CN118725588A

CN118725588A - Double-component reactive 3D printing wax material and preparation method and application method thereof

Info

Publication number: CN118725588A
Application number: CN202411230832.2A
Authority: CN
Inventors: 钱琪枫; 区宇辉; 裴文剑
Original assignee: Zhejiang Shanzhu Group Co ltd
Current assignee: Zhejiang Shanzhu Group Co ltd
Priority date: 2024-09-04
Filing date: 2024-09-04
Publication date: 2024-10-01

Abstract

The invention provides a bi-component reactive 3D printing wax material, a preparation method and a use method thereof, and particularly relates to the technical field of 3D printing materials. The double-component reactive 3D printing wax material comprises a component A and a component B; component A comprises refined paraffin wax, aromatic dihydroxy compound monomer, catalyst and antioxidant; component B comprises refined paraffin wax, carbonyl compound monomer and antioxidant. According to the invention, the aromatic dihydroxy compound monomer and the carbonyl compound monomer are separated by the two components, so that the melt viscosity of the printing wax material is reduced, the problem of fluidity of the traditional high polymer polycarbonate in MJP jet printing is effectively solved, and the printing process is smoother. The generated polycarbonate is combined with other components in the wax material, so that the integral mechanical property of the printing die is improved, the dimensional accuracy of the die is obviously improved, and the strict requirement of high-accuracy investment casting is met.

Description

Double-component reactive 3D printing wax material and preparation method and application method thereof

Technical Field

The invention relates to the technical field of 3D printing materials, in particular to a double-component reactive 3D printing wax material and a preparation method and a use method thereof.

Background

3D printing technology, a rapidly evolving rapid freeform technique, has demonstrated its importance in a number of fields. Multi-nozzle spray technology (MJP), a branch of 3D printing technology, is particularly suitable for printing models based on waxy materials. These models play an important role in investment casting because they can replace traditional mold opening methods, saving costs and shortening production cycles. At present, the MJP technology has been widely applied to the fields of medical instruments, jewelry, artware, model manufacturing, industrial casting, precision casting and the like.

However, the MJP technology faces some challenges in practical applications. The currently used wax materials are poor in thermal deformation performance and mechanical performance, so that the printed mold has larger deviation in form and position tolerance, and the requirement of high-precision investment casting cannot be met. In order to improve the mechanical properties of the 3D printing wax, fillers such as crosslinked polystyrene are often added. These fillers, while capable of significantly improving the mechanical properties of the material, have a relatively high melt viscosity and viscoelasticity themselves, which makes them difficult to print directly by 3D printing techniques such as mxp.

In view of this, the present invention has been made.

Disclosure of Invention

The invention aims to provide a bi-component reactive 3D printing wax material, which aims to solve at least one of the technical problems in the prior art.

The second purpose of the invention is to provide a preparation method of the bi-component reactive type 3D printing wax material.

The invention further aims to provide a use method of the two-component reactive type 3D printing wax material.

In order to solve the technical problems, the invention adopts the following technical scheme:

The first aspect of the invention provides a two-component reactive 3D printing wax material comprising a component A and a component B;

Wherein, the component A comprises refined paraffin wax, aromatic dihydroxy compound monomer, catalyst and antioxidant;

the component B comprises refined paraffin wax, carbonyl compound monomer and antioxidant.

Further, the component A or the component B independently comprises at least one of a mechanical modifier, liquid paraffin, tackifying resin, a nucleating agent and toner.

Further, the component A comprises, by weight, 50-70 parts of refined paraffin, 10-25 parts of aromatic dihydroxy compound monomers, 0.01-0.5 part of catalysts and 0.01-0.5 part of antioxidants;

The component B comprises 50-70 parts of refined paraffin, 10-25 parts of carbonyl compound monomer and 0.01-0.5 part of antioxidant.

Further, the component A also comprises at least one of 2-10 parts by weight of mechanical modifier, 1-5 parts by weight of liquid paraffin, 1-5 parts by weight of tackifying resin, 1-3 parts by weight of nucleating agent and 0.1-0.3 part by weight of toner.

The component B also comprises at least one of 2-10 parts of mechanical modifier, 3-10 parts of liquid paraffin, 1-5 parts of tackifying resin, 1-3 parts of nucleating agent and 0.1-0.3 part of toner according to parts by weight.

Further, the refined paraffin wax includes at least one of unsaturated hydrocarbon wax, natural vegetable wax, and synthetic wax.

The aromatic dihydroxy compound monomer comprises at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol Z and tetramethyl bisphenol F.

The catalyst includes at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrabutyl titanate.

The antioxidant comprises a thiol antioxidant.

The carbonyl compound monomer includes at least one of diphenyl carbonate, bis (4-methylphenyl) carbonate, bis (4-chlorophenyl) carbonate, and bis (4-nitrophenyl) carbonate.

Further, the mechanical modifier comprises at least one of palm wax, candelilla wax, butadiene-styrene copolymer and POE.

The tackifying resin includes at least one of terpene resins, rosins, rosin derivatives, petroleum resins, and modified petroleum resins.

The nucleating agent includes at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid, and palmitic acid. The toner includes at least one of an inorganic toner, an organic toner, a composite pigment, a fluorescent pigment, and a pearlescent pigment. The second aspect of the invention provides a preparation method of the bi-component reactive 3D printing wax material, which comprises the following steps:

a. Uniformly mixing the raw materials in the component A at 150-180 ℃ to obtain a molten liquid of the component A, and filtering and cooling to obtain the component A;

b. and uniformly mixing the raw materials in the component B at 110-130 ℃ to obtain a molten liquid of the component B, and filtering and cooling to obtain the component B.

The third aspect of the invention provides a use method of the bi-component reactive type 3D printing wax material, wherein in the multi-nozzle jet printing process, a nozzle with a plurality of nozzles is used for printing a component A and a component B respectively, under the heating condition, the component A and the component B are fused and react to form the layer structure, and finally a printing platform moves upwards to repeat the printing step to obtain a model.

Further, the separate printing is to print the component a and then the component B at the same position using two heads.

Or alternatively, the first and second heat exchangers may be,

The separate printing is to print the component A in a certain layer to form a continuous component A layer and then print the component B on the component A layer to form a component B layer by using two spray heads.

Further, the separate printing is to print the component A and the component B on the same layer in a dot matrix penetrating way by adopting different channels of a single spray head.

Compared with the prior art, the invention has at least the following beneficial effects:

According to the bi-component reactive type 3D printing wax material, the aromatic dihydroxy compound monomer and the carbonyl compound monomer are separated by the bi-components, so that the melt viscosity of the printing wax material is reduced, the problem of fluidity of the traditional high polymer polycarbonate in MJP jet printing is effectively solved, and the printing process is smoother. In the 3D printing process, the two monomers rapidly react under the action of a catalyst to generate the polycarbonate with high mechanical strength, high toughness and high thermal deformation resistance. The polycarbonate is combined with other components in the wax material, so that the integral mechanical property of the printing die is improved, the dimensional accuracy of the die is obviously improved, and the strict requirement of high-accuracy investment casting is met.

The preparation method provided by the invention ensures the uniformity of the melt of the component A and the component B in chemical and physical properties by mixing the raw materials in a specific temperature range, and is beneficial to realizing better reactivity and stability in the printing process. The filtering and cooling step further ensures the purity and solidification quality of the components and avoids the potential influence of impurities on the printing quality and the final product performance. The preparation method has simple process and large batch processing capacity, and is suitable for large-scale industrial production.

The application method provided by the invention ensures that the component A and the component B are uniformly distributed on the printing platform, and realizes tight combination among layers. Not only improves the printing efficiency, but also ensures the mechanical property and the dimensional stability of the printing piece through instant chemical reaction, so that the final 3D printing model has higher precision and durability.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

FIG. 1 shows that component A of example 1 was printed in a dot matrix;

FIG. 2 shows that component B was printed on the same location as component A in the form of a dot matrix in example 1.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations.

The component B comprises refined paraffin wax, carbonyl compound monomer and antioxidant. Component a and component B are isolated from each other and do not contact prior to printing.

The invention adopts a method of printing two components in sequence, can effectively realize the fusion of ink drops, and further promotes the occurrence of polymerization reaction. This method involves two different components which are ejected sequentially by the nozzle during printing and which merge rapidly after contact. Such fusion occurs not only at the surface of the ink droplets, but also because of the small volume of the ink droplets (typically between 1 and 6 picoliters), they have a large specific surface area, which helps to accelerate the mixing and reaction between the components.

In addition, paraffin wax, as part of the wax material, cools at a relatively slow rate, a property that provides more time for the ink droplets to fuse. This sufficient fusion is critical because it allows the monomers to bond more effectively during polymerization, ultimately producing a polycarbonate filler. The filler not only enhances the mechanical properties of the wax material, but also forms a composite structure which is particularly useful in multi-nozzle jet printing (MJP) technology because it can improve the accuracy and stability of the printed article.

By the two-component printing and fusion technology, the distribution and polymerization reaction of ink drops can be precisely controlled, so that a 3D printing product with specific performance is manufactured. The application of this method opens up new possibilities for high precision and functional 3D printing.

In one embodiment of the invention, the reaction that occurs during the process is as follows:

Polycarbonates are high performance thermoplastics that are typically formed from low viscosity monomers by melt transesterification. In the 3D printing process, the reaction can be performed inside the printing equipment, so that the phenomenon that the viscosity and the viscoelasticity of a material system are too high due to the fact that high-molecular-weight polycarbonate is directly added is avoided, and therefore the wax material is difficult to process through a 3D printing technology.

Because of their good melt flow properties, monomers are well compatible with waxes while maintaining high thermal stability. This property is critical to the 3D printing process because it ensures flowability and reactivity of the material during printing. In addition, the melt fluidity and thermal stability of the monomers enable them to smoothly perform a melt transesterification reaction during printing after being mixed with a wax material without affecting the printing quality due to temperature variation or improper reaction conditions.

The matching of the reaction process and the melt printing process ensures that monomers can react rapidly to form polycarbonate in the printing process, and meanwhile, the precision and the strength of a printed piece are maintained. In this way, the 3D printing technology can produce composite materials which have wax material characteristics and integrate excellent properties of polycarbonate, and the possibility of 3D printing in different application fields, such as precision manufacturing, medical equipment and high-end consumer products, is widened.

Typically, but not by way of limitation, the composition of component a may be as follows in parts by weight: the refined paraffin may be 50 parts, 55 parts, 60 parts, 65 parts, 67 parts, 68 parts, 69 parts or 70 parts, or may be any value within the range of 50 to 70 parts; the aromatic dihydroxy compound monomer may be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts or 25 parts, or may be any value within the range of 10 to 25 parts; the catalyst may be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.4 part, 0.45 part or 0.5 part, or may be any value within the range of 0.01 to 0.5 part; the antioxidant may be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.4 part, 0.45 part or 0.5 part, or may be any value within a range of 0.01 to 0.5 part.

Likewise, the composition of the component B can also be as follows in parts by weight: the refined paraffin may be 50 parts, 55 parts, 60 parts, 65 parts, 67 parts, 68 parts, 69 parts or 70 parts, or may be any value within the range of 50 to 70 parts; the carbonyl compound monomer may be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts or 25 parts, or may be any value within the range of 10 to 25 parts; the antioxidant may be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.4 part, 0.45 part or 0.5 part, or may be any value within a range of 0.01 to 0.5 part.

Further, the component A also comprises at least one of 2-10 parts of mechanical modifier, 3-10 parts of liquid paraffin, 1-5 parts of tackifying resin, 1-3 parts of nucleating agent and 0.1-0.3 part of toner according to parts by weight.

Further, the component B also comprises at least one of 2-10 parts of mechanical modifier, 3-10 parts of liquid paraffin, 1-5 parts of tackifying resin, 1-3 parts of nucleating agent and 0.1-0.3 part of toner according to parts by weight.

Typically, but not limited to, the component A may further comprise at least one of a mechanical modifier, liquid paraffin, tackifying resin, nucleating agent and toner, and specifically, the mechanical modifier may be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, and may also be any value in the range of 2 to 10 parts; the liquid paraffin may be 1 part, 2 parts, 3 parts, 4 parts or 5 parts, or any value within the range of 1 to 5 parts; the tackifying resin may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1 to 5 parts; the nucleating agent can be 1 part, 2 parts or 3 parts, or can be any value within the range of 1-3 parts; the toner may be 0.1 part, 0.2 part, 0.25 part, or 0.3 part, or may be any value within a range of 0.1 to 0.3 part.

The component B can also comprise at least one of mechanical modifier, liquid paraffin, tackifying resin, nucleating agent and toner, and the mechanical modifier can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or can be any value in the range of 2-10 parts; the liquid paraffin may be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any value within the range of 3 to 10 parts; the tackifying resin may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1 to 5 parts; the nucleating agent can be 1 part, 2 parts or 3 parts, or can be any value within the range of 1-3 parts; the toner may be 0.1 part, 0.2 part, 0.25 part, or 0.3 part, or may be any value within a range of 0.1 to 0.3 part.

Further, the refined paraffin wax includes at least one of unsaturated hydrocarbon wax, natural vegetable wax, synthetic wax, and low molecular weight polyethylene wax.

The antioxidant comprises a thiol antioxidant.

The nucleating agent includes at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid, and palmitic acid.

The toner includes at least one of an inorganic toner, an organic toner, a composite pigment, a fluorescent pigment, and a pearlescent pigment.

The second aspect of the invention provides a preparation method of the bi-component reactive 3D printing wax material, which comprises the following steps:

It should be noted that the equal volume mixing of component a and component B, and the adjustment of the corresponding proportions of reactive monomers in component a and component B, ensures that the stoichiometric ratio of the two components during the reaction is appropriate during printing, thereby helping to achieve optimal chemical reaction conditions and properties of the final product.

Or alternatively, the first and second heat exchangers may be,

Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict. The raw materials used in the present invention are commercially available unless otherwise specified.

The thiol antioxidant used in the following examples and comparative examples was tetrabutylthiuram disulfide, pale yellow powder, hubei Xingzheng technology Co., ltd.

Example 1

The embodiment provides a bi-component reactive 3D printing wax material, which is prepared by the following steps:

Component A: taking 600g of 90# refined paraffin, 217.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 95# microcrystalline wax, 50g of white wax oil and 5g of thiol antioxidant, adding into a beaker, heating to 160 ℃, mechanically stirring uniformly, adding 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a particle size of 3 mu m, cooling, sealing and preserving for later use.

Component B: adding 602.5g of 90# refined paraffin, 217.5g of diphenyl carbonate, 30g of 95# microcrystalline wax, 70g of white wax oil and 5g of thiol antioxidants into a beaker, heating to 120 ℃, mechanically stirring uniformly, adding 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a filtrate with a diameter of 3 mu m, cooling, sealing and preserving for later use.

The printing method comprises the following steps: in the 3D printing process, the model file is first imported into the slicing software of the MJP printer, which is responsible for breaking down the model into a series of printable slicing files. Next, the component a and the component B were printed using the head 1 and the head 2 of the MJP printer, respectively.

As shown in FIG. 1, a spray head 1 prints component A precisely in the form of a dot array onto a substrate or a previously printed structure. Next, as shown in fig. 2, the nozzle 2 prints droplets of component B of equal volume at the same location, ensuring that the two components are accurately aligned and fused. To achieve a more uniform fusion, the spray head 1 will adjust the spray position so that new component a drops are interspersed in the previously printed drop array. Subsequently, the spray head 2 sprays the component B again on the same location, ensuring that the two components are sufficiently contacted and mixed.

Under the action of a catalyst, the top layer is matched with infrared heating to 140 ℃, so that the rapid polymerization of the component A and the component B is promoted, and a composite structure of the polymer of the polycarbonate and the wax material is formed. After polymerization is completed, the infrared heating is turned off, the layer is cooled and solidified, and printing of the layer is completed.

Subsequently, the printing platform moves up by one layer of height, the printing and aggregation processes are repeated, and the model is built layer by layer. By this continuous, stacked printing technique, complex three-dimensional structures can be precisely fabricated until the entire model is printed.

Example 2

The present embodiment provides a two-component reactive 3D printing wax material, which is different from embodiment 1 in that the formulation of the two-component reactive 3D printing wax material is the same, and the printing method is as follows:

In the preparation of a 3D printing model, the model file is first imported into the slicing software of an mxp printer, which converts the model into a series of printable slicing paths. The printing process involves head 1 and head 2, which are responsible for printing component a and component B, respectively.

The jet 1 prints component a onto the substrate or onto a previously printed structure in the form of successive adjacent contacting droplets along a single straight path. Next, the head 2 prints the component B on the same straight line path in the same manner, ensuring that it coincides closely with the droplets of the component a, forming a continuous straight line. By alternately printing component a and component B, successive planes are gradually constructed.

While each layer is being printed, the catalyst and the top layer infrared heating system work cooperatively to maintain the temperature at 140 ℃, promote the chemical reaction and polymerization of component a and component B, and produce a composite structure of the polymer of polycarbonate and the wax. After polymerization is completed, the infrared heating is turned off, the layer is cooled and solidified, and printing of the layer is completed.

Subsequently, the printing platform moves upwards to the height of the next layer, the printing, polymerizing and cooling processes are continuously repeated, and the model is built layer by layer. This layer-by-layer printing method ensures that each layer is accurately combined with the next layer until the entire model is printed.

Example 3

in the preparation of a 3D printing model, the model file is first imported into the slicing software of the mxp printer, which is responsible for converting the model into a series of printable slicing paths. The printing process involves two jets, jet 1 being responsible for printing component a and jet 2 being responsible for printing component B.

At the beginning of printing, the head 1 first prints a layer of successive components a on the base plate, forming an initial print layer. Next, the spray head 2 prints a continuous layer of component B on the same location, ensuring that it quickly merges with the component a which has not yet been completely cooled. The instant fusion process promotes the chemical reaction and polymerization of the two components by the action of the catalyst and the temperature of the top infrared heating system to 140 ℃ to form a composite structure of the polymer of the polycarbonate and the wax.

After polymerization is completed, the infrared heating system is turned off, the layer is cooled and solidified, and printing of the current layer is completed. And then, the printing platform moves upwards to the height of a new layer, the printing, fusing, polymerizing and cooling processes are continuously repeated, and the model is built layer by layer. This continuous stack printing technique ensures that each layer is accurately bonded to the next layer until the printing of the entire model is completed.

Example 4

Component A: 300g of 95# refined paraffin, 250g of ceresin wax, 50g of beeswax, 217.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 85# microcrystalline wax, 50g of white wax oil and 5g of thiol antioxidant are taken, added into a beaker, heated to 160 ℃, mechanically stirred uniformly, then 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner are added, continuously stirred uniformly, a uniformly dispersed melt is obtained, the melt is filtered by a candle filter, then added into a container, the filter diameter is 3 mu m, and then cooled, sealed and stored for standby.

Component B: 302.5g of 95# refined paraffin, 250g of ceresin wax, 50g of beeswax, 217.5g of diphenyl carbonate, 30g of 85# microcrystalline wax, 70g of white wax oil and 5g of thiol antioxidants are added into a beaker, heated to 130 ℃, mechanically stirred uniformly, 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner are added, continuously stirred uniformly, a uniformly dispersed melt is obtained, the melt is filtered by a candle filter, then the melt is added into a container, the filter diameter is 3 mu m, and then the melt is cooled, sealed and stored for standby.

The printing method comprises the following steps: as in example 1.

Example 5

Component A: taking 600g of 90# refined paraffin, 180g of bisphenol A monomer, 37.5g of bisphenol S monomer, 2.5g of tetramethyl phosphorus acetate, 50g of 95# microcrystalline wax, 50g of white wax oil and 5g of mercaptan antioxidant, adding into a beaker, heating to 160 ℃, mechanically stirring uniformly, adding 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a filtrate with a diameter of 3 mu m, cooling, sealing and preserving for standby.

The printing method comprises the following steps: as in example 1.

Example 6

Component A: 700g of 90# refined paraffin, 117.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 95# microcrystalline wax, 50g of white wax oil and 5g of thiol antioxidant are taken, added into a beaker, heated to 160 ℃, mechanically stirred uniformly, then 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner are added, continuously stirred uniformly, a uniformly dispersed melt is obtained, filtered by a candle filter, added into a container, the filter diameter is 3 mu m, cooled and stored in a sealed manner for standby.

Component B: taking 702.5g of 90# refined paraffin, 117.5g of diphenyl carbonate, 30g of 95# microcrystalline wax, 70g of white wax oil and 5g of mercaptan antioxidants, adding into a beaker, heating to 120 ℃, mechanically stirring uniformly, adding 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a diameter of 3 mu m, cooling, sealing and preserving for later use.

The printing method comprises the following steps: as in example 1.

Comparative example 1

The comparative example provides a single-component 3D printing wax material, which is prepared by adding 90# refined paraffin wax 820g,95# microcrystalline wax 50g, white wax oil 50g and thiol antioxidant 5g into a beaker, heating to 160 ℃, mechanically stirring uniformly, adding hydrogenated rosin resin 50g, PE wax 20g and 112 toner 5g, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by a candle filter, adding into a container, filtering to obtain a filtrate with a diameter of 3 mu m, cooling, sealing and preserving for later use.

The printing method comprises the following steps: and (3) importing the 3D printing model file into slicing software of an MJP printer to generate a slicing file, spraying wax liquid drops by a single spray head to form a continuous liquid level, naturally cooling the wax, and printing layer by layer.

Comparative example 2

The comparative example provides a single-component 3D printing wax material, which is prepared by taking 5000 g of 85# refined paraffin wax, 50g of 90# microcrystalline wax, 20g of ethylene-vinyl acetate copolymer, 30g of white wax oil, 5g of thiol antioxidant, adding into a beaker, heating to 160 ℃, mechanically stirring uniformly, adding 40g of hydrogenated rosin resin, 10g of C5 tackifying resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a particle diameter of 3 mu m, cooling, sealing and preserving for standby.

Comparative example 3

The comparative example provides a single-component 3D printing wax material, which is prepared by adding 590g of 90# refined paraffin wax, 230g of polycarbonate powder particles, 50g of 95# microcrystalline wax, 50g of white wax oil, 5g of thiol antioxidants, 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner into a beaker, heating to 300 ℃, and mechanically stirring to obtain a uniformly dispersed melt, wherein the melt has poor fluidity and cannot be directly printed.

Comparative example 4

The comparative example provides a bi-component reactive 3D printing wax material, which is prepared by the following steps:

component A: taking 730g of 90# refined paraffin, 117.5g of bisphenol A diglycidyl ether, 70g of 95# microcrystalline wax and 5g of mercaptan antioxidants, adding into a beaker, heating to 120 ℃, mechanically stirring uniformly, adding 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner, continuously stirring uniformly to obtain uniformly dispersed melt, filtering by using a candle filter, adding into a container, filtering to obtain a filtrate with a diameter of 3 mu m, cooling, sealing and preserving for later use.

Component B: 780g of 90# refined paraffin, 40g of diethylenetriamine, 30g of 95# microcrystalline wax, 70g of white wax oil and 5g of mercaptan antioxidants are taken, added into a beaker, heated to 120 ℃, mechanically stirred uniformly, 50g of hydrogenated rosin resin, 20g of PE wax and 5g of 112 toner are added, continuously stirred uniformly to obtain uniformly dispersed melt, filtered by a candle filter, added into a container, filtered to a diameter of 3 mu m, cooled, sealed and stored for standby.

The printing method comprises the following steps: as in example 1.

Test example 1

In the examples and comparative examples, the viscosities of the component a and the component B were measured, respectively, and the viscosities after the reaction of the component a and the component B were measured. The viscosity of the single-component 3D printing wax material is expressed as the viscosity of component a.

The viscosity tester is An Dongpa MCR92 rotational viscosity tester, the measuring system uses a flat plate rotor, the shearing rate is 2000s ^-1, and the testing interval is 0.1mm.

The data obtained are shown in table 1 below.

TABLE 1

Test example 2

Thermal weight TGA testing was performed on the models printed from examples and comparative examples.

The thermogravimetric TGA test instrument is a Metrele TGA2 (SF) thermogravimetric analyzer, the heating rate is 10 ℃/min, the maximum temperature is 600 ℃, and the mass of the test sample is 20mg. Wherein T0 is the temperature corresponding to the initial sample mass loss of 1%, 350 ℃ is the lowest temperature for ensuring the volatilization of more than 99% of the wax component, T1 is the temperature at which the mass reduction rate corresponding to the sample after the volatilization of the wax component increases to 0.05%/min, and this temperature is considered as the initial temperature at which the decomposition of the residual polycarbonate starts to be accelerated. The data obtained are shown in table 2 below.

TABLE 2

The results in Table 2 verify the formation of polycarbonate in the component A and component B printed waxes. Comparative example 1 and comparative example 1, the sample of example 1 had a significant accelerated decomposition phase after T1, whereas comparative example 1 did not decompose at a higher rate after T1, corresponding to the two-component printing mode of example 1 to produce polycarbonate; examples 2-6 demonstrate the effect of different printing modes, types and amounts of reactive monomers on the amount of polycarbonate produced. Comparative example 2 shows the effect of wax without the addition of a filler of the polycarbonate type on the thermal stability of the sample; comparative example 3 demonstrates the thermal stability impact of adding polycarbonate powder particles directly to a printing wax on final sample properties; comparative example 4 demonstrates the effect of adding a non-polycarbonate monomer (epoxy monomer) to component a and component B on the thermal stability of the components.

Test example 3

The models printed in the examples and the comparative examples were subjected to mechanical tests, including in particular tensile strength, tensile modulus and deformation dimension tests.

The length of the tensile test strip is 80 x 10 x 4mm, the test instrument is an Instron universal tester 34TM-10, and the tensile rate is 10mm/min; the deformation dimension measuring instrument is an electronic oven and a vernier caliper. The data obtained are shown in table 3 below.

TABLE 3 Table 3

Table 3 shows a comparison of mechanical properties and thermal deformation resistance of the printed bars of the respective examples and comparative examples. Wherein the results of example 1 show the highest performance improvement, examples 2-6 show the different ways of printing, the type and content of reactive monomers, respectively, with different degrees of influence on the performance improvement. Comparative example 2 shows the effect of wax without the addition of polycarbonate filler on the mechanical and heat distortion resistance properties of the sample; comparative example 3 demonstrates the thermal stability impact of adding polycarbonate powder particles directly to a printing wax on the mechanical and heat distortion resistance properties of the final sample; comparative example 4 shows the effect of adding a non-polycarbonate monomer (epoxy monomer) to component a and component B on the mechanical and heat distortion resistance properties of the components.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims

1. The double-component reactive 3D printing wax material is characterized by comprising a component A and a component B;

2. The two-component reactive 3D printing wax of claim 1, wherein component a or component B each independently further comprises at least one of a mechanical modifier, liquid paraffin, tackifying resin, nucleating agent, and toner.

3. The two-component reactive 3D printing wax material according to claim 1, wherein the component A comprises, by weight, 50-70 parts of refined paraffin wax, 10-25 parts of an aromatic dihydroxy compound monomer, 0.01-0.5 part of a catalyst and 0.01-0.5 part of an antioxidant;

4. The two-component reactive 3D printing wax material according to claim 1, wherein the component A further comprises at least one of 2-10 parts by weight of a mechanical modifier, 1-5 parts by weight of liquid paraffin, 1-5 parts by weight of a tackifying resin, 1-3 parts by weight of a nucleating agent and 0.1-0.3 parts by weight of toner;

The component B also comprises at least one of 2-10 parts of mechanical modifier, 3-10 parts of liquid paraffin, 1-5 parts of tackifying resin, 1-3 parts of nucleating agent and 0.1-0.3 part of toner.

5. The two-component reactive 3D printing wax material of any of claims 1-4, wherein the refined paraffin wax comprises at least one of an unsaturated hydrocarbon wax, a natural vegetable wax, and a synthetic wax;

The aromatic dihydroxy compound monomer comprises at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol Z and tetramethyl bisphenol F;

The catalyst comprises at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrabutyl titanate;

The antioxidant comprises a thiol antioxidant;

6. The two-component reactive 3D printing wax of claim 2 or 4, wherein the mechanical modifier comprises at least one of palm wax, candelilla wax, butadiene styrene copolymer, and POE;

The tackifying resin comprises at least one of terpene resin, rosin derivatives, petroleum resin and modified petroleum resin;

The nucleating agent comprises at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid and palmitic acid;

7. A method for preparing the two-component reactive 3D printing wax material according to any one of claims 1 to 6, comprising the steps of:

8. The method for using the bi-component reactive type 3D printing wax material according to any one of claims 1-6, wherein in the multi-nozzle jet printing process, a nozzle with a plurality of nozzles is used for printing the component A and the component B respectively, the component A and the component B are fused and react to form the layer structure under the heating condition, and finally a printing platform moves upwards to repeat the printing step to obtain the model.

9. The method of claim 8, wherein the printing is printing component a and then component B at the same location using two heads;

Or alternatively, the first and second heat exchangers may be,

10. The method according to claim 8, wherein the separate printing is to print the component a and the component B on the same layer in a dot-matrix interpenetration manner by using different channels of a single nozzle.