Thermosetting resin material system for additive manufacturing and preparation method and application thereof

Abstract

The invention relates to the field of printing materials, in particular to a thermosetting material system for additive manufacturing and a preparation method and application thereof. Comprising resin A and resin B, the resin A and the resin B are mixed according to the weight ratio of 1.5: (1-4.5), the mixed product and filler are mixed and stirred according to the weight ratio of 1: (2-5), and a thermosetting resin system is obtained; compared with a traditional thermoplastic material, extrusion printing under the high-temperature condition is not needed, and the problem that a high-temperature-resistant material is seriously warped and deformed during high-temperature extrusion printing is solved; meanwhile, the problem that a thermosetting material is difficult to stack and form due to the fact that the thermosetting material cannot be quickly cured and formed during additive manufacturing is solved, high-temperature curing can be continuously carried out after extrusion, stacking and preliminary forming, and the problem that a traditional light curing-heat curing material system is limited by light curing efficiency is solved; and the printing efficiency is improved, and the method is suitable for printing and manufacturing of large-size products and has certain generalization performance.

Description

Technical Field

[0001] The present invention relates to the field of 3D printing materials, and in particular to a thermosetting resin material system for additive manufacturing, a preparation method and an application thereof. Background Art

[0002] With its personalized and rapid manufacturing characteristics, additive manufacturing technology is gradually moving from product selection, assembly and other development and verification to the industrial-grade application stage, and the size range of additive manufacturing has also expanded to the meter level; the industrial-grade screw extrusion large-size FDM printing technology is mainly used for the printing and manufacturing of industrial-grade large-size parts. Screw extrusion printing can make the material plasticized more fully. The printing material generally uses thermoplastic-based materials, which are easy to realize multi-material composites, have strong applicability and a wide range of applications.

[0003] However, the current thermoplastic material extrusion technology has great limitations. First of all, ordinary thermoplastic materials cannot meet the high temperature resistance requirements, especially in the field of autoclave composite materials. Since the autoclave involves high temperature and high pressure problems, for example, the medium temperature autoclave system, the temperature is generally 100-200 ° C, and the temperature inside the high temperature autoclave system exceeds 200 ° C. Therefore, ordinary thermoplastic materials cannot meet the autoclave process temperature requirements. Materials such as PEI, PPS and PEEK, although they can meet the high temperature resistance requirements, are on the one hand, the cost of the material itself is relatively high. On the other hand, the printing temperature of such materials is extremely high, so the equipment must be equipped with a high-precision high-temperature molding chamber. Therefore, the cost of printing equipment for such materials is also much higher than that of ordinary fused deposition printing equipment, resulting in extremely high printing and manufacturing costs for such materials.

[0004] In addition to cost issues, traditional thermoplastic materials also have a significant problem of large thermal expansion coefficients, which causes serious internal stress during the printing process and high-temperature use of the product. This internal stress will cause warping and deformation of the printed parts during the printing process, and in severe cases will lead to printing failure. When the product is used, this serious internal stress will lead to a lack of dimensional accuracy, especially when used as a mold, which will cause the final product to fail to meet the dimensional accuracy requirements of production.

[0005] Therefore, based on the above problems, traditional technology proposes the concept of using thermosetting resin systems to replace the original thermoplastic materials for printing. However, the existing thermosetting resin system requires a certain amount of time in the printing and curing process, and the fast-curing thermosetting resin material system is prone to clogging of the print head. Therefore, it is difficult for thermosetting resins to be directly deposited by 3D printing. Therefore, in order to achieve the printing of thermosetting resin systems, the current general method is to add a photocurable resin system to the resin system. During the extrusion of the resin system, the extruded material is instantly shaped and cured by an ultraviolet lamp, thereby meeting the needs of layer-by-layer deposition of 3D printing. However, the photocuring depth of a general photocurable resin system is generally 200 to 300 microns. Therefore, although this method achieves the printing of thermosetting resins, this method is limited by the photocuring technology itself, resulting in extremely low overall printing efficiency. Summary of the invention

[0006] In view of the problems mentioned in the prior art, the present invention proposes a thermosetting resin material system for additive manufacturing and a preparation method and application thereof to solve the problems in the background technology.

[0007] The invention discloses a method for preparing a thermosetting resin system for additive manufacturing, comprising resin A and resin B, wherein the resin A and the resin B are mixed at a weight ratio of 1.5:(1-4.5), the mixed product is mixed and stirred with a filler at a weight ratio of 1:(2-5), and the thermosetting resin system is obtained after uniform stirring; the resin A comprises a high temperature resistant epoxy resin and a polyamine; the resin B comprises an epoxy resin and an amine compound.

[0008] Preferably, the filler is one or more of alumina ceramics, silica powder, cordierite or aramid fiber powder.

[0009] Preferably, the high temperature resistant epoxy resin and the polyamine are mixed and stirred in a weight ratio of 3:(1-2).

[0010] Preferably, the high temperature resistant epoxy resin is one or more of AG80 resin, AG70 resin, AFG90 resin or F51 resin.

[0011] Preferably, the polyamine includes one or more of methylcyclopentanediamine, 4,4-diaminophenylsulfone or diaminodiphenylmethane.

[0012] Preferably, the epoxy resin and the amine compound are mixed in a weight ratio of 3:(1-3).

[0013] Preferably, the epoxy resin is one or more of epoxy resin E44, epoxy resin E51, epoxy resin E12 or epoxy resin E20.

[0014] Preferably, the amine compound is one or more of isophoronediamine, ethylenediamine or triethylenetetramine.

[0015] A thermosetting resin system prepared based on the above preparation method.

[0016] An application of the thermosetting resin system in 3D printing.

[0017] Compared with the prior art, the present invention has achieved the following technical effects:

[0018] Compared with the thermosetting resin system of the conventional technology, the thermosetting resin system of the present invention does not flow and deform itself when the thermosetting resin system is extruded without pressure. At the same time, it can be quickly cured after extrusion with the help of the residual heat of the extrusion process, thereby helping the thermosetting resin system to be initially shaped. The hardness and strength of the thermosetting resin system after initial shaping are significantly improved. Therefore, the thermosetting resin system after initial shaping can meet the requirements of layer-by-layer stacking of additive manufacturing. At the same time, since the thermosetting resin system contains a certain proportion of resin A, the resin A does not undergo a curing reaction in this process, so the initial shaping The surface of the thermosetting resin system after molding is still in a wet state, and the resin A with a certain degree of fluidity is distributed on its surface. Therefore, it can be ensured that during the subsequent high-temperature curing, the layers are secondary cured using the resin A that still has a certain degree of fluidity, thereby ensuring the interlayer bonding force of the printed product. At the same time, the resin A with a certain degree of fluidity between the layers can effectively avoid the problem of interlayer pore defects caused by the poor fluidity of the extruded molten resin in the traditional resin melt deposition process during the subsequent curing process, thereby ensuring the excellent high temperature resistance of the final printed product and the uniformity of the mechanical properties in multiple directions, and ensuring that the products manufactured by the present invention can be used in high temperature environments.

[0019] The ceramic filler added to the thermosetting resin system of the present invention causes the thermosetting resin system to lose its overall fluidity, leaving only a small amount of resin with a certain fluidity on its surface. This can utilize the stackability of the thermosetting resin system itself to ensure that the additive manufacturing layer-by-layer stacking process is completed smoothly. At the same time, the thermosetting resin system can ensure that the thermosetting resin system is quickly fixed during the stacking process, as well as the mechanical properties and high temperature resistance of the product after subsequent high-temperature curing. Moreover, with the stackability of the thermosetting resin system itself, efficient printing and manufacturing can be carried out without being limited by photocuring efficiency. Therefore, the present invention is suitable for printing and manufacturing of large-size products. Combined with subsequent subtractive processing technology, large-size, high-temperature resistant products can be obtained at low cost and high efficiency, and are particularly suitable for the mold field. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1This is the DSC data diagram of the present invention. DETAILED DESCRIPTION

[0021] The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are only used to explain the present invention, rather than to limit the present invention. It should also be noted that, for ease of description, only parts related to the present invention, rather than all structures, are shown in the accompanying drawings.

[0022] In the description of the present invention, unless otherwise clearly specified and limited, the terms "connected", "connected", and "fixed" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0023] In the description of this embodiment, the terms "upper", "lower", "right", etc., directions or positional relationships are based on the directions or positional relationships shown in the drawings, and are only for the convenience of description and simplification of operation, rather than indicating or implying that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and therefore cannot be understood as limiting the present invention. In addition, the terms "first" and "second" are only used to distinguish in the description and have no special meaning.

[0024] Example 1

[0025] The invention discloses a method for preparing a thermosetting resin system for additive manufacturing, comprising resin A and resin B, wherein the resin A and the resin B are mixed at a weight ratio of 1.5:(1-4.5), the mixed product is mixed and stirred with a filler at a weight ratio of 1:(2-5), and the thermosetting resin system is obtained after uniform stirring; the resin A comprises a high temperature resistant epoxy resin and a polyamine; the resin B comprises an epoxy resin and an amine compound.

[0026] The filler is one or more of alumina ceramics, silica powder, cordierite or aramid fiber powder.

[0027] The high temperature resistant epoxy resin and the polyamine are mixed and stirred in a weight ratio of 3:(1-2).

[0028] The high temperature resistant epoxy resin is one or more of AG80 resin, AG70 resin, AFG90 resin or F51 resin.

[0029] The polyamine includes one or more of methylcyclopentanediamine, 4,4-diaminophenylsulfone or diaminodiphenylmethane.

[0030] The epoxy resin and the amine compound are mixed in a weight ratio of 3:(1-3).

[0031] The epoxy resin is one or more of epoxy resin E44, epoxy resin E51, epoxy resin E12 or epoxy resin E20.

[0032] The amine compound is one or more of isophoronediamine, ethylenediamine or triethylenetetramine.

[0033] A method for using the thermosetting resin system in a 3D printing mold comprises the following steps:

[0034] S1: The thermosetting resin system is extruded and deposited at 60-80°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured and shaped in 5-10 minutes by residual temperature. After layer-by-layer deposition, a rough mold body is obtained. In this embodiment, the screw print head is a common mechanism in 3D printing and will not be elaborated in detail.

[0035] S2: performing step curing on the rough mold body, wherein the step curing is (80-100)°C / (30-60)min, (140-160)°C / (30-60)min, and (190-200)°C / (90-120)min; obtaining a cured mold body;

[0036] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0037] like Figure 1 As shown, it is concluded from the DSC data that the thermosetting resin system of the present invention has extremely high heat resistance, and its Tg is roughly calculated to be over 300°C.

[0038] Example 2

[0039] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0040] The selected resin A is prepared by mixing AG80 resin and methylcyclopentanediamine at a weight ratio of 3:1 at 40°C.

[0041] The selected resin B is prepared by mixing epoxy resin E44 and isophorone diamine in a weight ratio of 1:1.

[0042] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1.5:1.

[0043] The obtained mixed product is mixed with alumina ceramics in a weight ratio of 1:2, and stirred evenly to obtain a thermosetting resin system.

[0044] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0045] S1: The thermosetting resin system is extruded and deposited at 60°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 5 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0046] S2: performing step curing on the rough mold body, wherein the step curing is performed at 80° C. for 30 min, 140° C. for 30 min, and 190° C. for 90 min, to obtain a cured mold body;

[0047] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0048] Example 3

[0049] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0050] The selected resin A is prepared by mixing and stirring AG70 resin and 4,4-diaminophenylsulfone at a weight ratio of 3:2 at 60°C.

[0051] The selected resin B is prepared by mixing epoxy resin E51 and ethylenediamine in a weight ratio of 1.5:4.5.

[0052] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1:3.

[0053] The obtained mixed product is mixed with cordierite at a weight ratio of 1:5, and stirred evenly to obtain a thermosetting resin system.

[0054] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0055] S1: The thermosetting resin system is extruded and deposited at 80°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 10 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0056] S2: performing step curing on the rough mold body, wherein the step curing is 100° C., 30 min, 160° C., 60 min, and 200° C., 120 min, to obtain a cured mold body;

[0057] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0058] Example 4

[0059] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0060] The selected resin A is prepared by mixing AFG90 resin and diaminodiphenylmethane at a weight ratio of 3:1.5 at 50°C.

[0061] The selected resin B is prepared by mixing epoxy resin E12 and triethylenetetramine in a weight ratio of 3:2.

[0062] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1.5:3.

[0063] The obtained mixed product was mixed with aramid fiber powder in a weight ratio of 1:3, and stirred evenly to obtain a thermosetting resin system.

[0064] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0065] S1: The thermosetting resin system is extruded and deposited at 60°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 7 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0066] S2: performing step curing on the rough mold body, wherein the step curing is performed at 90° C., 45 min, 150° C., 45 min, and 195° C., 100 min, to obtain a cured mold body;

[0067] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0068] Example 5

[0069] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0070] The selected resin A is prepared by mixing and stirring F51 resin and methylcyclopentanediamine at a weight ratio of 3:1.2 at 45°C.

[0071] The selected resin B is prepared by mixing epoxy resin E20 and triethylenetetramine in a weight ratio of 1:1.

[0072] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1.5:3.

[0073] The obtained mixed product was mixed with silicon dioxide powder in a weight ratio of 1:4, and stirred evenly to obtain a thermosetting resin system.

[0074] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0075] S1: The thermosetting resin system is extruded and deposited at 75°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 8 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0076] S2: performing step curing on the rough mold body, wherein the step curing is 100° C., 50 min, 140° C., 50 min, and 200° C., 120 min, to obtain a cured mold body;

[0077] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0078] Example 6

[0079] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0080] The selected resin A is prepared by mixing and stirring F51 resin and methylcyclopentanediamine at a weight ratio of 3:1.8 at 45°C.

[0081] The selected resin B is prepared by mixing epoxy resin E20 and triethylenetetramine in a weight ratio of 3:1.

[0082] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1.5:3.5.

[0083] The obtained mixed product was mixed with alumina ceramics at a weight ratio of 1:4.5, and stirred evenly to obtain a thermosetting resin system.

[0084] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0085] S1: The thermosetting resin system is extruded and deposited at 80°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 5 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0086] S2: performing step curing on the rough mold body, wherein the step curing is performed at 95° C. for 60 min, 155° C. for 60 min, and 210° C. for 110 min, to obtain a cured mold body;

[0087] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0088] Example 6

[0089] The present invention provides a method for preparing a thermosetting resin system for additive manufacturing, comprising adding a filler to resin A and resin B to obtain a thermosetting resin system, and specifically comprising the following steps:

[0090] The selected resin A is prepared by mixing and stirring F51 resin and methylcyclopentanediamine at a weight ratio of 3:1.4 at 50°C.

[0091] The selected resin B is prepared by mixing epoxy resin E20 and triethylenetetramine in a weight ratio of 1:1.

[0092] The obtained resin A and resin B were mixed and stirred at a weight ratio of 1.5:2.

[0093] The obtained mixed product was mixed with silicon dioxide powder in a weight ratio of 1:2.5, and stirred evenly to obtain a thermosetting resin system.

[0094] The use of the thermosetting resin system in the 3D printing mold of this embodiment includes the following steps:

[0095] S1: The thermosetting resin system is extruded and deposited at 60°C according to a preset path using a screw print head. The extruded thermosetting resin system is initially cured for 5 minutes by residual temperature and deposited layer by layer to obtain a rough mold body.

[0096] S2: performing step curing on the rough mold body, wherein the step curing is 100° C., 30 min, 150° C., 30 min, and 200° C., 120 min, to obtain a cured mold body;

[0097] S3: performing milling and polishing on the solidified mold blank to obtain a mold.

[0098] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a thermosetting resin material system for additive manufacturing, characterized in that: The method comprises resin A and resin B, wherein the resin A and the resin B are mixed at a weight ratio of 1.5:(1-4.5), the mixed product and the filler are mixed and stirred at a weight ratio of 1:(2-5), and the thermosetting resin system is obtained after being stirred evenly; The resin A includes a high temperature resistant epoxy resin and a polyamine; the resin B includes an epoxy resin and an amine compound.

2. A method for preparing a thermosetting resin material system for additive manufacturing according to claim 1, characterized in that: The filler is one or more of alumina ceramics, silica powder, cordierite or aramid fiber powder.

3. The method for preparing a thermosetting resin material system for additive manufacturing according to claim 1, characterized in that: The high temperature resistant epoxy resin and the polyamine are mixed and stirred in a weight ratio of 3:(1-2).

4. The method for preparing a thermosetting resin material system for additive manufacturing according to claim 3, characterized in that: The high temperature resistant epoxy resin is one or more of AG80 resin, AG70 resin, AFG90 resin or F51 resin.

5. The method for preparing a thermosetting resin material system for additive manufacturing according to claim 3, characterized in that: The polyamine includes one or more of methylcyclopentanediamine, 4,4-diaminophenylsulfone or diaminodiphenylmethane.

6. The method for preparing a thermosetting resin material system for additive manufacturing according to claim 1, characterized in that: The epoxy resin and the amine compound are mixed in a weight ratio of 3:(1-3).

7. A method for preparing a thermosetting resin material system for additive manufacturing according to claim 6, characterized in that: The epoxy resin is one or more of epoxy resin E44, epoxy resin E51, epoxy resin E12 or epoxy resin E20.

8. The method for preparing a thermosetting resin material system for additive manufacturing according to claim 6, characterized in that: The amine compound is one or more of isophoronediamine, ethylenediamine or triethylenetetramine.

9. A thermosetting resin material system prepared according to the preparation method according to any one of claims 1 to 8.

10. Use of the thermosetting resin material system according to claim 9 in 3D printing.

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