Isotropic glass fiber reinforced photocuring material and preparation method thereof

Abstract

The invention discloses an isotropic glass fiber reinforced photocuring material and a preparation method thereof, and the preparation method comprises the following specific steps: firstly, treating glass fiber by adopting a chemical grafting modification means to prepare alkylated modified glass fiber; then, bisphenol A epoxy acrylate, a monofunctional acrylate monomer and a photoinitiator are mixed, the alkylated modified glass fibers are added to serve as a reinforcing phase, and the isotropic photocuring material is obtained through a photocuring 3D printing technology. The alkylated modified glass fiber is used as a reinforcing phase, chemical bonding between the fiber and a matrix is enhanced, the tensile strength of a printed product is remarkably improved, and anisotropy is reduced. According to the innovation, by optimizing the combination mechanism of the modified glass fibers and the resin matrix, the isotropy is kept while the mechanical property of the material is enhanced, and it is indicated that the application prospect of the photocuring 3D printing product in the industrial field is widened.

Description

Technical Field

[0001] The invention relates to an isotropic glass fiber reinforced photocurable material and a preparation method thereof, in particular to enhancing the isotropic mechanical properties of a photosensitive acrylic resin system by alkylating modified glass fibers, and belongs to the technical field of chemical industry and polymer materials. Background Art

[0002] Photocuring 3D printing is an advanced computer-controlled visible light or ultraviolet light-induced liquid photosensitive resin, which is polymerized layer by layer at precisely selected locations on the printing platform to construct a three-dimensional structure. This technology can be divided into stereolithography (SLA), digital light processing (DLP), liquid crystal display (LCD), continuous liquid interface manufacturing (CLIP) and high area rapid printing (HARP), etc. They are all characterized by high efficiency, high resolution and easy separation of printed structures, and support the recycling of uncured resin, showing significant advantages in industrial applications.

[0003] However, the mechanical properties of the commonly used photocurable 3D printing acrylic resin are not ideal, which restricts its wide application in medical equipment, electronic components, automotive parts and aerospace fields. This is due to two factors: the inherent structural characteristics of acrylic materials and the relatively weak interlayer bonding force caused by the layer-by-layer stacking molding technology of photocurable 3D printing, which makes the mechanical properties of the samples show significant anisotropy, especially the performance in the vertical printing direction is significantly lower than that in the horizontal direction.

[0004] Therefore, improving the mechanical properties of photocurable 3D printing resins to meet a wider range of usage needs has become a research hotspot in the current scientific research field. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides an isotropic glass fiber reinforced photocurable material and a preparation method thereof, using alkylated modified glass fiber as a reinforcing phase to enhance the chemical bonding between the fiber and the matrix, significantly improving the tensile strength of the printed product and reducing the anisotropy.

[0006] To achieve the above object, the technical solution adopted in the present invention is:

[0007] The first object of the present invention is to provide an isotropic glass fiber reinforced photocurable material, which is a photosensitive resin in which alkylated modified glass fibers are distributed, and the content of the alkylated modified glass fibers is 10-30wt.% of the photosensitive resin, wherein the tensile strength anisotropy of the isotropic glass fiber reinforced photocurable material is not higher than 9.3%, and the elongation at break anisotropy is lower than not higher than 9.0%.

[0008] The second object of the present invention is to provide the use of alkylated modified glass fiber in the preparation of isotropic glass fiber reinforced photocurable material, wherein the isotropic glass fiber reinforced photocurable material is the isotropic glass fiber reinforced photocurable material as described above, and the alkylated modified glass fiber is obtained by grafting reaction of glass fiber and silane coupling agent.

[0009] The third object of the present invention is to provide a method for preparing an isotropic glass fiber reinforced light-curable material, the preparation method comprising the following steps:

[0010] Mixing bisphenol A epoxy acrylate, monofunctional acrylate monomer and photoinitiator to obtain photosensitive resin;

[0011] Alkyl modified glass fiber is added to the photosensitive resin, the content of the alkyl modified glass fiber is 10-30wt.% of the photosensitive resin, and then dispersed and mixed to obtain an alkyl modified glass fiber reinforced photosensitive resin solution, which is 3D printed and post-cured to prepare a composite material, namely an isotropic glass fiber reinforced photocurable material; the alkyl modified glass fiber is obtained by grafting reaction of glass fiber and silane coupling agent.

[0012] A fourth object of the present invention is to provide an isotropic glass fiber reinforced photocurable material as described above or prepared by any of the methods described above for use in medical equipment, electronic components, automotive parts or aerospace fields.

[0013] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0014] 1. Glass fiber GF is an inorganic non-metallic material with excellent performance. It is added to the photosensitive resin matrix as a reinforcing phase to significantly improve the mechanical properties. On this basis, the present invention uses a silane coupling agent to undergo a grafting reaction with it to obtain an alkylated modified glass fiber. The alkylated modified glass fiber is used as a reinforcing phase to further enhance the chemical bonding between the fiber and the matrix, which not only significantly improves the tensile strength of the printed product, but also reduces the anisotropy. This innovation optimizes the bonding mechanism between the modified glass fiber and the resin matrix to achieve the mechanical properties of the enhanced material while maintaining isotropy, indicating that the application prospects of photocurable 3D printed products in the industrial field will be broadened.

[0015] 2. The present invention provides a novel glass fiber reinforced photosensitive acrylic resin system designed for photocuring DLP 3D printing. The system utilizes the bridging effect of GF between layers to effectively make up for the lack of interfacial bonding force in the layer-by-layer stacking manufacturing process. The method is easy to operate and has a significant effect on improving the anisotropy of photosensitive acrylic. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the reasons for the anisotropy of mechanical properties of light-curing 3D printed parts.

[0017] Figure 2 It is a schematic diagram of the principle of the present invention.

[0018] Figure 3 1 is a viscosity curve of the printing solution with different GF addition amounts provided in Experimental Example 1 of the present invention.

[0019] Figure 4 It is the UV light curing photo-DSC curve of the printing solution with different GF addition amounts provided in Experimental Example 1 of the present invention.

[0020] Figure 5 This is the relationship between the curing depth and the UV exposure energy provided in Experimental Example 1 of the present invention.

[0021] Figure 6 This is a 3D printing process diagram of the modified GF reinforced sample provided in Example 1 of the present invention.

[0022] Figure 7 It is the infrared spectrum of GF before and after modification provided in Example 1 of the present invention.

[0023] Figure 8 It is the thermogravimetric analysis curve of GF before and after modification provided in Example 1 of the present invention.

[0024] Fig. 9 It is the anisotropy of the tensile properties of the modified GF composite material provided in Example 1 of the present invention.

[0025] Fig.10 It is the tensile fracture cross section of the modified GF reinforced sample printed in the horizontal direction provided in Example 1 of the present invention.

[0026] Fig.11 It is the tensile fracture cross section of the modified GF reinforced sample printed in the vertical direction provided in Example 1 of the present invention.

[0027] Fig.12 This is the 3D printed nut and bolt model provided in Example 1 of the present invention.

[0028] Fig.13 This is the 3D printed hollow structure model provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] In the process of DLP 3D printing, each layer of photosensitive resin is cured and then the next layer is added, so the bonding force between the layers is limited. This lack of interlayer bonding makes the printed parts show extremely obvious anisotropy in mechanical properties, such as Figure 1This anisotropy will lead to the aggravation of stress concentration when the part is subjected to complex stress, which will have an adverse effect on the overall performance of the part.

[0030] At present, the main solutions to the anisotropy of mechanical properties of photocurable 3D printed products include toughening of core-shell particles, building dual-curing networks, and introducing dynamic covalent bonds. These strategies aim to enhance interlayer bonding, but toughening of core-shell particles cannot eliminate the anisotropy of elongation at break; dual-curing systems require additional heating treatment; and the introduction of dynamic disulfide bonds requires the design and synthesis of specific structures, and their tensile strength is relatively low.

[0031] Based on this situation, the present invention provides a new alkylated modified glass fiber reinforced photosensitive acrylate resin system designed for photocuring DLP 3D printing, such as Figure 2 As shown, the system utilizes the bridging effect of alkylated modified GF between layers to effectively make up for the lack of interfacial bonding force in the layer-by-layer stacking manufacturing process.

[0032] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and embodiments. However, this should not be understood as limiting the scope of the present invention to the following examples. Various substitutions or changes made according to common technical knowledge and customary means in the art without departing from the above-mentioned method concept of the present invention should be included in the scope of the present invention.

[0033] Example

[0034] The first aspect of the present invention is to provide an isotropic glass fiber reinforced photocurable material, which is a photosensitive resin in which alkylated modified glass fibers are distributed, and the content of the alkylated modified glass fibers is 10-30wt.% of the photosensitive resin, wherein the tensile strength anisotropy of the isotropic glass fiber reinforced photocurable material is not higher than 9.3%, and the elongation at break anisotropy is not higher than 9.0%.

[0035] Preferably, the content of the alkylated modified glass fiber is 20-30 wt.% of the photosensitive resin. More preferably, the content of the alkylated modified glass fiber is 30 wt.% of the photosensitive resin.

[0036] Optionally, in one embodiment of the present invention, the anisotropy of the tensile strength of the isotropic glass fiber reinforced photocurable material is not higher than 7.5%, and the anisotropy of the elongation at break is not higher than 7.0%.

[0037] Preferably, the anisotropy of the tensile strength of the isotropic glass fiber reinforced light-curable material is not higher than 5.0%, and the anisotropy of the elongation at break is not higher than 3.5%.

[0038] Optionally, in one embodiment of the present invention, the tensile strength of the isotropic glass fiber reinforced photocurable material is higher than 70 MPa.

[0039] Optionally, in one embodiment of the present invention, the elongation at break of the isotropic glass fiber reinforced photocurable material is higher than 6%.

[0040] Optionally, in one embodiment of the present invention, the isotropic glass fiber reinforced light-curable material is -1 and 2902cm -1 There are CH2 asymmetric and symmetric vibration peaks at 1054cm -1 There is a Si-O-Si stretching vibration peak at 1411 cm -1 There is a CH bending vibration peak of -CH3 at .

[0041] The second aspect of the present invention is to propose the use of alkylated modified glass fiber in the preparation of isotropic glass fiber reinforced photocurable material, the isotropic glass fiber reinforced photocurable material is the isotropic glass fiber reinforced photocurable material as described above, and the alkylated modified glass fiber is obtained by grafting reaction of glass fiber and silane coupling agent.

[0042] Optionally, in one embodiment of the present invention, the grafting reaction between the glass fiber and the silane coupling agent specifically comprises the following steps:

[0043] (a) treating the glass fiber with acetone at room temperature for 12-48 hours to remove surface pollutants, then washing with water and drying to obtain pretreated glass fiber;

[0044] (b) adjusting the pH value of the 95% ethanol aqueous solution to 3±0.5 with an acidic solution, adding a silane coupling agent and the pretreated glass fiber, and performing a grafting reaction to obtain a grafted product;

[0045] (c) After the reaction is completed, the grafted product is washed and dried to obtain an alkylated modified glass fiber.

[0046] Optionally, in one embodiment of the present invention, based on 5 g equivalent of glass fiber, the amount of the 95% ethanol aqueous solution added is 50-100 ml.

[0047] Optionally, in one embodiment of the present invention, the acidic solution is one or more of hydrochloric acid, sulfuric acid or nitric acid solution.

[0048] Optionally, in one embodiment of the present invention, the content of the alkylated modified glass fiber is 10-30 wt. % of the photosensitive resin.

[0049] Preferably, the content of the alkylated modified glass fiber is 20-30 wt.% of the photosensitive resin. More preferably, the content of the alkylated modified glass fiber is 30 wt.% of the photosensitive resin.

[0050] Optionally, in one embodiment of the present invention, the reaction temperature of the grafting reaction is 0 to 50° C., and the reaction time is 5 to 12 hours.

[0051] Optionally, in one embodiment of the present invention, the silane coupling agent includes at least one of KH570, KH540 and KH590.

[0052] Optionally, in one embodiment of the present invention, the mass ratio of the silane coupling agent to the glass fiber is 0.1 to 0.3:1.

[0053] The third aspect of the present invention is to provide a method for preparing an isotropic glass fiber reinforced light-curable material, the preparation method comprising the following steps:

[0054] Mixing bisphenol A epoxy acrylate, monofunctional acrylate monomer and photoinitiator to obtain photosensitive resin;

[0055] Alkyl modified glass fiber is added to the photosensitive resin, dispersed, and mixed to obtain an alkyl modified glass fiber reinforced photosensitive resin solution, which is 3D printed and post-cured to prepare a composite material, namely an isotropic glass fiber reinforced photocurable material; the alkyl modified glass fiber is obtained by the grafting reaction of glass fiber and silane coupling agent.

[0056] Optionally, in one embodiment of the present invention, the monofunctional acrylate monomer includes one or more of isobornyl acrylate, dicyclopentadiene acrylate, hydroxyethyl acrylate, diethoxy acrylate, and tetrahydrofuran acrylate.

[0057] Optionally, in one embodiment of the present invention, the photoinitiator includes one or more of 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.

[0058] Optionally, in one embodiment of the present invention, the mass ratio of the bisphenol A epoxy acrylate, the monofunctional acrylate monomer and the photoinitiator is 24-36:4-16:0.4-0.8.

[0059] Optionally, in one embodiment of the present invention, the dispersion time is 1 to 5 minutes.

[0060] Optionally, in one embodiment of the present invention, the post-curing time is 10 to 50 seconds.

[0061] Optionally, in one embodiment of the present invention, the grafting reaction between the glass fiber and the silane coupling agent specifically comprises the following steps:

[0062] (a) treating the glass fiber with acetone at room temperature for 12-48 hours to remove surface pollutants, then washing with water and drying to obtain pretreated glass fiber;

[0063] (b) adjusting the pH value of the 95% ethanol aqueous solution to 3±0.5 with an acidic solution, adding a silane coupling agent and the pretreated glass fiber, and performing a grafting reaction to obtain a grafted product;

[0064] (c) After the reaction is completed, the grafted product is washed and dried to obtain an alkylated modified glass fiber.

[0065] Optionally, in one embodiment of the present invention, based on 5 g equivalent of glass fiber, the amount of the 95% ethanol aqueous solution added is 50-100 ml.

[0066] Optionally, in one embodiment of the present invention, the acidic solution is one or more solutions of hydrochloric acid, sulfuric acid or nitric acid.

[0067] Optionally, in one embodiment of the present invention, the reaction temperature of the grafting reaction is 0 to 50° C., and the reaction time is 5 to 12 hours.

[0068] Preferably, the reaction temperature of the grafting reaction is 20 to 50° C., and the reaction time is 6 to 12 hours.

[0069] Optionally, in one embodiment of the present invention, the silane coupling agent includes at least one of KH570, KH540 and KH590.

[0070] Optionally, in one embodiment of the present invention, the mass ratio of the silane coupling agent to the glass fiber is 0.1 to 0.3:1.

[0071] The fourth aspect of the present invention is to propose the application of the isotropic glass fiber reinforced photocurable material as described above or prepared by any of the methods described above in the fields of medical equipment, electronic components, automotive parts or aerospace.

[0072] The present invention will be further described below in conjunction with the accompanying drawings and Examples. According to the following examples, the present invention can be better understood. However, it is easy for those skilled in the art to understand that the specific material ratios, process conditions and results described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0073] Experimental Example 1 Preparation of unmodified GF-reinforced photocurable composite material

[0074] In order to explore the process conditions for the preparation of modified GF materials for photocurable composite materials, the present invention first uses GF as raw material and studies the influence of different GF addition amounts on the preparation of GF-enhanced photocurable composite materials, in order to provide a reference for the process conditions of the modified GF materials for the preparation of modified GF-enhanced photocurable composite materials on the one hand and on the other hand.

[0075] The specific preparation method of the GF reinforced light-cured composite material in this experimental example is as follows:

[0076] (a) bisphenol A epoxy acrylate (24 g), dicyclopentadiene acrylate (16 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.8 g) were mixed to obtain a photosensitive resin;

[0077] (b) Then, 0, 4, 8, 12, 16, and 20 g of GF were added to the photosensitive resin, respectively (correspondingly, the amount of GF added was 0 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, and 50 wt.%. In the present invention, the amount of GF added refers to the mass ratio of GF to the photosensitive resin, and the amount of modified GF added subsequently refers to the mass ratio of modified GF to the photosensitive resin), and dispersed in a high-speed disperser at 3000 r / min for 2 min to obtain a uniformly mixed GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF enhanced photocurable composite material.

[0078] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 20 seconds.

[0079] See attached Figure 3 , which is the viscosity curve of the printing solution with different GF addition amounts provided in Experimental Example 1 of the present invention. It can be seen from the figure that when the GF addition amount is 50wt.%, the shear rate is 1s -1 When the viscosity of the resin system reaches 9.8Pa·s, it is difficult to print, while the viscosity of the printing solution with 0-40wt% is up to 6.8Pa·s, which can meet the requirements of DLP 3D printing. Therefore, in other performance tests of GF-enhanced light-curable composite materials, the addition amount of GF is 0-40wt%.

[0080] See attached Figure 4, which is the UV light curing photo-DSC curve of the printing solution with different GF addition amounts provided in Experimental Example 1 of the present invention. It can be seen from the figure that under UV irradiation, the printing solution reacts rapidly and basically reaches the peak value within 10 seconds. Among them, as the amount of GF added in the printing solution increases, the peak value of the exothermic peak gradually decreases, and the time required to reach the peak value also gradually decreases, indicating that the curing speed decreases with the increase of GF addition amount.

[0081] See attached Figure 5 , which is the relationship between the curing depth and the ultraviolet exposure energy provided in Experimental Example 1 of the present invention. As can be seen from the figure, the transmission depth (Dp) and the critical ultraviolet exposure energy (Ec), that is, the minimum energy required to start curing, can be obtained by fitting the curing depth (Cd) of the printing solution and the logarithm of the ultraviolet exposure energy E according to the Jacob equation:

[0082]

[0083] The higher the GF content, the lower the curing depth Cd of the composite material.

[0084] Referring to Table 1, which shows the transmission depth and critical UV exposure energy provided by Experimental Example 1 of the present invention, as the content of GF-KH570-1 increases, the Dp and Ec values ​​show a downward trend, which means that the formation of the solidified layer starts earlier.

[0085] Table 1 Transmission depth and critical UV exposure energy in Experimental Example 1

[0086]

[0087]

[0088] See Table 2, which is the tensile properties of the initial GF composite material provided in Experimental Example 1 of the present invention. The resin material with 30wt.% GF added has the highest tensile strength (64.2MPa). Compared with the sample prepared from pure resin (GF addition amount is 0wt.%), it has increased by 43.9%. Moreover, the tensile strength does not increase with the increase of GF content in the resin. It reaches a peak value at 30wt%, and then decreases with the increase of GF content in the resin. The present invention aims to prepare an isotropic photocurable material with good mechanical properties. When 30wt% GF is added, the composite material has the highest tensile strength. Therefore, in the subsequent embodiments, in the preparation process of the modified GF reinforced photocurable composite material, the addition amount of GF is controlled in the range of 0-30wt%, and the influencing factors of anisotropy are explored on the basis of ensuring good mechanical properties.

[0089] Table 2 Tensile properties of initial GF composites

[0090]

[0091] Example 1 Preparation of modified GF reinforced photocurable composite material

[0092] The embodiment of the present invention takes the process conditions of the above-mentioned experimental example 1 as a reference, adopts the modified GF as a raw material, and prepares the modified GF reinforced light-cured composite material.

[0093] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0094] 1) Preparation of alkylated modified glass fiber GF-KH570-1

[0095] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0096] Add 50 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with hydrochloric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1 g of KH570 silane coupling agent, and stir continuously at room temperature for 12 hours to obtain a grafted product.

[0097] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-1). GF-KH570-1 was used to prepare modified GF composite materials.

[0098] 2) Preparation of GF-KH570-1 reinforced light-cured composites

[0099] Bisphenol A epoxy acrylate (24 g), dicyclopentadiene acrylate (16 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.8 g) were mixed to obtain a photosensitive resin;

[0100] Then, 12 g of GF-KH570-1 (corresponding to an addition amount of GF-KH570-1 of 30 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 2 min using a high-speed disperser to obtain a uniformly mixed GF-KH570-1 enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-1 enhanced photocurable composite material.

[0101] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 20 seconds.

[0102] See attached Figure 6, which is a 3D printing process diagram of the modified GF reinforced sample provided in Example 1 of the present invention, using KH-570 modified GF as a reinforcement, epoxy acrylate and dicyclopentadiene acrylate as a matrix, and using DLP 3D printing to prepare a modified GF reinforced composite material.

[0103] See attached Figure 7 , which is the infrared spectrum of GF before and after modification when the addition amount is 30wt.% provided in Example 1 of the present invention, 2985cm -1 and 2902cm -1 The CH2 asymmetric and symmetric vibration peaks appear at 1054cm -1 The stretching vibration peak of Si-O-Si appears at 1411 cm -1 The new peak at is the CH bending vibration peak of -CH3, indicating that KH570 was successfully grafted onto the GF surface.

[0104] See attached Figure 8 It is the thermogravimetric analysis curve of GF before and after modification when the addition amount is 30wt.% provided in Example 1 of the present invention. The mass loss of GF grafted with KH570 occurs at 250-500°C, and the mass loss reaches 1.6%.

[0105] Referring to Table 3, it is the tensile properties in different directions of the modified GF-KH570-1 composite material provided in Example 1 of the present invention when the addition amount is 30wt.%. When 30wt% GF-KH570 is added, the tensile strength of the printed sample reaches 74.5MPa, which is 67.0% higher than that of the resin sample and 16.0% higher than that of the GF reinforced composite material.

[0106] Table 3 Tensile properties of modified GF-KH570-1 composite materials in different directions

[0107]

[0108] See attached Fig. 9 , which is the tensile property anisotropy of the modified GF-KH570-1 composite material provided in Example 1 of the present invention when the addition amount is 30wt.%, and the anisotropy of the printed material is calculated according to the following formula:

[0109]

[0110] Compared with the pure resin printed sample (39.2%), the tensile strength anisotropy of the printed sample containing 30wt% GF prepared in Experimental Example 1 was greatly reduced to 9.5%, and the anisotropy of the elongation at break was reduced to 9.4%. After the GF was modified in Example 1, the tensile strength anisotropy of the reinforced printed sample was further reduced to 4.2%, and the anisotropy of the elongation at break was reduced to 3.0%.

[0111] See attached Fig.10 , 11 , they are respectively the tensile fracture cross sections of the modified GF-KH570-1 reinforced sample printed in the horizontal direction and the tensile fracture cross sections of the modified GF-KH570-1 reinforced sample printed in the vertical direction provided in Example 1 of the present invention. GF-KH570-1 is randomly distributed in the resin as a whole, and some fibers will penetrate different layers, thereby improving the interlayer adhesion and thus improving the mechanical strength in this direction.

[0112] See attached Fig.12 , which is the 3D printed nut and bolt model provided in Example 1 of the present invention.

[0113] See attached Fig.13 , which is the 3D printed hollow structure model provided in Example 1 of the present invention.

[0114] Example 2 Preparation of modified GF reinforced photocurable composite material

[0115] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0116] 1) Preparation of alkylated modified glass fiber GF-KH570-2

[0117] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0118] Add 100 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with nitric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1.5 g of KH570 silane coupling agent, and stir continuously at 30°C for 8 hours to obtain a grafted product.

[0119] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-2). GF-KH570-2 was used to prepare modified GF composite materials.

[0120] 2) Preparation of GF-KH570-2 reinforced light-cured composites

[0121] Bisphenol A epoxy acrylate (32 g), dicyclopentadiene acrylate (8 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.4 g) were mixed to obtain a photosensitive resin;

[0122] Then, 12 g of GF-KH570-2 (corresponding to the addition amount of GF-KH570-2 being 30 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 5 min using a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-2 enhanced photocurable composite material.

[0123] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 30 seconds.

[0124] The GF-KH570-2 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 4.3% and a breaking elongation anisotropy of 2.8%.

[0125] Example 3 Preparation of modified GF reinforced photocurable composite material

[0126] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0127] 1) Preparation of alkylated modified glass fiber GF-KH570-3

[0128] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0129] Add 70 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with hydrochloric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1.5 g of KH570 silane coupling agent, and stir continuously at room temperature for 8 hours to obtain a grafted product.

[0130] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (GF-KH570-3). GF-KH570-3 was used to prepare modified GF composite materials.

[0131] 2) Preparation of GF-KH570-3 reinforced light-cured composites

[0132] Bisphenol A epoxy acrylate (32 g), dicyclopentadiene acrylate (8 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.8 g) were mixed to obtain a photosensitive resin;

[0133] Then, 8 g of GF-KH570-3 (correspondingly, the addition amount of GF-KH570-3 is 20 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 2 min using a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-3 enhanced photocurable composite material.

[0134] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing. The total curing time was about 30 seconds.

[0135] The GF-KH570-3 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 6.7% and a breaking elongation anisotropy of 6.4%.

[0136] Example 4 Preparation of modified GF reinforced light-cured composite material

[0137] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0138] 1) Preparation of alkylated modified glass fiber GF-KH570-4

[0139] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0140] Add 100 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with sulfuric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1 g of KH570 silane coupling agent, and stir continuously at 50°C for 8 hours to obtain a grafted product.

[0141] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (GF-KH570-4). GF-KH570-4 was used to prepare modified GF composite materials.

[0142] 2) Preparation of GF-KH570-4 reinforced light-cured composites

[0143] Bisphenol A epoxy acrylate (24 g), hydroxyethyl acrylate (16 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.4 g) were mixed to obtain a photosensitive resin;

[0144] Then, 8 g of GF-KH570-4 (correspondingly, the addition amount of GF-KH570-4 was 20 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 3 min using a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-4 enhanced photocurable composite material.

[0145] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 40 seconds.

[0146] The GF-KH570-4 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 7.1% and a breaking elongation anisotropy of 6.9%.

[0147] Example 5 Preparation of modified GF reinforced photocurable composite material

[0148] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0149] 1) Preparation of alkylated modified glass fiber GF-KH570-5

[0150] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0151] Add 100 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with nitric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1 g of KH570 silane coupling agent, and stir continuously at 50°C for 8 hours to obtain a grafted product.

[0152] After the reaction was completed, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-5). GF-KH570-5 was used to prepare modified GF composite materials.

[0153] 2) Preparation of GF-KH570-5 reinforced light-cured composites

[0154] Bisphenol A epoxy acrylate (24 g), bisethoxy acrylate (16 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.4 g) were mixed to obtain a photosensitive resin;

[0155] Then, 12 g of GF-KH570-5 (corresponding to the addition amount of GF-KH570-5 being 30 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 3 min using a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-5 enhanced photocurable composite material.

[0156] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 40 seconds.

[0157] The GF-KH570-5 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 4.8%, and a breaking elongation anisotropy of 3.3%.

[0158] Example 6 Preparation of modified GF reinforced photocurable composite material

[0159] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0160] 1) Preparation of alkylated modified glass fiber GF-KH570-6

[0161] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0162] Add 80 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with sulfuric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1.5 g of KH570 silane coupling agent, and stir continuously at room temperature for 6 hours to obtain a grafted product.

[0163] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-6). GF-KH570-6 was used to prepare modified GF composite materials.

[0164] 2) Preparation of GF-KH570-6 reinforced light-cured composites

[0165] Bisphenol A epoxy acrylate (28 g), hydroxyethyl acrylate (12 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.4 g) were mixed to obtain a photosensitive resin;

[0166] Then, 4 g of GF-KH570-6 (correspondingly, the addition amount of GF-KH570-6 is 10 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 2 min by a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-6 enhanced light-cured composite material;

[0167] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 20 seconds.

[0168] The GF-KH570-6 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 9.3% and a breaking elongation anisotropy of 8.9%.

[0169] Example 7 Preparation of modified GF reinforced photocurable composite material

[0170] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0171] 1) Preparation of alkylated modified glass fiber GF-KH570-7

[0172] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0173] Add 50 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with sulfuric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 1 g of KH570 silane coupling agent, and stir continuously at room temperature for 10 hours to obtain a grafted product.

[0174] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-7). GF-KH570-7 was used to prepare modified GF composite materials.

[0175] 2) Preparation of GF-KH570-7 reinforced light-cured composites

[0176] Bisphenol A epoxy acrylate (36 g), bisethoxy acrylate (4 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.8 g) were mixed to obtain a photosensitive resin;

[0177] Then, 8 g of GF-KH570-7 (corresponding to an addition amount of GF-KH570-7 of 20 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 2 min using a high-speed disperser to obtain a uniformly mixed GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-7 enhanced photocurable composite material.

[0178] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing. The total curing time was about 30 seconds.

[0179] The GF-KH570-7 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 7.3% and a breaking elongation anisotropy of 6.6%.

[0180] Example 8 Preparation of modified GF reinforced photocurable composite material

[0181] The specific preparation method of the modified GF reinforced light-cured composite material in this embodiment is as follows:

[0182] 1) Preparation of alkylated modified glass fiber GF-KH570-8

[0183] 6 g of initial GF was first treated with acetone at room temperature for 24 h to remove surface pollutants. The treated product was washed with deionized water and then dried in an oven at 60° C. for 12 h to obtain pretreated glass fiber.

[0184] Add 50 mL of 95% ethanol aqueous solution into a beaker, adjust the pH to about 3 with hydrochloric acid solution, transfer the mixed solution into a single-necked flask, add 5 g of pretreated glass fiber, add 0.5 g of KH570 silane coupling agent, and stir continuously at room temperature for 12 hours to obtain a grafted product.

[0185] After the reaction, the grafted product was washed with ethanol and then dried in an oven at 60° C. for 12 h to obtain KH570 modified glass fiber (denoted as GF-KH570-8). GF-KH570-8 was used to prepare modified GF composite materials.

[0186] 2) Preparation of GF-KH570-8 reinforced light-cured composites

[0187] Bisphenol A epoxy acrylate (32 g), tetrahydrofuran acrylate (8 g) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (0.8 g) were mixed to obtain a photosensitive resin;

[0188] Then, 4 g of GF-KH570-8 (correspondingly, the addition amount of GF-KH570-8 was 10 wt.%) was added to the photosensitive resin, and dispersed at 3000 r / min for 2 min using a high-speed disperser to obtain a uniformly mixed modified GF enhanced photosensitive resin solution. After removing the bubbles, the solution was poured into a commercial 405 nm DLP 3D printer to prepare a GF-KH570-8 enhanced photocurable composite material.

[0189] After printing, ethanol was used to clean the remaining resin solution on the surface of the sample, and then a full-band crawler light curing machine was used for post-curing, and the total curing time was 40 seconds.

[0190] The GF-KH570-8 reinforced photocurable composite material sample prepared in this embodiment has a tensile strength anisotropy of 9.1% and a breaking elongation anisotropy of 9.0%.

[0191] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An isotropic glass fiber reinforced light-curable material, characterized in that: The isotropic glass fiber reinforced photocurable material is a photosensitive resin in which alkylated modified glass fibers are distributed, wherein the content of the alkylated modified glass fibers is 10-30wt.% of the photosensitive resin, wherein the tensile strength anisotropy of the isotropic glass fiber reinforced photocurable material is not higher than 9.3%, and the elongation at break anisotropy is not higher than 9.0%.

2. The isotropic glass fiber reinforced light-curable material according to claim 1, characterized in that: The content of the alkylated modified glass fiber is 20-30wt.%, preferably 30wt.% of the photosensitive resin; and / or Preferably, the tensile strength anisotropy of the isotropic glass fiber reinforced photocurable material is not higher than 7.5%, and the elongation at break anisotropy is not higher than 7.0%; more preferably, the tensile strength anisotropy of the isotropic glass fiber reinforced photocurable material is not higher than 5.0%, and the elongation at break anisotropy is not higher than 3.5%; and / or Preferably, the tensile strength of the isotropic glass fiber reinforced photocurable material is higher than 70 MPa; and / or Preferably, the elongation at break of the isotropic glass fiber reinforced photocurable material is higher than 6%; and / or Preferably, the isotropic glass fiber reinforced light-curable material is -1 and 2902cm -1 There are CH2 asymmetric and symmetric vibration peaks at 1054cm -1 There is a Si-O-Si stretching vibration peak at 1411 cm -1 There is a CH bending vibration peak of -CH3 at .

3. Use of alkylated modified glass fiber in the preparation of isotropic glass fiber reinforced photocurable material, characterized in that: The isotropic glass fiber reinforced photocurable material is the isotropic glass fiber reinforced photocurable material as claimed in claim 1 or 2, and the alkylated modified glass fiber is obtained by a grafting reaction between glass fiber and a silane coupling agent.

4. A method for preparing an isotropic glass fiber reinforced light-curable material, characterized in that: Described preparation method comprises the following steps: Mixing bisphenol A epoxy acrylate, monofunctional acrylate monomer and photoinitiator to obtain photosensitive resin; Alkyl modified glass fiber is added to the photosensitive resin, wherein the alkyl modified glass fiber accounts for 10-30wt.% of the photosensitive resin, and then dispersed and mixed to obtain an alkyl modified glass fiber reinforced photosensitive resin solution, which is 3D printed and post-cured to prepare a composite material, namely an isotropic glass fiber reinforced photocurable material; the alkyl modified glass fiber is obtained by grafting reaction of glass fiber and silane coupling agent.

5. The preparation method according to claim 4, characterized in that: The monofunctional acrylate monomer includes one or more of isobornyl acrylate, dicyclopentadiene acrylate, hydroxyethyl acrylate, diethoxy acrylate, tetrahydrofuran acrylate; and / or Preferably, the photoinitiator comprises one or more of 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and / or Preferably, the mass ratio of the bisphenol A epoxy acrylate, the monofunctional acrylate monomer and the photoinitiator is 24-36:4-16:0.4-0.

8.

6. The preparation method according to claim 4, characterized in that: The content of the alkylated modified glass fiber is 20-30wt.%, preferably 30wt.% of the photosensitive resin; and / or The dispersion time is 1 to 5 minutes; and / or Preferably, the post-curing time is 10 to 50 seconds.

7. The preparation method according to claim 4, characterized in that: The grafting reaction of the glass fiber and the silane coupling agent specifically comprises the following steps: (a) treating the glass fiber with acetone at room temperature for 12-48 hours to remove surface pollutants, then washing with water and drying to obtain pretreated glass fiber; (b) adjusting the pH value of the 95% ethanol aqueous solution to 3±0.5 with an acidic solution, adding a silane coupling agent and the pretreated glass fiber, and performing a grafting reaction to obtain a grafted product; (c) After the reaction is completed, the grafted product is washed and dried to obtain an alkylated modified glass fiber.

8. The preparation method according to claim 7, characterized in that: Based on 5g equivalent of glass fiber, the amount of the 95% ethanol aqueous solution added is 50-100ml; and / or Preferably, the acidic solution is one or more solutions of hydrochloric acid, sulfuric acid or nitric acid.

9. The preparation method according to claim 7, characterized in that: Preferably, the reaction temperature of the grafting reaction is 0 to 50° C., and the reaction time is 5 to 12 hours; and / or Preferably, the silane coupling agent includes at least one of KH570, KH540 and KH590; and / or Preferably, the mass ratio of the silane coupling agent to the glass fiber is 0.1-0.3:

1.

10. Use of the isotropic glass fiber reinforced photocurable material as claimed in claim 1 or 2, or prepared by the method as claimed in any one of claims 4 to 9 in the fields of medical equipment, electronic components, automotive parts or aerospace.

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