A recyclable 3D-printable polymer component with surface activity, its preparation method and application

Abstract

The present invention discloses a recyclable 3D-printable surface-active polymer component, its preparation method, and its application, relating to the technical field of 3D printing liquid resin materials. The method comprises mixing an acrylate monomer with a RAFT agent, a dynamic crosslinker, and a photoinitiator to form a 3D printing photosensitive resin solution. After 3D printing and curing, a three-dimensional surface-active polymer component is obtained. The resulting material exhibits excellent recyclability and the ability to directly functionalize the surface, and can be manufactured with high precision using DLP 3D printing technology.

Description

Technical Field

[0001] The present invention belongs to the field of material technology and relates to the preparation of 3D printing liquid resin materials, and specifically to a surface-active polymer component that can be recycled in 3D printing, and a preparation method and application thereof. Background Art

[0002] Stereolithography 3D printing technology offers advantages such as high precision, complex structural fabrication, rapid manufacturing speed, and adaptability to a wide range of materials, making it one of the most attractive additive manufacturing methods. In recent years, 3D printing based on the principles of photo-stereolithography has been widely applied to advanced functional materials such as shape memory polymers, photochromic / photoluminescent materials, conductive polymers, biomedical materials, and recyclable materials, leading the application of 3D printing in various fields such as biomedicine, actuators / sensors, robotics, and aerospace.

[0003] In recent years, reversible deactivation radical polymerization (RDRP) has been introduced into photocuring-based 3D printing. The three-dimensional structures constructed using these methods, due to the dynamic chemical bonds within their polymer networks, are capable of undergoing network rearrangement under specific conditions. More interestingly, the 3D structures printed using this method can directly "insert" new functional monomers into the existing polymer network, exhibiting novel properties. Furthermore, the RDRP method introduces reversible covalent bonds into the polymer chain, including alkyl-pseudohalogen bonds in atom transfer radical polymerization (ATRP) and alkyl-sulfide bonds in reversible addition-fragmentation chain transfer (RAFT) polymerization. These reversible covalent bonds enable the material to exhibit self-healing behavior through polymer network reorganization under specific conditions. The polymer chains produced using the RDRP method exhibit a more uniform polymer network in photocuring 3D printing, which contributes to improved mechanical properties.

[0004] Photocuring 3D printing technology requires the formation of a cross-linked network, which makes reprocessing and recycling difficult. Therefore, the reprocessing and recycling of photocuring 3D printed structures have gradually become a concern for researchers. By introducing a dynamic covalent polymer network, the material can be made thermally recyclable. However, recycled materials are usually not directly involved in the next step of photocuring 3D printing. To this end, the present invention provides a surface-active polymer component that can be recycled in 3D printing, as well as a preparation method and application thereof. Summary of the Invention

[0005] In order to solve the deficiencies in the above-mentioned background technology, mainly because the photocuring 3D printing technology requires the formation of a cross-linked network, which brings difficulties to reprocessing and recycling, the material can be made heat-recyclable by introducing a dynamic covalent polymer network. However, there is a technical problem that recycled materials cannot usually be directly involved in the next step of photocuring 3D printing. The present invention provides a surface-active polymer part that can be recycled by 3D printing, a preparation method and application thereof, and the material prepared by this method has good recyclability and direct surface functionalization capabilities, and can be manufactured with high precision by DLP 3D printing technology.

[0006] In order to achieve the above objectives, the first aspect of the present invention provides a composition for preparing a surface-active polymer part that can be recycled and 3D printed, wherein the composition comprises: an acrylate monomer, a RAFT agent, a dynamic crosslinker, and a photoinitiator.

[0007] Preferably, the RAFT agent is dibenzyl trithiocarbonate;

[0008] The dynamic cross-linking agent is 4,6,11-trioxy-3,7,10-trioxatride-12-en-1-yl prop-2-enoate (BAM);

[0009] The photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0010] Preferably, the acrylic acid ester monomer includes 2-hydroxyethyl acrylate.

[0011] Preferably, the molar ratio of the RAFT agent to the acrylate monomer is 1:25-100;

[0012] The molar ratio of the dynamic crosslinking agent to the acrylate monomer is 1:1 to 19;

[0013] The mass ratio of the photoinitiator to the acrylate monomer is 2-4:100.

[0014] The second aspect of the present invention provides the use of the above-mentioned composition in the preparation of surface-active polymer parts that can be recycled and 3D printed.

[0015] A third aspect of the present invention provides a surface-active polymer part that can be recycled and 3D printed, wherein the polymer part is prepared from a raw material comprising the above-mentioned composition;

[0016] The polymer parts can be recycled and printed in a circular manner.

[0017] A fourth aspect of the present invention provides a method for preparing a surface-active polymer component that can be recycled and 3D printed, comprising the following steps:

[0018] Acrylate monomers are mixed with RAFT agents, dynamic crosslinkers and photoinitiators to form a 3D printing photosensitive resin solution. After photocuring 3D printing, a three-dimensional polymer part with surface activity is obtained.

[0019] Preferably, the recovery method comprises the following steps:

[0020] The 3D printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen to obtain a recovery solution;

[0021] Ether was added to the recovered solution to obtain a precipitate;

[0022] The precipitate contains the same acrylic acid ester monomer as that used to prepare the polymer component.

[0023] A fifth aspect of the present invention provides a method for recovering a polymer component. In the process of obtaining the precipitate, the volume ratio of the recovery solution to the ether is 1:10~20.

[0024] A sixth aspect of the present invention provides a cyclic printing method for polymer parts, the cyclic printing method comprising the following steps:

[0025] The 3D printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen to obtain a recovery solution;

[0026] Adding ether to the recovered solution to obtain a precipitate; wherein the precipitate contains the same acrylate monomer used to prepare the polymer component;

[0027] The precipitate is mixed with an acrylate monomer and / or a hydrophobic monomer, a dynamic crosslinking agent, and a photoinitiator to form a 3D printing photosensitive resin solution. After photocuring 3D printing, a three-dimensional polymer product with surface activity is obtained again.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The present invention provides a recyclable 3D-printable surface-active polymer component, as well as its preparation method and application. This involves curing a printable precursor solution consisting of a hydroxyl-containing acrylate monomer (HEA), a dynamic crosslinker (BAM) containing an ester bond, a RAFT agent, and a photoinitiator, through controlled free radical polymerization under UV light to form a three-dimensional polymer network. The resulting polymer material, due to the presence of trithioester bonds within the network, allows for direct insertion of new (meth)acrylate monomers into the material under UV conditions. Furthermore, under high temperature, the trithioester groups within the network drive molecular chain rearrangement and dynamic exchange between the dynamic crosslinker (BAM) and hydroxyl groups. Furthermore, the presence of dynamic ester bonds allows the material to dissolve in ethylene glycol at high temperatures. The recycled macromolecules, which still contain trithioester groups, can be recycled to enable the 3D printing process again by reintroducing monomers, crosslinkers, and initiators. Furthermore, the mechanical properties of the material are controllable. This enables the preparation of a recyclable, controllable, and DLP 3D-printable active polymer material. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a flow chart of the present invention.

[0031] Figure 2 It is a graph showing the change in mechanical properties of the polymer products provided in Examples 1-4 and Examples 15 to 17.

[0032] Figure 3 Schematic diagram of the internal network rearrangement of the polymer material provided in the embodiment at high temperature.

[0033] Figure 4 Schematic diagram of the polymer component material provided in the embodiment dissolving in ethylene glycol at high temperature over time.

[0034] Figure 5 These are photos of the polymer products provided in Examples 5-8 dissolved in ethylene glycol at different times.

[0035] Figure 6 This is the NMR result of the active poly (2-hydroxyethyl acrylate) macromolecular chain provided in Example 9.

[0036] Figure 7 These are the mechanical properties of the polymer parts provided in Examples 10-12.

[0037] Figure 8 These are the contact angle test results of the material printed in Example 13 and the material printed in Example 2.

[0038] Figure 9 This is a physical picture of the surface functionalization of the material prepared in Example 14. DETAILED DESCRIPTION

[0039] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below with reference to specific embodiments and drawings, but the embodiments are not intended to limit the present invention.

[0040] The present invention provides a composition for preparing a surface-active polymer part that can be recycled in 3D printing. The composition comprises: an acrylate monomer, a RAFT agent, a dynamic crosslinking agent, and a photoinitiator.

[0041] According to the present invention, the RAFT agent is dibenzyl trithiocarbonate (DBTTC);

[0042] The dynamic cross-linking agent is 4,6,11-trioxy-3,7,10-trioxatride-12-en-1-yl prop-2-enoate (BAM);

[0043] The photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO).

[0044] According to the present invention, the acrylic acid ester monomer includes 2-hydroxyethyl acrylate.

[0045] According to the present invention, the reaction ratio of the RAFT agent to the acrylate monomer is 1:25-100;

[0046] The molar ratio of the dynamic crosslinking agent to the acrylate monomer is 1:1 to 19;

[0047] The ratio of the photoinitiator to the acrylate monomer is 2-4:100.

[0048] The present invention provides the use of the above composition in preparing a surface-active polymer component that can be recycled and 3D printed.

[0049] The present invention provides a surface-active polymer part that can be recycled and 3D-printed. The polymer part is prepared from a raw material containing the above-mentioned composition; the polymer part can be recycled and printed in a recycling manner.

[0050] The present invention provides a method for preparing the above-mentioned surface-active polymer parts that can be recycled and 3D printed, comprising the following steps:

[0051] Acrylate monomers are mixed with RAFT agents, dynamic crosslinkers and photoinitiators to form a 3D printing photosensitive resin solution. After photocuring 3D printing, a three-dimensional polymer part with surface activity is obtained.

[0052] The acrylate monomer, RAFT agent, dynamic crosslinker and photoinitiator all have the meanings and mass ratios described above.

[0053] The 3D printing of the present invention adopts a light-curing 3D printer. The laser selected in the light-curing 3D printing process is ultraviolet light, and the ultraviolet post-curing treatment time is 60 minutes. The parameters of 3D printing are: exposure time 15-20 seconds, bottom layer exposure time 20-30 seconds, and layer thickness 0.05-0.1 mm.

[0054] The present invention provides a method for recycling the above-mentioned recyclable 3D-printed polymer parts with surface activity, the recycling method comprising the following steps:

[0055] The 3D-printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen conditions to obtain a recovered solution; the nitrogen plays a protective role.

[0056] Ether was added to the recovered solution to obtain a precipitate;

[0057] The precipitate contains the same acrylic acid ester monomer as that used to prepare the polymer component.

[0058] Furthermore, in the process of obtaining the precipitate, the volume ratio of the recovered solution to the diethyl ether is 1:10~20.

[0059] See also Figure 1 As shown, the present invention provides a cyclic printing method for the above-mentioned 3D-printable polymer parts with surface activity, and the cyclic printing method comprises the following steps:

[0060] The 3D printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen to obtain a recovery solution;

[0061] Adding ether to the recovered solution to obtain a precipitate; wherein the precipitate contains the same acrylate monomer used to prepare the polymer component;

[0062] The precipitate is mixed with an acrylate monomer and / or a hydrophobic monomer, a dynamic crosslinker, and a photoinitiator to form a 3D printing photosensitive resin solution. After photocuring and 3D printing, a three-dimensional polymer component with surface activity is obtained. The hydrophobic monomer is n-butyl acrylate. It should be noted that the recovered product is a macromolecular segment containing trisulfide, which can replace the original DBTTC (RAFT agent). Therefore, DBTTC is added during the cyclic printing process.

[0063] The 3D-printed polymer component with surface activity is prepared by using the above-mentioned method for preparing a recyclable 3D-printed polymer component with surface activity.

[0064] According to the present invention, the hydrophobic monomer includes n-butyl acrylate or benzyl acrylate. By adding the hydrophobic monomer during recycling printing, the hydrophilic and hydrophobic properties of the material are altered. Acrylate, due to its double bond, can be incorporated into the recycled macromolecular segments through a dynamic reaction of trisulfide under ultraviolet light, which is the principle behind the feasibility of recycling printing.

[0065] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0066] It should be noted that the experimental methods used in the present invention are all conventional methods unless otherwise specified; the reagents and materials used are all commercially available unless otherwise specified.

[0067] Example 1

[0068] DBTTC (0 mmol), BAM (5 mmol), 2-hydroxyethyl acrylate (95 mmol) and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was added to a 3D printer and then photocuring printing was performed.

[0069] Example 2

[0070] DBTTC (1 mmol), BAM (5 mmol), 2-hydroxyethyl acrylate (95 mmol) and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was added to a 3D printer and then photocuring printing was performed.

[0071] Example 3

[0072] DBTTC (2 mmol), BAM (5 mmol), 2-hydroxyethyl acrylate (95 mmol) and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was added to a 3D printer and then photocuring printing was performed.

[0073] Example 4

[0074] DBTTC (4 mmol), BAM (5 mmol), 2-hydroxyethyl acrylate (95 mmol) and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was added to a 3D printer and then photocuring printing was performed.

[0075] Among them, in Examples 1 to 4, the 3D printing parameters are: exposure time 20s, bottom layer exposure time 30s, and layer thickness 0.1mm.

[0076] Example 5

[0077] Take 1g of the printed sample prepared in Example 1, put it into 10ml of ethylene glycol solution, introduce nitrogen, and heat to 150°C with stirring.

[0078] Example 6

[0079] Take 1g of the printed sample prepared in Example 2, put it into 10ml of ethylene glycol solution, introduce nitrogen, and heat to 150°C with stirring.

[0080] Example 7

[0081] Take 1g of the printed sample prepared in Example 3, put it into 10ml of ethylene glycol solution, introduce nitrogen, and heat to 150°C with stirring.

[0082] Example 8

[0083] Take 1g of the printed sample prepared in Example 4 and place it in 10ml of ethylene glycol solution, introduce nitrogen, and heat to 150°C with stirring.

[0084] Example 9

[0085] The dissolved solution of Example 8 was dropped into diethyl ether (volume ratio 1:10) at a speed of 8000 r / min. After centrifugation for 10 minutes, the viscous liquid precipitate was centrifuged to obtain a viscous liquid product, which was then subjected to nuclear magnetic resonance testing.

[0086] Example 10

[0087] The product obtained in Example 9 (1 mmol), 2-hydroxyethyl acrylate (70 mmol), BAM (5 mmol) and TPO (2 mmol) were mixed evenly and placed in a 3D printer for printing.

[0088] Example 11

[0089] The product obtained in Example 9 (2 mmol), 2-hydroxyethyl acrylate (45 mmol), BAM (5 mmol) and TPO (2 mmol) were mixed evenly and placed in a 3D printer for printing.

[0090] Example 12

[0091] The product obtained in Example 9 (2 mmol), 2-hydroxyethyl acrylate (40 mmol), BAM (10 mmol) and TPO (2 mmol) were mixed evenly and placed in a 3D printer for printing.

[0092] The 3D printing parameters in Examples 10 to 12 were: exposure time 16 s, bottom layer exposure time 26 s, and layer thickness 0.1 mm.

[0093] Example 13

[0094] The product obtained in Example 9 (1 mmol), 2-hydroxyethyl acrylate (70 mmol), BAM (5 mmol), n-butyl acrylate (40 mmol) and TPO (2 mmol) were mixed evenly and placed in a 3D printer for printing. It should be noted that n-butyl acrylate is a typical hydrophobic monomer and its addition can change the contact angle of the material. Figure 8 shown.

[0095] Example 14

[0096] The 3D structure printed in Example 13 was immersed in a DMF solution (concentration: 15 wt%) containing pyrrole-methyl methacrylate (PyMMA), hydroxyethyl acrylate (HEA) (PyMMA:HEA = 1:9), and TPO (3% of the combined mass of PyMMA and HEA). The structure was irradiated under UV light for 1 hour. After removal, it was rinsed with DMF.

[0097] Examples 1-4 were conducted to examine the effects of the chain transfer reagent DBTTC on the mechanical properties of the material;

[0098] Figure 2 The mechanical properties of the polymer products provided in Examples 1-4 and 15 to 17 are shown in FIG. Figure 2 It can be seen that with the increase of chain transfer agent content, the stiffness of the material decreases, but the elongation at break and toughness increase significantly, indicating that the addition of chain transfer agent makes the molecular chains inside the material more uniform, reduces the resistance to chain movement, and thus exhibits better mechanical properties.

[0099] Figure 3 The schematic diagram of the internal network rearrangement of the polymer component material provided in the embodiment at high temperature shows that under heating conditions, the covalent trithiocarbonate bonds and ester bonds in the polymer network undergo a dynamic exchange reaction. That is, due to the heating effect, the C=S bond of the TTC unit in the polymer network breaks, generating thiocarbonylthio radical fragments and polymer chains with active free radicals. Afterwards, the polymer chains with active free radicals can undergo a degenerative exchange reaction (shuffling process) with other thiocarbonylthio radical fragments. In addition, the hydroxyl group of HEA undergoes an ester exchange reaction with the ester group of BAM, and the polymer network rearranges and reorganizes. The hydroxyl group of HEA acts as a nucleophile to perform nucleophilic substitution on the carbonyl carbon in the ester group, and the original ester bond dissociates to generate a new hydroxyl chemical.

[0100] Figure 4This is a schematic diagram of the polymer component material provided in the examples dissolving in ethylene glycol at high temperature over time. Due to the presence of dynamic hydroxyl-ester bonds in the cured sample, the material can react with ethylene glycol at high temperatures, thereby opening the cross-linking structure and transforming the insoluble three-dimensional cross-linked thermosetting polymer network into a soluble linear polymer. Figure 4 This is clearly described. In addition, the material does not degrade, but only de-crosslinks under high temperature conditions.

[0101] Figure 5 The dissolution of the polymer parts provided in Examples 5-8 at different times. Under the same crosslinking density, the dissolution rate gradually increases with the increase of DBTTC ratio. Example 4 dissolved within 4 hours, while Example 1, which does not contain DBTTC, still could not dissolve after 24 hours. In addition, the reasons for the inability to dissolve are: (1) The materials of Examples 1-4 contain less crosslinking agent (dynamic reaction) and do not contain DBTTC, resulting in a slower dynamic reaction rate and inability to dissolve within 24 hours; (2) Example 1 does not contain DBTTC, and its photocuring process is a simple free radical polymerization process, while Examples 2-4 contain DBTTC, which is a controlled free radical polymerization process, and the polymer network is more uniform.

[0102] Figure 6 This is the test result of Example 9. The results show that the dissolved macromolecular product is poly (2-hydroxyethyl acrylate) active macromolecular chain, and the molecular weight calculated by nuclear magnetic resonance is about 3190.

[0103] Figure 7 The mechanical testing results of Examples 10-12 were obtained by reprinting materials using reactive poly(2-hydroxyethyl acrylate), 2-hydroxyethyl acrylate, BAM, and TPO. The results demonstrate that the mechanical properties of materials printed using this strategy can be controlled by adjusting the reactive poly(2-hydroxyethyl acrylate) macromolecular chains and the relative contents of 2-hydroxyethyl acrylate and BAM. Comparing Examples 10 and 11 (under the same crosslinking conditions), the material prepared in Example 10 exhibits longer molecular chains, resulting in stronger chain hindrance and higher modulus and breaking strength. Comparing Examples 10 and 12, the higher the crosslinking degree, the higher the modulus and strength. Since the mechanical testing results of Examples 10-12 are similar to those of Examples 1, 2, and 15, it can be assumed that recycled printed materials can be restored to the properties of the original printed material.

[0104] Figure 8The following are the contact angle test results of the material printed in Example 13 and the material printed in Example 2. Specifically, the contact angle comparison chart shows the material printed again using active poly (2-hydroxyethyl acrylate), 2-hydroxyethyl acrylate, BAM, butyl acrylate, and TPO, and the material printed using 2-hydroxyethyl acrylate, BAM, and TPO. In Example 13, n-butyl acrylate was added, which is a typical hydrophobic monomer that can change the contact angle of the material. The contact angle of the material printed in Example 2 increased from 53.5° to 87.8°. Therefore, this example demonstrates that in addition to the controllable mechanical properties, this strategy can also change the functional properties of the material by adding different monomers.

[0105] Figure 9 The material prepared in Example 14, specifically the material printed with 2-hydroxyethyl acrylate, BAM and TPO, emits obvious blue fluorescence under ultraviolet conditions, indicating that the material can be functionalized by directly inserting monomers, which proves the activity of the material. It should be noted that Figure 9 (a) is a photo of the polymer product provided in Example 14 under white light conditions, Figure 9 (b) is a photograph of the polymer product provided in Example 14 under ultraviolet light in a dark room.

[0106] The present invention also provides other embodiments to verify the effectiveness of the experimental process of the present invention:

[0107] Example 15

[0108] DBTTC (2 mmol), BAM (10 mmol), 2-hydroxyethyl acrylate (90 mmol), and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was then added to a 3D printer and subjected to photocuring. The 3D printing parameters were: exposure time 17 seconds, bottom exposure time 20 seconds, and layer thickness 0.05 mm. After printing, the printed 3D structure was removed from the resin tank and post-cured with UV light for 60 minutes. It was then dissolved and recovered in a 120°C ethylene glycol solution under nitrogen.

[0109] Example 16

[0110] DBTTC (2 mmol), BAM (20 mmol), 2-hydroxyethyl acrylate (80 mmol), and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was then added to a 3D printer and subjected to photocuring. The 3D printing parameters were: exposure time 15 seconds, bottom exposure time 20 seconds, and layer thickness 0.05 mm. After printing, the printed 3D structure was removed from the resin tank and post-cured with UV light for 60 minutes. It was then dissolved in an ethylene glycol solution at 140°C under nitrogen and dialyzed.

[0111] Example 17

[0112] DBTTC (2 mmol), BAM (50 mmol), 2-hydroxyethyl acrylate (50 mmol), and TPO (2 mol) were mixed and shaken to obtain a printing resin. The resin was then added to a 3D printer and subjected to photocuring. The 3D printing parameters were: exposure time 18 seconds, bottom exposure time 20 seconds, and layer thickness 0.1 mm. After printing, the printed 3D structure was removed from the resin tank and post-cured under UV light for 60 minutes. It was then dissolved in an ethylene glycol solution at 170°C under nitrogen and dialyzed.

[0113] Example 18

[0114] The product from Example 9 (1 mmol), 2-hydroxyethyl acrylate (70 mmol), BAM (5 mmol), benzyl acrylate (50 mmol), and TPO (2 mmol) were mixed and placed in a 3D printer for printing. The 3D printing parameters were: exposure time 15 s, bottom layer exposure time 20 s, and layer thickness 0.15 mm.

[0115] Examples 15-17 obtained polymer materials with different cross-linking degrees by photocuring printing. Figure 2 The corresponding mechanical properties and Figure 5 The dissolution rate is given; Example 18 is a supplement to Example 13. At the same time, Figure 8 The addition of a hydrophobic monomer (n-butyl acrylate) causes a change in the contact angle of the material; Figure 9 This is a photo showing fluorescent properties under ultraviolet light after adding fluorescent monomers, thereby changing the functional properties of recycled printing materials by adding acrylate monomers.

[0116] The present invention describes preferred embodiments and their effects. However, those skilled in the art, once informed of the basic inventive concept, may make additional changes and modifications to these embodiments. Therefore, it is intended that the appended claims be interpreted to include the preferred embodiments as well as all changes and modifications that fall within the scope of the invention.

[0117] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A composition for preparing a surface-active polymer part that can be recycled and 3D printed, characterized in that: The composition comprises: an acrylate monomer, a RAFT agent, a dynamic crosslinking agent and a photoinitiator; The RAFT agent is dibenzyl trithiocarbonate; The dynamic crosslinking agent is 4,6,11-trioxy-3,7,10-trioxatride-12-en-1-yl prop-2-enoate; The photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; The acrylic acid ester monomer includes 2-hydroxyethyl acrylate.

2. The composition according to claim 1, characterized in that The molar ratio of the RAFT agent to the acrylate monomer is 1:25-100; The molar ratio of the dynamic crosslinking agent to the acrylate monomer is 1:1 to 19; The mass ratio of the photoinitiator to the acrylate monomer is 2-4:

100.

3. Use of the composition according to claim 1 or 2 in the preparation of surface-active polymer parts that can be recycled and 3D printed.

4. A surface-active polymer component that can be recycled and 3D printed, characterized in that: The polymer product is prepared from a raw material comprising the composition according to claim 1 or 2; The polymer parts can be recycled and printed in a circular manner.

5. The method for preparing a surface-active polymer component capable of being recyclable and 3D printed according to claim 4, wherein: The following steps are involved: Acrylate monomers are mixed with RAFT agents, dynamic crosslinkers and photoinitiators to form a 3D printing photosensitive resin solution. After photocuring 3D printing, a three-dimensional polymer part with surface activity is obtained.

6. The method for recycling polymer products according to claim 4, characterized in that: The recovery method comprises the following steps: The 3D printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen to obtain a recovery solution; Ether was added to the recovered solution to obtain a precipitate; The precipitate contains the same acrylic acid ester monomer as that used to prepare the polymer component.

7. The method for recycling polymer products according to claim 6, characterized in that: During the process of obtaining the precipitate, the volume ratio of the recovered solution to the diethyl ether is 1:10-20.

8. The cyclic printing method for polymer parts according to claim 4, characterized in that: The cyclic printing method comprises the following steps: The 3D printed polymer parts with surface activity are placed in an ethylene glycol solution at 120-170°C and dissolved under nitrogen to obtain a recovery solution; Adding ether to the recovered solution to obtain a precipitate; wherein the precipitate contains the same acrylate monomer used to prepare the polymer component; The precipitate is mixed with an acrylate monomer and / or a hydrophobic monomer, a dynamic crosslinking agent, and a photoinitiator to form a 3D printing photosensitive resin solution. After photocuring 3D printing, a three-dimensional polymer product with surface activity is obtained again.

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