional printer device is used, 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 movement In terms of mechanism; the computer control and drive system is used for 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 mechanism includes X-axis motor and screw Composed of guide rails; 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 forming work On the platform support frame, the Z axis is vertically fixed on the base; the working platform mechanism is composed of the forming work platform, the forming work platform support frame and the leveling nut; the forming work platform is installed on the X axis movement mechanism, which has a suitable friction coefficient , can well fix the first layer of printing materials; the forming work platform support frame 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 The height of the forming work platform can be adjusted to ensure that the plane of the forming work platform is perpendicular to the discharge port of the nozzle; the screw extrusion mechanism is vertical or horizontal, which includes a feeding cylinder, a screw extrusion device and a screw extrusion device The connected nozzle system; 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 a cooling device Composition; 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 nozzle outlet The diameter 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 fiber-level 3D printing method based on reactive extrusion, the mass ratio of 1:1 valerolactam, caprolactam and additives acetyl caprolactam 5wt% and 35wt% plasticizer clay and A mixture of rare earths, wherein the mass ratio of clay to 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 to obtain the target polymerization with a number average molecular weight of 20,000 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 a single screw with an aspect ratio of 12, equal pitch, and a screw The angle is 14°, the screw groove depth is 1.5mm, 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 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 100°C for 60 minutes to obtain the final product, and the 3D printing adopts a three-dimensional printer device, including a screw extrusion mechanism and a three-dimensional motion mechanism arranged in sequence , 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 automatic control and Drive; 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 is composed of Y-axis motor and 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 working platform The mechanism is composed of a forming work platform, a support frame of the forming work platform and a leveling nut; the forming work 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; the support frame of the forming work platform It is fixedly connected with the Y-axis motion mechanism, and at the same time, it is 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 vertical or horizontal, which includes a feed cylinder, a screw extrusion device and a nozzle system connected to the screw extrusion device; the supply cylinder includes a supply tube connected to the screw extrusion device Material cylinder, the material supply 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, and the number of nozzles includes one. It 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 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 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. fibre-grade is based on a 3D Method of printing for reactive extrursion, it is characterized in that: carry out polyreaction under catalyst action after melted to lactam monomers and/or internal ester monomer and auxiliary agent, plasticizer, it is thus achieved that subject polymer；Then described subject polymer is printed through fusion sediment 3D, successively pile up and form 3 D workpiece；Described 3 D workpiece after heat treatment obtains final products；

Described plasticizer is more than one in dibutyl phthalate, citrate, gallium chloride, lithium chloride, calcium chloride, clay, rare earth；

Described heat treatment refers to and keeps 3-60min at 100-180 DEG C。

2. a kind of fibre-grade according to claim 1 is based on the 3D Method of printing of reactive extrursion, it is characterized in that, described lactam monomers is more than one in valerolactam, caprolactam, oenantholcatam, spicy inner formyl amine, certain herbaceous plants with big flowers lactams, ten lactams, 11 lactams, lauric lactam；Described internal ester monomer is more than one in valerolactone, caprolactone, heptalactone, caprylolactone, certain herbaceous plants with big flowers lactone, ten lactones, undecalactone, dodecalactone；Described catalyst is more than one in sodium hydroxide, potassium hydroxide, organo-metallic compound；Described organo-metallic compound is the stable compound that a kind of combination in a kind of and sodium in methyl, ethyl, propyl group, butyl, phenyl, potassium, calcium, magnesium is formed；Described auxiliary agent is more than one in vinylcaprolactam, isocyanates, carbamate, carbonic ester and sulphonic acid ester。

3. a kind of fibre-grade according to claim 1 is based on the 3D Method of printing of reactive extrursion, it is characterized in that, the temperature of described polyreaction is 150-300 DEG C, catalyst loading is 0.01-1wt%, additive dosage is 0.1-5wt%, described plasticizer addition is 10-40wt%, and the number-average molecular weight of described subject polymer is 1000-20000。

4. a kind of fibre-grade according to claim 1 is based on the 3D Method of printing of reactive extrursion, it is characterized in that, described polyreaction completes in screw extruder, and described screw extruder includes screw rod, connects the extruder motor of screw rod, heating collar, temperature sensor and dosing pump；Described screw rod is the one in single screw rod, twin screw, three screw rods, and draw ratio is 12-48, uniform pitch, and helical angle is 14-18 °, and spiral groove depth is 1.5-3.5mm, and surface roughness is Ra0.4-0.8；The extruder motor of described connection screw rod is fixedly mounted on the right side of screw rod, is fixed by vertically supporting axle；Described heating collar and temperature sensor are arranged on outside screw rod。

5. a kind of fibre-grade according to claim 1 is based on the 3D Method of printing of reactive extrursion, it is characterised in that the step that described 3D prints includes:

(1) adopt CAD or CAM software design product figure on computers, then carry out the AUTOMATIC ZONING slicing treatment of model, obtain the panel data information of each processing aspect, and be converted into the coordinate G code of molding；

(2) described subject polymer is fed forward, and is controlled by dosing pump accurate quantification and extruded to shaped platform by nozzle system, and shaped platform does X-Y plane motion under computer system control；Curing molding is started after the temperature of polymer of extrusion is lower than solidification temperature, become the cross section of profiled member a layer thickness, terminate one layer deposition material rapid solidification and with adjacent material molding bonded, shaped platform is at the height of Z axis Move Up One Layer, carry out the deposition of next layer, so successively pile up and form 3 D workpiece。

6. a kind of fibre-grade according to claim 5 is based on the 3D Method of printing of reactive extrursion, it is characterised in that the translational speed of described shaped platform is 10-10000mm/s；Described dosing pump melt flow is 0.1-3000L/h, and precision is ± 0.1%。

7. a kind of fibre-grade according to claim 1 is based on the 3D Method of printing of reactive extrursion, it is characterized in that, described 3D prints and adopts 3 D-printing machine, controlling and drive system including the Screw Extrusion mechanism set gradually, three-dimensional motion mechanism, workbench mechanism and computer, described Screw Extrusion mechanism maintains static relative to work platforms and profiled member；Described workbench mechanism is arranged on three-dimensional motion mechanism；It is automatically controlling and driving for complete machine that described computer controls with drive system。

8. a kind of fibre-grade according to claim 7 is based on the 3D Method of printing of reactive extrursion, it is characterised in that described three-dimensional motion mechanism is made up of X-axis motion, Y-axis motion and Z axis motion；Described X-axis motion includes X-axis motor and lead screw guide rails composition；Described Y-axis motion includes y-axis motor and lead screw guide rails composition；Described Z axis motion includes Z axis motor and lead screw guide rails composition；Described X-axis is supported and fixed on Y-axis feed screw nut, and Y-axis is supported and fixed on shaping work platform frame, and Z axis is vertically fixed on pedestal。

9. a kind of fibre-grade according to claim 7 is based on the 3D Method of printing of reactive extrursion, it is characterised in that described workbench mechanism is made up of shaping work platform, shaping work platform frame and leveling nut；Described shaping work stage+module, on described X-axis motion, has suitable coefficient of friction, it is possible to well fixing ground floor printed material；Described shaping work platform frame is connected with described Y-axis motion, simultaneously affixed with Z axis moving slide block, it is possible to do upper and lower rectilinear motion with Z axis；Described leveling nut can regulate the height of molding work platforms, it is ensured that the perpendicularity requirement to shower nozzle discharging opening of the shaping work platform plane。

10. a kind of fibre-grade according to claim 7 is based on the 3D Method of printing of reactive extrursion, it is characterised in that described Screw Extrusion mechanism is vertical or horizontal, and it includes material feed drum, screw extrusion apparatus and the nozzle system being connected with screw extrusion apparatus；Described material feed drum includes the material feed drum being connected with screw extrusion apparatus, and the rounded funnel-form of material feed drum, outside arranges drying heater；Described nozzle system is made up of conveyance conduit, nozzle, rotating disk, stop valve and chiller；Described nozzle is installed on conveyance conduit end, nozzle number at least includes one, it is generally circular in shape, one or more in rectangle, triangle, rhombus, comprising 1-1000 spray orifice on nozzle, spray orifice is generally circular in shape, one or more in rectangle, triangle, rhombus, cross, in-line, Y shape, and spray orifice outlet diameter is 10-500 μm, nozzle chiller installed above simultaneously, chiller is ring blowing or cross air blasting, and pathogenic wind-warm is 15-25 DEG C, and wind speed is 0.01-0.1m/s；Described stop valve is installed on above the chiller of shower nozzle。