A process and apparatus for preparing thermoset polymer materials using 3D printing technology

Abstract

The application relates to a high polymer material polymerization heat control process and device, in particular to a process and equipment for preparing thermosetting high polymer materials by using 3D printing technology. Raw materials include monomers, initiators, crosslinking agents, auxiliary crosslinking agents and functional monomers, and the application is characterized in that the following steps are included: in the first step, the raw materials are uniformly mixed and then subjected to a prepolymerization reaction to obtain a slurry product. By adopting the process, the thermosetting high polymer materials prepared by using the 3D printing technology have excellent performance, the low-dielectric-constant and low-dielectric-loss thermosetting high polymer materials are prepared, local polymerization heat is well controlled under the 3D printing technology stacking mode, the polymerization heat stacking problem during one-time large-size polymerization is avoided, material explosion polymerization is avoided, and the yield of finished products is improved.

Description

Technical Field

[0001] This application relates to a process and apparatus for controlling the polymerization heat of polymer materials, and more particularly to a process and equipment for preparing thermosetting polymer materials using 3D printing technology. Background Technology

[0002] Bulk polymerization produces various types of thermosetting polymers that possess inherently excellent properties such as low dielectric constant, low dielectric loss, low density, good heat resistance, and good light transmittance. However, bulk polymerization often employs a multi-stage batch polymerization process, making the control of the heat of polymerization crucial. Due to the autoacceleration phenomenon caused by the gel effect during polymerization, the material is highly susceptible to explosive polymerization, resulting in low yield and making it impossible to manufacture large-sized, complex structural prototypes.

[0003] The preparation process of bulk polymer materials is always severely limited by the heat runaway of polymerization, making the preparation process difficult to control and resulting in low yield. Summary of the Invention

[0004] The purpose of this application is to propose a process and equipment for preparing thermosetting polymer materials using 3D printing technology to eliminate the above-mentioned defects and avoid explosive polymerization of materials.

[0005] One of the technical solutions of this application is implemented as follows: a process and equipment for preparing thermosetting polymer materials using 3D printing technology, wherein the raw materials include monomers, initiators, crosslinking agents, co-crosslinking agents, and functional monomers, characterized by including the following steps: The first step is to mix the raw materials evenly and then carry out a prepolymerization reaction to obtain a slurry product; The second step is to feed the slurry product obtained in the first step into the 3D printing device. The third step involves using a 3D printing device to spray the slurry-like product obtained in the first step into the molding die for the polymerization reaction through a printing nozzle. The fourth step involves the 3D printing device from the third step injecting material into the mold to induce a polymerization reaction. After the polymerization reaction, the material is cooled to obtain a thermosetting polymer material prepared using 3D printing technology.

[0006] Furthermore, in the fourth step, the jetting rate of the 3D printing device is 0.05 ml per minute to 5 ml per minute, and the displacement accuracy of the printing nozzle in each direction is no greater than ±0.5 mm.

[0007] Furthermore, the monomers in the raw materials are methyl methacrylate, bisphenol A, stilbene, acrylonitrile, or acetonitrile; the initiator is azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, cumene hydroperoxide, or benzophenone; the crosslinking agent is allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, or divinylbenzene; the co-crosslinking agent is triisocyanurate triacrylate, trimethylolpropane trimethacrylate, or caprolactone methacrylate; the functional monomer is polybutadiene, glass fiber powder, silane coupling agent, or 3,5-bis(2-cyano-2-yl)toluene; the order of adding the raw materials in the first step is monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer, and the purity of all five components is 99.9% or higher.

[0008] Furthermore, the raw materials, by weight, include 100 parts of monomer, 0.5 to 10 parts of initiator, 0.5 to 7 parts of crosslinking agent, 0.5 to 3 parts of co-crosslinking agent, and 0.01 to 5 parts of functional monomer; in the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 1 to 5 hours.

[0009] Furthermore, the temperature of the prepolymerization reaction stage in the first step is controlled between 20 degrees Celsius and 80 degrees Celsius, with an initial temperature of 20 degrees Celsius, a heating rate of less than or equal to 1 degree Celsius per hour, a prepolymerization reaction time of greater than or equal to 60 hours, and an ending temperature of 80 degrees Celsius. After the prepolymerization reaction is completed, the conversion rate of the polymerized monomers should be 30-40%.

[0010] Furthermore, the mold material in steps three and four should be radiation-resistant, but not metal; in step four, the temperature control rate of the polymerization reaction is 0.1 degrees Celsius per hour, the starting temperature of the polymerization reaction is 40 degrees Celsius, and the ending temperature of the polymerization reaction is 180 degrees Celsius.

[0011] Furthermore, the mold is a cuboid of 50 cm × 50 cm × 5 cm or a cylinder with a diameter of 50 cm and a height of 50 cm.

[0012] The second technical solution of this application is implemented as follows: an apparatus for preparing thermosetting polymer materials using 3D printing technology, including a feeder, a reactor, and a 3D printing device; The feeder includes: Material storage tanks are used to store various raw materials. Metering pumps are used to weigh various raw materials to meet the required batch distribution ratios. Prepolymerization reactor, a reaction vessel used for prepolymerization reactions. Heater, used to heat the prepolymerization reactor; 3D printing equipment includes: The feeding device is used to transport the slurry after prepolymerization reaction in the prepolymerization reactor to the printing nozzle. The printing nozzle sprays the pre-polymerized slurry outwards and into the mold. The controller is used to control the movement of the printhead in all directions. The reactor includes: The mold is used to hold the slurry ejected from the print head, providing a reaction site for the polymerization reaction and shaping the final product. The temperature control unit is used to control the temperature of the polymerization reaction with precision.

[0013] By implementing the above technical solution, this application has produced high-performance thermosetting polymer materials with low dielectric constant and low dielectric loss through the use of this process to prepare thermosetting polymer materials using 3D printing technology. Under the stacking method of 3D printing technology, the local polymerization heat is well controlled, avoiding the problem of polymerization heat accumulation during one-time large-size polymerization, avoiding material bursting, and improving the yield. Attached Figure Description

[0014] The specific structure of this application is given by the following figures and embodiments: Figure 1 This is a schematic diagram of the final product of Embodiment 8 of this application; Figure 2 This is a schematic diagram of Embodiment 10 of this application.

[0015] Legend: 1. Feeder, 2. 3D printing device, 3. Reactor. Detailed Implementation

[0016] This application is not limited to the following embodiments, and the specific implementation method can be determined according to the technical solution of this application and the actual situation.

[0017] Example 1: A method for preparing thermosetting polymer materials using 3D printing technology includes monomers, initiators, crosslinking agents, co-crosslinking agents, and functional monomers. The process for preparing thermosetting polymer materials using 3D printing technology includes the following steps: First, the raw materials are mixed evenly and then subjected to a prepolymerization reaction to obtain a slurry product; Second, the slurry product obtained in the first step is fed into a 3D printing device; Third, the slurry product obtained in the first step is sprayed into a polymerization mold through a printing nozzle using the 3D printing device; Fourth, when the 3D printing device in the third step begins to spray into the mold, the material in the mold undergoes a polymerization reaction, and after the polymerization reaction, it is cooled to obtain the thermosetting polymer material prepared using 3D printing technology.

[0018] Compared to existing technologies that use molten polymers as raw materials for 3D printing additive manufacturing, where the molten polymer material is ejected from the printing nozzle and then cooled and solidified to form a thermoplastic polymer sample of the desired shape, this application has significant advantages in heat release control. It achieves excellent control of localized polymerization heat during the "small-batch, multiple-stage" deposition of 3D printing technology, avoiding the problem of polymerization heat accumulation during large-scale, one-time polymerization and preventing material bursting. Furthermore, this process can produce complex structural samples, such as using raw materials with different refractive indices to print Luneburg lenses.

[0019] Example 2, as an optimization of the above example, in the fourth step, the jetting rate of the 3D printing device is 0.05 ml per minute to 5 ml per minute, and the displacement accuracy of the printing nozzle of the 3D printing device in each direction is no greater than ±0.5 mm.

[0020] Example 3, as an optimization of the above examples, uses methyl methacrylate, bisphenol A, stilbene, acrylonitrile, or acetonitrile as the monomer in the raw materials; azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, cumene hydroperoxide, or benzophenone as the initiator; allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, or divinylbenzene as the crosslinking agent; triisocyanurate triacrylate, trimethylolpropane trimethacrylate, or caprolactone methacrylate as the co-crosslinking agent; and polybutadiene, glass fiber powder, silane coupling agent, or 3,5-bis(2-cyano-2-yl)toluene as the functional monomer. The order of adding the raw materials in the first step is monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer, and the purity of all five components is 99.9% or higher.

[0021] Example 4, as an optimization of the above example, the mold material in the third and fourth steps should be a radiation-resistant material, but does not include metal; the temperature control rate of the polymerization reaction in the fourth step is 0.1 degrees Celsius per hour, the starting temperature of the polymerization reaction is 40 degrees Celsius, and the ending temperature of the polymerization reaction is 180 degrees Celsius.

[0022] After the material reaches 180 degrees Celsius, the reaction continues for 1 to 6 hours. After the reaction, there is no obvious change in the appearance of the material.

[0023] Example 5, as an optimization of Examples 1 to 4, includes 100 parts by weight of monomer, 0.5 to 10 parts by initiator, 0.5 to 7 parts by crosslinking agent, 0.5 to 3 parts by co-crosslinking agent, and 0.01 to 5 parts by functional monomer. In the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 1 to 5 hours.

[0024] Example 6, as an optimization of Examples 1 to 4, includes 100 parts by weight of monomer, 0.5 or 10 parts of initiator, 0.5 or 7 parts of crosslinking agent, 0.5 or 3 parts of co-crosslinking agent, and 0.01 or 5 parts of functional monomer. In the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 1 hour or 5 hours.

[0025] Example 7, as an optimization of Examples 1 to 4, includes 100 parts by weight of monomer, 2 parts by initiator, 1 part by crosslinking agent, 0.8 parts by co-crosslinking agent, and 0.1 parts by functional monomer. In the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 2 hours.

[0026] Example 8, as an optimization of Examples 1 to 4, includes 100 parts by weight of monomer, 8 parts by initiator, 6 parts by crosslinking agent, 2.6 parts by co-crosslinking agent, and 4 parts by functional monomer. In the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 4 hours.

[0027] Example 9, as an optimization of the above examples, the mold is a cuboid of 50 cm × 50 cm × 5 cm or a cylinder with a diameter of 50 cm and a height of 50 cm. Figure 1 The product shown is made using a 50cm×50cm×5cm rectangular mold. Its mechanical properties were tested, and the material density was 1.02 g / cm³, the compressive strength was 113 MPa, and the dielectric constant was 2.21.

[0028] The thermosetting polymer materials obtained in the above embodiments of this application have a high yield. These products exhibit low dielectric constant, low dielectric loss, good heat resistance, and good light transmittance. For example, the parameters of the thermosetting polymer materials obtained in Examples 6 and 8, and comparative sample 1, are shown in Table 1 after testing; comparative sample 1 is a commercially available cross-linked polymethyl methacrylate polymer.

[0029] The process of preparing thermosetting polymer materials using 3D printing technology avoids the problem of polymerization heat accumulation during one-time large-scale polymerization, prevents material bursting, and improves the yield. The resulting products also possess naturally excellent properties such as low dielectric constant, low dielectric loss, low density, good heat resistance, and good light transmittance.

[0030] In summary, the process of preparing thermosetting polymer materials using 3D printing technology not only maintains excellent performance but also achieves good control of localized polymerization heat, avoiding the problem of polymerization heat accumulation during one-time large-scale polymerization, preventing material bursting, and improving the yield.

[0031] Example 10: An apparatus for preparing thermosetting polymer materials using 3D printing technology, characterized in that it includes a feeder, a reactor, and a 3D printing device; The dispenser includes: Material storage tanks are used to store various raw materials. Metering pumps are used to weigh various raw materials to meet the required batch distribution ratios. Prepolymerization reactor, a reaction vessel used for prepolymerization reactions. Heater, used to heat the prepolymerization reactor; 3D printing equipment includes: The feeding device is used to transport the slurry after prepolymerization reaction in the prepolymerization reactor to the printing nozzle. The printing nozzle sprays the pre-polymerized slurry outwards and into the mold. The controller is used to control the movement of the printhead in all directions. The reactor includes: The mold is used to hold the slurry ejected from the print head, providing a reaction site for the polymerization reaction and shaping the final product. The temperature control unit is used to control the temperature of the polymerization reaction with precision.

[0032] In this article, terms such as "up," "down," "front," "back," "left," and "right" are used only to indicate the relative positional relationship between related parts, rather than to define the absolute position of these related parts.

[0033] The above technical features constitute the embodiments of this application, which have strong adaptability and implementation effect. Non-essential technical features can be added or removed according to actual needs to meet the needs of different situations. Table 1

Claims

1. A process for preparing thermosetting polymer materials using 3D printing technology, wherein the raw materials include monomers, initiators, crosslinking agents, co-crosslinking agents, and functional monomers, characterized in that... Includes the following steps: The first step is to mix the raw materials evenly and then carry out a prepolymerization reaction to obtain a slurry product; The second step is to feed the slurry product obtained in the first step into the 3D printing device. The third step involves using a 3D printing device to spray the slurry-like product obtained in the first step into the molding die for the polymerization reaction through a printing nozzle. The fourth step involves the 3D printing device from the third step injecting material into the mold to undergo a polymerization reaction. After the polymerization reaction, the material is cooled to obtain a thermosetting polymer material prepared using 3D printing technology. The monomers in the raw materials are methyl methacrylate, styrene, or acrylonitrile; the initiator is azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, or cumene hydroperoxide; the crosslinking agent is allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, or divinylbenzene; the co-crosslinking agent is triisocyanurate triacrylate, trimethylolpropane trimethacrylate, or caprolactone methacrylate; and the functional monomer is polybutadiene or a silane coupling agent. The order of adding the raw materials in the first step is monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer. The purity of all five components is 99.9% or higher.

2. The process for preparing thermosetting polymer materials using 3D printing technology according to claim 1, characterized in that: In the fourth step, the jetting rate of the 3D printing device is 0.05 ml per minute to 5 ml per minute, and the displacement accuracy of the printing nozzle in each direction is no greater than ±0.5 mm.

3. The process for preparing thermosetting polymer materials using 3D printing technology according to claim 1, characterized in that: The raw materials, by weight, include 100 parts of monomer, 0.5 to 10 parts of initiator, 0.5 to 7 parts of crosslinking agent, 0.5 to 3 parts of co-crosslinking agent, and 0.01 to 5 parts of functional monomer. In the first step, the required amounts of monomer, initiator, crosslinking agent, co-crosslinking agent, and functional monomer are mixed by mechanical stirring and ultrasonic assistance for 1 to 5 hours.

4. A process for preparing thermosetting polymer materials using 3D printing technology according to claim 1, 2, or 3, characterized in that: The temperature of the prepolymerization reaction stage in the first step is controlled between 20 degrees Celsius and 80 degrees Celsius. The starting temperature is 20 degrees Celsius, the heating rate is less than or equal to 1 degree Celsius per hour, the prepolymerization reaction time is greater than or equal to 60 hours, and the ending temperature is 80 degrees Celsius. After the prepolymerization reaction is completed, the conversion rate of the polymerized monomer should be 30-40%.

5. A process for preparing thermosetting polymer materials using 3D printing technology according to claim 1, 2, or 3, characterized in that: The mold material in steps three and four should be radiation-resistant, but not metal; the temperature control rate of the polymerization reaction in step four is 0.1 degrees Celsius per hour, the starting temperature of the polymerization reaction is 40 degrees Celsius, and the ending temperature of the polymerization reaction is 180 degrees Celsius.

6. A process for preparing thermosetting polymer materials using 3D printing technology according to claim 1, 2, or 3, characterized in that: The mold is a cuboid with a diameter of 50 cm × 50 cm × 5 cm or a cylinder with a diameter of 50 cm and a height of 50 cm.

7. The apparatus for preparing thermosetting polymer materials using 3D printing technology according to claim 1, characterized in that: Includes feeders, reactors, and 3D printing equipment; The dispenser includes: Material storage tanks are used to store various raw materials. Metering pumps are used to weigh various raw materials to meet the required batch distribution ratios. Prepolymerization reactor, a reaction vessel used for prepolymerization reactions. Heater, used to heat the prepolymerization reactor; 3D printing equipment includes: The feeding device is used to transport the slurry after prepolymerization reaction in the prepolymerization reactor to the printing nozzle. The printing nozzle sprays the pre-polymerized slurry outwards and into the mold. The controller is used to control the movement of the printhead in all directions. The reactor includes: A mold is used to hold the slurry ejected from the printhead, providing a reaction site for the polymerization reaction and shaping the final product. Temperature control unit, used to control the temperature of the polymerization reaction with precision.

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