Preparation method of a two-component 3D printing elastomer material containing microcapsule structure

Abstract

The application discloses a preparation method of a dual-component 3D printing elastomer material containing microcapsule structures, relates to the technical field of 3D printing materials, and discloses that the dual-component 3D printing elastomer material comprises component A and component B; component A comprises a photocuring oligomer, a chain extender and a leveling agent; and component B comprises a modified photoinitiator, a curing agent and polycaprolactone microcapsules; the capsule shell of the polycaprolactone microcapsules is polycaprolactone; and the capsule core is a polyurethane prepolymer and an epoxy resin. The dual-component 3D printing elastomer material provided by the application can store component A and component B separately before use, and the two components can be mixed during use, so that the reaction between the two components during storage can be avoided, and the storage period is prolonged. In addition, the Irgacure 819 modified by TiO2 has a higher photocuring rate, and rapid photocuring can be achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of 3D printing materials, and particularly relates to a preparation method of a two-component 3D printing elastomer material containing a microcapsule structure. BACKGROUND

[0002] In recent years, with the rapid development of additive manufacturing technology, i.e. 3D printing, its application in industrial production and innovative design is increasingly widespread. 3D printing technology builds three-dimensional objects by layering materials, providing unprecedented freedom for the design and manufacture of complex structures. In the field of elastomers, this technology has shown great potential. Elastomers are indispensable in many applications due to their excellent elasticity and deformation capacity, such as personalized medical devices, advanced insoles, and soft robotic components.

[0003] Traditional elastomer manufacturing methods, such as thermoforming or injection molding, are often limited by molds, making it difficult to easily achieve the manufacture of complex geometries, and the cost is relatively high in small batch production. With the advancement of FDM (Fused Deposition Modeling), SLA (Stereo Lithography Apparatus) and SLS (Selective Laser Sintering) 3D printing technologies, it is possible to directly use digital models to quickly manufacture complex geometric elastomer parts. These technologies not only simplify the product development process, but also improve the feasibility of customized products. Especially for elastomer components with complex internal structures or gradient performance requirements, 3D printing provides an economical and efficient and flexible solution.

[0004] In the light curing molding technology, the photoinitiator generates free radicals by absorbing light energy, which in turn initiates the polymerization of monomers to form solid materials. However, when oxygen is present, it can react with these free radicals, interrupting the growth of the polymerization chain and preventing the curing reaction from proceeding, thereby affecting the printing speed and efficiency. In addition, some photoinitiators in the pre-mixed resin may chemically react with other components in the resin during storage, affecting the final curing effect.

[0005] Therefore, it is a technical problem to be solved in the field to provide an elastomer material that is convenient to store, has a long storage period, and has a high light curing rate. SUMMARY

[0006] In view of the short shelf life and low light curing rate of existing 3D printing elastomer materials, the application provides a preparation method of a two-component 3D printing elastomer material containing a microcapsule structure. Specifically, the technical solution of the application includes the following contents:

[0007] One of the purposes of the present application is to provide a kind of two-component 3D printing elastomer material containing microcapsule structure, comprising component A and component B, the component A includes polyethylene glycol diacrylate, chain extender and leveling agent, the component B includes modified photoinitiator, curing agent and polycaprolactone microcapsule.

[0008] Further, the component A includes polyethylene glycol diacrylate 20-50 parts by weight, chain extender 1-5 parts and leveling agent 0.5-1.2 parts;The component B includes modified photoinitiator 1-2.5 parts, curing agent 1-5 parts and polycaprolactone microcapsule 25-60 parts.

[0009] The second purpose of the present application is to provide a kind of preparation method of two-component 3D printing elastomer material containing microcapsule structure, the preparation method comprises the following steps:

[0010] Preparation of component A: polyethylene glycol diacrylate is dispersed in organic solvent, chain extender and leveling agent are added, and stirring reaction is carried out at 40-45 DEG C environment for 1-2 h, and the component A is prepared after vacuum degassing after reaction.

[0011] Preparation of component B: modified photoinitiator is dispersed in organic solvent, and after ultrasonic, polycaprolactone microcapsule and curing agent are added, and stirring reaction is carried out at 40-45 DEG C environment for 1-2 h, and the component B is prepared after vacuum degassing after reaction.

[0012] Component A and component B, when used, are mixed in a weight ratio of component A: component B=1:1.5-3 to obtain two-component 3D printing elastomer material precursor, which is poured into 3D printer for printing, then placed in 120 DEG C oven and heated for 5 h, and then naturally cooled, to prepare the two-component 3D printing elastomer material.

[0013] Further, the chain extender includes at least one of 1,4-butanediol, ethylene glycol or 1,3-propanediol.

[0014] Further, the leveling agent is Tego-410.

[0015] Further, the curing agent is diaminodichlorodiphenylmethane.

[0016] Further, the organic solvent is acetone.

[0017] Further, the ultrasonic includes ultrasonic power 40-80 W and ultrasonic time 15-30 min.

[0018] Further, the vacuum degassing time is 30-60 min.

[0019] Further, the preparation method of the modified photoinitiator comprises the following steps:

[0020] Disperse 10 parts by weight of Ti02particles in 50 parts by weight of deionized water, add 100 parts by weight of 65% nitric acid solution, stir and react at 80°C for 2 hours, wash and dry to obtain hydroxylated Ti02;

[0021] Disperse 10 parts by weight of hydroxylated Ti02in 50 parts by weight of ethanol, add 5 parts by weight of 3-aminopropyl triethoxysilane, stir and react at 80°C for 4 hours, wash and dry to obtain aminated Ti02;

[0022] Disperse 20 parts by weight of Irgacure 819 in 50 parts by weight of acetone, add 10 parts by weight of maleic anhydride and stir for 5 minutes, then add 1 part by weight of triethylamine, control the temperature at 60°C in a nitrogen atmosphere, and stir and react for 12 hours to prepare carboxylated Irgacure 819.

[0023] Disperse 10 parts by weight of aminated Ti02and 20 parts by weight of carboxylated Irgacure 819 in 50 parts by weight of acetone, add 10 parts by weight of EDC and 5 parts by weight of NHS, stir and react at 60°C for 2 hours to prepare a modified photoinitiator.

[0024] Further, the preparation method of the polycaprolactone microcapsule comprises the following steps:

[0025] Dissolve 10 parts by weight of polyether polyol in 50 parts by weight of N,N-dimethylformamide, add 12 parts by weight of diisocyanate and 0.1 part by weight of dibutyltin dilaurate, stir and react at 150°C for 2 hours in a nitrogen atmosphere to obtain a polyurethane prepolymer; dissolve 10 parts by weight of the polyurethane prepolymer and 10 parts by weight of epoxy resin in 100 parts by weight of ethyl acetate to obtain a mixed solution; disperse 0.5 parts by weight of Span-80 in 100 parts by weight of deionized water, add the above-mentioned mixed solution, stir and react at 10000 rpm for 5 minutes to form a stable oil / water emulsion; dissolve 20 parts by weight of polycaprolactone in 50 parts by weight of chloroform, add to the oil / water emulsion, and stir and react at 10000 rpm for 5 minutes to prepare the polycaprolactone microcapsule.

[0026] Further, the diisocyanate includes at least one of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, or hexamethylene diisocyanate.

[0027] Further, the polyether polyol includes at least one of polytetrahydrofuran diol or polypropylene glycol.

[0028] Further, the epoxy resin is at least one of bisphenol A epoxy resin, brominated epoxy resin, and phenolic epoxy resin.

[0029] Compared with the prior art, the application has the following advantages:

[0030] (1) The two-component 3D printing elastomer material provided by the application is more conducive to prolonging the shelf life by storing the two components separately. In use, the material is first subjected to preliminary shaping by using rapid light curing technology, and then subjected to further processing by over-heat curing. By virtue of the dual curing mechanism of ultraviolet light curing and heat curing, not only can the shrinkage deformation caused by pure heat curing be reduced, but also the material can maintain high dimensional accuracy in the final curing state.

[0031] (2) TiO2, as an excellent semiconductor material, exhibits significant light absorption ability, especially in the ultraviolet region. By connecting TiO2 to Irgacure 819 through an amide bond, the modified Irgacure 819 can effectively absorb more light energy, thereby improving the light initiation efficiency. In addition, TiO2 has photocatalytic activity and can generate electron-hole pairs under ultraviolet light irradiation. These electron-hole pairs can promote the decomposition of Irgacure 819, accelerate the generation of free radicals, and reduce the time required for curing, thereby realizing rapid light curing. By applying 3-aminopropyl triethoxysilane, the dispersibility and compatibility of TiO2 can be improved, effectively reducing the agglomeration phenomenon, and further enhancing the overall performance of the material.

[0032] (3) By wrapping the polyurethane prepolymer and epoxy resin inside the low-melting-point capsule shell to form polycaprolactone microcapsules, the contact reaction between the curing agent and the epoxy resin can be prevented, which affects the 3D printing effect, and the contact reaction between the chain extender and the polyurethane prepolymer after mixing of component A and component B during the light curing process can also be avoided.

[0033] (4) When the two-component 3D printing elastomer material prepared by the application is used, component A and component B are mixed, and after ultraviolet light irradiation, the modified photoinitiator can initiate the polymerization of polyethylene glycol diacrylate, realizing rapid ultraviolet light curing and high-precision printing. Subsequently, during the heat curing process, the capsule shell of the polycaprolactone microcapsules melts, releasing the polyurethane prepolymer and the epoxy resin. At high temperatures, the chain extender reacts with the polyurethane prepolymer, and the epoxy resin reacts with the curing agent, and secondary curing is carried out, which can make the crosslinking more compact and improve the overall stability of the elastomer material. DETAILED DESCRIPTION

[0034] The technical solutions of the application will be described clearly and completely below through embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0035] Unless otherwise indicated, the starting materials and reagents used in the present application are commercially available or can be prepared by known methods.

[0036] Preparation Example:

[0037] The preparation method of the modified photoinitiator comprises the following steps:

[0038] 10 parts by weight of TiO2 particles were dispersed in 50 parts by weight of deionized water, 100 parts by weight of 65% nitric acid solution was added, and the reaction was stirred at 80°C for 2h, and then hydroxylated TiO2 was obtained after washing and drying;

[0039] 10 parts by weight of hydroxylated TiO2 were dispersed in 50 parts by weight of ethanol, 5 parts by weight of 3-aminopropyl triethoxysilane was added, and the reaction was stirred at 80°C for 4h, and then aminated TiO2 was obtained after washing and drying;

[0040] 20 parts by weight of Irgacure 819 were dispersed in 50 parts by weight of acetone, 10 parts by weight of maleic anhydride was added and stirred for 5min, then 1 part by weight of triethylamine was added, and the temperature was controlled at 60°C in a nitrogen atmosphere, and the reaction was stirred for 12h to prepare carboxylated Irgacure 819;

[0041] 10 parts by weight of aminated TiO2 and 20 parts by weight of carboxylated Irgacure 819 were dispersed in 50 parts by weight of acetone, 10 parts by weight of EDC and 5 parts by weight of NHS were added, and the reaction was stirred at 60°C for 2h to prepare the modified photoinitiator.

[0042] The preparation method of the polycaprolactone microcapsule comprises the following steps:

[0043] 10 parts by weight of polytetrahydrofuran diol were dissolved in 50 parts by weight of N,N-dimethylformamide, 12 parts by weight of isophorone diisocyanate and 0.1 part by weight of dibutyltin dilaurate were added, and the reaction was stirred at 150°C for 2h under a nitrogen atmosphere to obtain a polyurethane prepolymer; 10 parts by weight of the polyurethane prepolymer and 10 parts by weight of bisphenol A epoxy resin were dissolved in 100 parts by weight of ethyl acetate to obtain a mixed solution; 0.5 parts by weight of Span-80 was dispersed in 100 parts by weight of deionized water, the above-mentioned mixed solution was added, and the reaction was stirred at 10000 rpm for 5min to form a stable oil / water emulsion; 20 parts by weight of polycaprolactone was dissolved in 50 parts by weight of chloroform and added to the oil / water emulsion, and the reaction was stirred at 10000 rpm for 5min to prepare the polycaprolactone microcapsule.

[0044] Example 1:

[0045] A preparation method of a two-component 3D printing elastomer material containing a microcapsule structure, specifically comprising the following processes:

[0046] Preparation of component A:

[0047] Take 20 parts by weight of polyethylene glycol diacrylate dispersed in 100 parts by weight of acetone, add 1 part by weight of 1,4-butanediol and 0.5 parts by weight of Tego-410, stir at 40°C for 1h, then vacuum degassing treatment for 30min, discharge into barrels, nitrogen sealing packaging, the barrel is inverted storage, prepared component A.

[0048] Preparation of component B:

[0049] Take 1 part by weight of modified photoinitiator dispersed in 100 parts by weight of acetone, ultrasonic 15min in 40W power, after ultrasonic end add 25 parts by weight of polycaprolactone microcapsule and 1 part by weight of diaminodichlorodiphenyl methane, stirring at 40°C for 1h, vacuum degassing treatment for 30min, discharge into barrels, nitrogen sealing packaging, the barrel is inverted storage, prepared component B.

[0050] In use, component A and component B are mixed in a weight ratio of 1:1.5 to obtain a two-component 3D printing elastomer material precursor containing microcapsule structure, which is poured into a 3D printer for printing, then placed in an oven at 120°C for heating for 5h, and then naturally cooled to room temperature to prepare a two-component 3D printing elastomer material.

[0051] Example 2:

[0052] A method for preparing a two-component 3D printing elastomer material containing microcapsule structure, specifically comprising the following processes:

[0053] Preparation of component A:

[0054] Take 30 parts by weight of polyethylene glycol diacrylate dispersed in 100 parts by weight of acetone, add 3 parts by weight of ethylene glycol and 0.8 parts by weight of Tego-410, stir at 42°C for 1.5h, then vacuum degassing treatment for 45min, discharge into barrels, nitrogen sealing packaging, the barrel is inverted storage, prepared component A.

[0055] Preparation of component B:

[0056] Take 1.8 parts by weight of modified photoinitiator dispersed in 100 parts by weight of acetone, ultrasonic 20min in 60W power, after ultrasonic end add 50 parts by weight of polycaprolactone microcapsule and 3 parts by weight of diaminodichlorodiphenyl methane, stirring at 42°C for 1.5h, vacuum degassing treatment for 45min, discharge into barrels, nitrogen sealing packaging, the barrel is inverted storage, prepared component B.

[0057] In use, the component A and component B are mixed according to the weight ratio of 1:2 to obtain a microcapsule structure containing two-component 3D printing elastomer material precursor, which is poured into a 3D printer for printing, then placed in an oven at 120℃ for heating for 5h, and then naturally cooled to obtain a two-component 3D printing elastomer material.

[0058] Example 3:

[0059] A preparation method of a microcapsule structure containing two-component 3D printing elastomer material, specifically comprising the following processes:

[0060] Preparation of component A:

[0061] 50 parts by weight of polyethylene glycol diacrylate is dispersed in 100 parts by weight of acetone, 5 parts by weight of 1,3-propanediol and 1.2 parts by weight of Tego-410 are added, and after stirring and reacting at 45℃ for 2h, vacuum degassing treatment is performed for 60min, the material is discharged and packed in a barrel, and then the barrel is sealed with nitrogen and stored upside down to obtain component A.

[0062] Preparation of component B:

[0063] 2.5 parts by weight of modified photoinitiator is dispersed in 100 parts by weight of acetone, and ultrasonic treatment is performed at a power of 80W for 30min, 60 parts by weight of polycaprolactone microcapsule and 5 parts by weight of diamino dichlorodiphenyl methane are added after ultrasonic treatment, and stirring and reaction is performed at 45℃ for 2h, vacuum degassing treatment is performed for 60min, the material is discharged and packed in a barrel, and then the barrel is sealed with nitrogen and stored upside down to obtain component B.

[0064] In use, the component A and component B are mixed according to the weight ratio of 1:3 to obtain a microcapsule structure containing two-component 3D printing elastomer material precursor, which is poured into a 3D printer for printing, then placed in an oven at 120℃ for heating for 5h, and then naturally cooled to obtain a two-component 3D printing elastomer material.

[0065] Example 4:

[0066] A preparation method of a microcapsule structure containing two-component 3D printing elastomer material, specifically comprising the following processes:

[0067] Preparation of component A:

[0068] 35 parts by weight of polyethylene glycol diacrylate is dispersed in 100 parts by weight of acetone, 5 parts by weight of 1,4-butanediol and 1.2 parts by weight of Tego-410 are added, and after stirring and reacting at 45℃ for 2h, vacuum degassing treatment is performed for 40min, the material is discharged and packed in a barrel, and then the barrel is sealed with nitrogen and stored upside down to obtain component A.

[0069] Preparation of component B:

[0070] Take 2.5 parts by weight of modified photoinitiator and disperse in 100 parts by weight of acetone, ultrasonic 30 min in 80W power, after ultrasonic, add 50 parts by weight of polycaprolactone microcapsule and 5 parts by weight of diamino dichlorodiphenyl methane, stirring reaction in 45℃ environment for 2h, vacuum degassing treatment for 40 min, discharge barrel, nitrogen sealing packaging, the barrel is inverted storage, prepared components B.

[0071] When using, component A and component B are mixed according to weight ratio 1:2 to obtain a two-component 3D printing elastomer material precursor containing microcapsule structure, which is poured into a 3D printer for printing, then placed in an oven at 120℃ for 5h, and then naturally cooled to room temperature to prepare a two-component 3D printing elastomer material.

[0072] Comparative example 1:

[0073] A method for preparing a two-component 3D printing elastomer material containing microcapsule structure, specifically including the following processes:

[0074] The modified photoinitiator in example 4 is replaced by Irgacure 819, and the rest of the conditions remain the same as example 4.

[0075] Comparative example 2:

[0076] A method for preparing a two-component 3D printing elastomer material containing microcapsule structure, specifically including the following processes:

[0077] The polycaprolactone microcapsule in example 4 is replaced by urea-formaldehyde microcapsule, and the rest of the conditions remain the same as example 4. The preparation method of urea-formaldehyde microcapsule specifically includes the following steps:

[0078] 40 parts by weight of 37% formaldehyde solution is added to the reaction kettle, the pH value is adjusted to 4, 20 parts by weight of urea particles is added, and the reaction is carried out at 60℃ for 30 min to prepare urea-formaldehyde resin emulsion; 10 parts by weight of polytetrahydrofuran diol is dissolved in 50 parts by weight of N,N-dimethylformamide, 12 parts by weight of isophorone diisocyanate and 0.1 parts by weight of dibutyltin dilaurate are added, and the mixture is stirred at 150℃ for 2h under nitrogen atmosphere to obtain polyurethane prepolymer; 10 parts by weight of polyurethane prepolymer and 10 parts by weight of bisphenol A epoxy resin are dispersed in 100 parts by weight of ethyl acetate to obtain a mixed solution, 20 parts by weight of the above urea-formaldehyde resin emulsion and 0.5 parts by weight of Span-80 are added, the pH value is adjusted to 4.5, and the reaction is carried out at 60℃ for 4h to prepare urea-formaldehyde microcapsule.

[0079] Comparative example 3:

[0080] A method for preparing a two-component 3D printing elastomer material containing microcapsule structure, specifically including the following processes:

[0081] Take 2.5 parts by weight of modified photoinitiator and disperse in 200 parts by weight of acetone, ultrasonic for 30 min in 80W power, after ultrasonic, add 35 parts by weight of polyethylene glycol diacrylate, 5 parts by weight of 1,4-butanediol, 1.2 parts by weight of Tego-410, 50 parts by weight of polycaprolactone microcapsule and 5 parts by weight of diaminodichlorodiphenyl methane, stirring reaction at 45℃ environment for 2h, vacuum degassing treatment for 40min, discharge barrel, nitrogen sealing packaging, the barrel is inverted storage, prepared single component 3D printing elastomer material precursor.

[0082] When using, the 3D printing elastomer material precursor is poured into the 3D printer for printing forming, and then placed in the oven at 120℃ for heating for 5h, and then naturally cooled to prepare the single component 3D printing elastomer material.

[0083] Test example 1: viscosity test and curing time test

[0084] Viscosity test: at 25℃ environment, using NDT-8s digital rotary viscometer according to GB / T1024-1988 test;

[0085] Curing time: the two-component 3D printing elastomer material precursor prepared by examples 1-4 and comparative examples 1-2 and the single-component 3D printing elastomer material precursor prepared by comparative example 3 are coated on the pretreated glass sheet by four-blade wet film preparation device, the coating thickness is 250μm, cured by ultraviolet light irradiation, timed by stopwatch, record the curing time, touch the composition irradiated by laser beam with a certain pressure with fingers, not sticky hand is considered to be cured.

[0086] The specific test data is shown in table 1:

[0087] Table 1. Viscosity and curing time test data

[0088]

[0089]

[0090] From the data in table 1, the viscosity of the two-component 3D printing elastomer material prepared by examples 1-4 before curing is less than 20MPa·s, which has good flowability in 25℃ environment, in addition, the two-component 3D printing elastomer material prepared by examples 1-4 has the ability of fast curing under ultraviolet light irradiation, therefore, the two-component 3D printing elastomer material prepared by the present application can adapt to higher printing speed and finer printing details.

[0091] Test example 2: performance test

[0092] The two-component 3D printing elastomer materials prepared from Examples 1-4 and Comparative Examples 1-2 and the single-component 3D printing elastomer material prepared from Comparative Example 3 were respectively subjected to tensile strength, impact strength and shrinkage rate tests.

[0093] Tensile property test: tested by using a CMT4204 tensile machine according to GB / T 1040.3-2006 standard, with a tensile rate of 20 mm / min;

[0094] Impact property test: tested by using an XBL-5.5D cantilever beam digital testing machine according to GB / T 1843-2008 standard, with an impact energy of 5.5 J and an impact speed of 3.5 m / s;

[0095] Shrinkage rate test: tested by using a SMK-401 density meter according to a density method.

[0096] Specific test data are shown in Table 2.

[0097] Table 2. Performance test data

[0098]

[0099]

[0100] From the data in Table 2, it can be seen that the two components of the two-component 3D printing elastomer material containing microcapsule structure prepared by the present application can be stored for 12-16 months when the two components are stored separately before curing, and has a relatively long storage effective period; after curing, the tensile strength is 38.4-42.9 MPa, and the impact strength is 6.27-7.92 KJ / m 2 , which shows excellent toughness performance, and the shrinkage rate is only 2.26-3.63%, which can meet the requirements of precise printing.

[0101] The above examples have described the technical solutions and beneficial effects of the present application in detail, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the present application.

Claims

1. A bi-component 3D printing elastomeric material containing microcapsule structures, characterized in that, Component A and Component B, the Component A comprising polyethylene glycol diacrylate, chain extender and leveling agent, the Component B comprising modified photoinitiator, curing agent and polycaprolactone microcapsule; The preparation method of the modified photoinitiator comprises the following steps: 10 parts by weight of TiO2 particles are dispersed in 50 parts by weight of deionized water, 100 parts by weight of 65% nitric acid solution is added, and stirring reaction is carried out at 80℃ for 2h, and after washing and drying, hydroxylated TiO2 is obtained; 10 parts by weight of hydroxylated TiO2 is dispersed in 50 parts by weight of ethanol, 5 parts by weight of 3-aminopropyl triethoxysilane is added, and stirring reaction is carried out at 80℃ for 4h, and after washing and drying, aminated TiO2 is obtained; 20 parts by weight of Irgacure 819 is dispersed in 50 parts by weight of acetone, 10 parts by weight of maleic anhydride is added and stirred for 5min, then 1 part by weight of triethylamine is added, and stirring reaction is carried out at 60℃ for 12h in a nitrogen atmosphere to prepare carboxylated Irgacure 819; 10 parts by weight of aminated TiO2 and 20 parts by weight of carboxylated Irgacure 819 are dispersed in 50 parts by weight of acetone, 10 parts by weight of EDC and 5 parts by weight of NHS are added, and stirring reaction is carried out at 60℃ for 2h to prepare the modified photoinitiator; The preparation method of the polycaprolactone microcapsule comprises the following steps: 50 parts by weight of polyether polyol is dissolved in 500 parts by weight of N,N-dimethylformamide, 7 parts by weight of diisocyanate and 0.4 parts by weight of dibutyltin dilaurate are added, and stirring reaction is carried out at 150℃ for 4h in a nitrogen atmosphere to obtain a polyurethane prepolymer; 10 parts by weight of the polyurethane prepolymer and 10 parts by weight of epoxy resin are dissolved in 100 parts by weight of ethyl acetate to obtain a mixed solution; 5 parts by weight of Span-80 is dispersed in 500 parts by weight of deionized water, the above-obtained mixed solution is added, and stirring reaction is carried out at 10000rpm for 5min to form a stable oil / water emulsion; 20 parts by weight of polycaprolactone is dissolved in 50 parts by weight of chloroform and added to the oil / water emulsion, and stirring reaction is carried out at 10000rpm for 5min to prepare the polycaprolactone microcapsule.

2. A dual component 3D printing elastomeric material containing microcapsule structure according to claim 1, characterized in that, The Component A comprises polyethylene glycol diacrylate 20-50 parts, chain extender 1-5 parts and leveling agent 0.5-1.2 parts by weight; The Component B comprises modified photoinitiator 1-2.5 parts, curing agent 1-5 parts and polycaprolactone microcapsule 25-60 parts.

3. A bi-component 3D printing elastomeric material containing microcapsule structures according to claim 1 or 2, characterized in that, The shell of the polycaprolactone microcapsule is polycaprolactone, and the core of the polycaprolactone microcapsule comprises polyurethane prepolymer and epoxy resin.

4. The dual component 3D printing elastomeric material containing microcapsule structure of claim 1, wherein, The epoxy resin is at least one of bisphenol A epoxy resin, brominated epoxy resin and phenolic epoxy resin.

5. A dual component 3D printing elastomeric material containing microcapsule structure according to claim 1 or 2, wherein, The chain extender comprises at least one of 1,4-butanediol, ethylene glycol or 1,3-propanediol.

6. A bi-component 3D printing elastomeric material containing microcapsule structures according to claim 1 or 2, wherein, The leveling agent is Tego-410.

7. A two-component 3D-printed elastomer material with a microcapsule structure as described in claim 1 or 2, characterized in that, The curing agent is diamino dichlorodiphenyl methane.

8. The method of claim 1, wherein the method further comprises the step of: 8.

1. mixing the microcapsules with the second component to form a second mixture; and 8.

2. mixing the second mixture with the first component to form the dual- component 3D printing elastomeric material. The preparation method comprises the following steps: Preparation of component A: polyethylene glycol diacrylate is dispersed in an organic solvent, a chain extender and a leveling agent are added, and stirring is carried out at 40-45℃ for 1-2h, and after the reaction is completed, vacuum degassing is carried out to obtain the component A; Preparation of component B: the modified photoinitiator is dispersed in an organic solvent, and after ultrasonic treatment, polycaprolactone microcapsules and a curing agent are added, and stirring is carried out at 40-45℃ for 1-2h, and after the reaction is completed, vacuum degassing is carried out to obtain the component B; The component A and the component B are mixed in a weight ratio of component A: component B = 1: 1.5-3 to obtain the dual-component 3D printing elastomer material.

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