A semi-acetal ester-based thermosetting resin material, a preparation method and application thereof

Abstract

The application discloses a semi-acetal ester-based thermosetting resin material and a preparation method and application thereof. The preparation method comprises the following steps: subjecting a uniform mixed reaction system comprising at least one copolymerized monomer containing an unsaturated double bond, at least one multifunctional vinyl ether crosslinking agent and an initiator to in-situ polymerization and dynamic crosslinking reaction at 0-160 DEG C to prepare the semi-acetal ester-based thermosetting resin material, and the terminal group of the at least one copolymerized monomer is a carboxyl group. The linear polymer skeleton of the semi-acetal ester-based thermosetting resin material has a network structure formed by semi-acetal ester bonds-COOC(CH3)O-. The preparation method is simple in operation, free of solvent participation, free of purification, green and environment-friendly, easy for industrialized production, and the prepared product has excellent mechanical properties, thermal properties and reworkability. The application achieves the technical effect that high molecular polymer materials can be processed and molded, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of polymer material synthesis and processing technology, specifically to a rapidly reprocessable hemiacetal-based thermosetting resin material, its preparation method, and its molding and processing method. Background Technology

[0002] Thermoplastics are polymeric materials formed from monomer raw materials through addition polymerization or condensation polymerization. Their inherent shape can be altered by simple heating, and they offer diverse recycling and processing options. Currently, polymeric materials are widely used in our lives, primarily composed of thermosetting resins. Thermosetting resins are covalently cross-linked three-dimensional polymer networks formed through a cross-linking and curing process using various cross-linking agents. Initially liquid during the manufacturing process, they soften and flow upon first heating. Upon reaching a certain temperature, a chemical cross-linking reaction occurs, causing them to solidify and harden—a process that is irreversible. Due to their excellent thermal, mechanical, chemical resistance, and dimensional stability, thermosetting resins are widely used in coatings, adhesives, composite materials, and electronic packaging materials, and are irreplaceable in many applications. However, their permanently cross-linked networks make them difficult to recycle or reprocess after use. Currently, the main disposal methods are landfill and incineration, which are detrimental to the sustainable development of materials.

[0003] In recent decades, the introduction of dynamic covalent bonds into thermosetting resins has attracted considerable attention. Due to their cross-linked networks, these resins possess the high performance characteristics of thermosetting materials; and because of the presence of dynamic bonds, they can be reprocessed like thermoplastics, exhibiting properties such as self-healing, biodegradability, recyclability, weldability, and deformability. To date, numerous applications of dynamic bonds have been explored in the production of thermosetting resins. However, due to the slow rate of network rearrangement, most reported thermosetting resins containing dynamic bonds require lengthy reprocessing times at high temperatures, which not only damages their networks and thus reduces their performance but also consumes significant amounts of energy. Furthermore, they are limited to thermoforming and are not suitable for continuous reprocessing methods such as extrusion and injection molding.

[0004] Recent years have witnessed efforts to accelerate the dynamic exchange of dynamic bonds in thermosetting resins, and some continuous reprocessing of such resins has been achieved. Despite significant progress, developing thermosetting resins that combine rapid reprocessability and high performance, especially through simple and green methods to prepare such polymer networks, remains a major challenge.

[0005] In summary, existing technologies for preparing thermosetting cross-linked polymer materials suffer from the drawback of being unable to re-process the materials below their decomposition temperature. Furthermore, these technologies are cumbersome, energy-intensive, and have low atomic conversion rates. Summary of the Invention

[0006] The main objective of this invention is to provide a rapidly reprocessable hemiacetal-based thermosetting resin material and its preparation method, thereby overcoming the technical defects of existing technologies in the preparation of thermosetting crosslinked polymer materials, such as cumbersome processes, high energy consumption, low atomic conversion rate, and the need for reprocessing and molding, and thus solving this technical problem.

[0007] To achieve the above-mentioned objectives, the technical solution adopted by the present invention includes:

[0008] Some embodiments of the present invention provide a method for preparing a hemiacetal-based thermosetting resin material, comprising:

[0009] A hemiacetal-based thermosetting resin material is prepared by in-situ polymerization and dynamic crosslinking reaction of a homogeneous mixture containing at least one comonomer with unsaturated double bonds, at least one multifunctional vinyl ether crosslinking agent, and a polymerization initiator at 0–160°C. The end group of at least one comonomer is -COOH.

[0010] In some embodiments, the comonomer has a structure as shown in formula (I):

[0011]

[0012] Among them, R1 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R a replace;

[0013] R2 is selected from C 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R b replace;

[0014] R3 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R c replace;

[0015] The R a R b R c Selected independently from C 1- C 10 alkyl, C 2- C 10 alkenyl, C 1- C 10 heteroalkyl or C 2- C 10 heteroene group;

[0016] R4 is selected from

[0017] L1 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 Heteroalkylene groups, where L2 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 heteroalkyl groups;

[0018] R5 is selected from H or COOH.

[0019] In some embodiments, the vinyl ether crosslinking agent has a structure as shown in formula (II):

[0020]

[0021] Where k≥0, l≥1;

[0022] R6 is selected from H and C. 1- C 15 alkylene or C 1- C 15 heteroalkylene, the C 1- C 15 alkylene or C 1- C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 R d replace;

[0023] R7 is selected from H, C1-C 15 alkylene or C1-C 15 Heteroalkylene compounds, the C1-C 15 alkylene or C1-C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 Re replace;

[0024] R8 is selected from H, C1-C 15 alkylene or C 1- C 15 Heteroalkylene compounds, the C1-C 15 alkylene or C1-C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 R f replace;

[0025] R9 is selected from H, C1-C 15 alkyl, C 1- C 15 heteroalkyl groups or -OC2H3, wherein C1-C 15 Alkyl or C1-C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R g replace;

[0026] R 10 Selected from H, C1-C 15 alkyl, C 1- C 15 heteroalkyl groups or -OC2H3, wherein C1-C 15 Alkyl or C1-C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R h replace;

[0027] The R d R e R f R g R h Selected independently from C 1- C 10 alkyl, C 2- C 10 alkenyl, C 1- C 10 heteroalkyl or C 2- C 10 Heterene groups.

[0028] Some embodiments of the present invention also provide hemiacetal-based thermosetting resin materials prepared by the aforementioned method.

[0029] Furthermore, the linear polymer skeleton of the hemiacetal-based thermosetting resin material has a network structure formed by hemiacetal bonds -COOC(CH3)O-.

[0030] Furthermore, the hemiacetal-based thermosetting resin material has a structure as shown in formula (A) and / or formula (B):

[0031]

[0032] Where co represents copolymerization; p or q represents the degree of polymerization of the comonomer, with p and q ranging from 1 to 1000; y represents the type of comonomer, with y ranging from 0 to 10, k≥0, l≥1;

[0033] The R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 These are mutually independent and can be the same or different. The terms R1, R2, R3, R4, R5, R6, R7, R8, R9, and R... 10 As defined in the preparation scheme described above in this invention.

[0034] Some embodiments of the present invention also provide the application of the hemiacetal-based thermosetting resin material in the preparation of continuously processable cross-linked polymer materials.

[0035] Furthermore, the present invention also provides a method for preparing a continuously processable cross-linked polymer material, comprising:

[0036] Provided the hemiacetal-based thermosetting resin material;

[0037] The hemiacetal-based thermosetting resin material is pulverized and then subjected to twin-screw extrusion at a temperature higher than the glass transition temperature and lower than the decomposition temperature to reprocess it into a cross-linked polymer material.

[0038] Compared with the prior art, the present invention has at least the following advantages:

[0039] 1) By introducing dynamic hemiacetal bonds, this invention endows thermosetting materials with the advantage of being recyclable. At the same time, the cross-linking structure improves the mechanical properties, thermal properties and solvent resistance of the material, and also makes the material reprocessable.

[0040] 2) The in-situ polymerization and dynamic cross-linking preparation process of the polymer network in this invention is simple to operate, reduces the process flow, and can be produced on a large scale using existing chemical equipment. It has the advantages of being easy to implement, green, efficient and high-yield.

[0041] 3) Due to the reprocessability of dynamic covalent networks and the scalability of the preparation process, the development of the hemiacetal-based thermosetting resin material of the present invention can promote the development of reprocessable thermosetting materials, which is of great significance to the development of the entire polymer materials field and plays an important role in environmental protection. Attached Figure Description

[0042] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0043] Figure 1 The FTIR spectrum of the hemiacetal-based thermosetting resin material of formula (1) prepared in Example 1 of this invention. Detailed Implementation

[0044] To address the aforementioned technical problems, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly provides a method for preparing hemiacetal-based thermosetting resin materials and its reprocessing techniques. This invention utilizes the dynamic characteristics of rapid dissociation of hemiacetal esters to achieve continuous reprocessing of high-performance hemiacetal-based thermosetting resin materials. Furthermore, a simple, green, and efficient synthesis method—in-situ polymerization and dynamic crosslinking (ISPDC)—has been developed to produce hemiacetal-based thermosetting resin materials. The raw materials used in this invention, including (meth)acrylic acid monomers, (meth)acrylate monomers, styrene monomers, and various divinyl ether crosslinking agents, are all commercially available. The entire preparation process is solvent-free, requires no purification, and has a high atomic conversion rate, offering significant economic and ecological advantages. The hemiacetal-based thermosetting resin material is based on a dynamic covalent cross-linking network formed by methacrylic monomers, vinyl ether cross-linking agents, and styrene monomers, which introduces hemiacetal bonds, endowing the material with excellent mechanical properties, thermal properties, and solvent resistance. At the same time, the hemiacetal bonds can undergo rapid dissociation and exchange under high temperature conditions, making the polymer reprocessable and allowing it to be reprocessed in a twin-screw extruder.

[0045] The following will provide a further explanation of the technical solution, its implementation process, and its principles.

[0046] One aspect of the present invention provides a method for preparing a hemiacetal-based thermosetting resin material, comprising:

[0047] A hemiacetal-based thermosetting resin material is prepared by in-situ polymerization and dynamic crosslinking reaction of a homogeneous mixture containing one or more comonomers with unsaturated double bonds, at least one multifunctional vinyl ether crosslinking agent, and a polymerization initiator at 0–160°C. The hemiacetal-based thermosetting resin material is obtained, wherein the terminal group of at least one comonomer is -COOH.

[0048] In some embodiments, the comonomer has a structure as shown in formula (I):

[0049]

[0050] Among them, R1 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R a replace;

[0051] R2 is selected from C 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R b replace;

[0052] R3 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R c replace;

[0053] The R a R b R c Selected independently from C 1- C 10 alkyl, C 2- C 10 alkenyl, C 1- C 10 heteroalkyl or C 2- C 10 heteroene group;

[0054] R4 is selected from

[0055] L1 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 Heteroalkylene groups, where L2 is selected from single bonds, C 1- C 15 alkylene or C 1- C15 heteroalkyl groups;

[0056] R5 is selected from H or COOH.

[0057] In some preferred embodiments, the comonomer may include acrylic monomers, but is not limited thereto.

[0058] In some embodiments, L1 is selected from single bonds, -C2H4-, -C3H6-, -C4H8-, and -C6H. 12 -、-C 12 H 24 - or -C2H4-O-C2H4- etc., but not limited to these.

[0059] Furthermore, the L2 is selected from -CH2-O-C2H4-, -CH2-O-C3H6-, -CH2-O-C4H8-, and -CH2-O-C5H. 10 -,-CH2-O-C6H 12 -、-CH2-O-C7H 14 -,-CH2-O-C8H 16 -、-CH2-O-C9H 18 -, -CH2-OC 10 H 20 -, -CH2-OC 11 H 22 -, -CH2-OC 12 H 24 -, -CH2-OC 13 H 26 - or -CH2-O-C2H4-O-C2H4- etc., but not limited to these.

[0060] In some more specific embodiments, the comonomer represented by formula (I) includes methacrylic acid monomers, acrylic acid monomers, or acrylate monomers as shown in formula (III), or styrene monomers as shown in formula (IV), and at least one comonomer has an R 12 It is COOH;

[0061]

[0062] L1 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 Heteroalkylene groups, where L2 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 heteroalkyl groups;

[0063] R 11 Selected from H or C 1- C3 alkyl group; R 12 Selected from H or COOH.

[0064] Wherein, L1, L2, etc., are as defined in this invention.

[0065] In some preferred embodiments, the methacrylic monomer, acrylic monomer, or acrylate monomer represented by formula (III) includes any one or more combinations of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate, tetrahydrofuran methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl acrylate, lauryl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, etc., but is not limited thereto.

[0066] In some preferred embodiments, the styrene monomers represented by formula (Ⅳ) include any one or a combination of two or more of styrene, 2-bromostyrene, 4-chlorostyrene, etc., but are not limited thereto.

[0067] In some preferred embodiments, the vinyl ether crosslinking agent includes any one or a combination of two or more of diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane divinyl ether, trimethylpropane trivinyl ether, tetravinyl ether, and multifunctional vinyl ether resins, but is not limited thereto.

[0068] In some embodiments, the vinyl ether crosslinking agent has a structure as shown in formula (II):

[0069]

[0070] Where k≥0, l≥1;

[0071] R6 is selected from H and C. 1- C 15 alkylene or C 1- C 15 heteroalkylene, the C 1- C 15 alkylene or C 1- C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 R d replace;

[0072] R7 is selected from H, C1-C 15 alkylene or C1-C15 Heteroalkylene compounds, the C1-C 15 alkylene or C1-C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 R e replace;

[0073] R8 is selected from H, C1-C 15 alkylene or C 1- C 15 Heteroalkylene compounds, the C1-C 15 alkylene or C1-C 15 The heteroalkylene group is optionally surrounded by 1, 2 or 3 R f replace;

[0074] R9 is selected from H, C1-C 15 alkyl, C 1- C 15 heteroalkyl groups or -OC2H3, wherein C1-C 15 Alkyl or C1-C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R g replace;

[0075] R 10 Selected from H, C1-C 15 alkyl, C 1- C 15 heteroalkyl groups or -OC2H3, wherein C1-C 15 Alkyl or C1-C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R h replace;

[0076] The R d R e R f R g R h Selected independently from C 1- C 10 alkyl, C 2- C 10 alkenyl, C 1- C 10 heteroalkyl or C 2- C 10 Heteroalkenes, etc., but not limited to these.

[0077] Furthermore, R6, R7, and R8 are selected from -C2H4-O-C2H4-, -C2H4-O-C2H4-O-C2H4-, And so on, but not limited to these.

[0078] In some preferred embodiments, a method for preparing a reprocessable hemiacetal-based thermosetting resin material includes: placing one or more comonomers containing unsaturated double bonds, at least one polymerization initiator, and at least one multifunctional vinyl ether crosslinking agent into a pot, mixing them thoroughly and uniformly, and performing polymerization and crosslinking reactions at a temperature of 0–160°C to obtain the reprocessable hemiacetal-based thermosetting resin material.

[0079] In some more specific embodiments, the preparation method of the hemiacetal-based thermosetting resin material is an in-situ polymerization dynamic crosslinking technology, specifically including the following steps:

[0080] The comonomer shown in formula (I), the vinyl ether crosslinking agent shown in formula (II), and the polymerization initiator are uniformly mixed to form the uniformly mixed reaction system. After a pre-reaction, the material is cured at high temperature to obtain the hemiacetal-based thermosetting resin material.

[0081] In some preferred embodiments, the total molar ratio of the comonomer to the vinyl ether crosslinking agent is 2 to 100:1, preferably 5 to 20:1, at which point the vinyl ether crosslinking agent reacts most completely and has the highest degree of crosslinking.

[0082] In some preferred embodiments, the polymerization initiator includes any one or a combination of two or more of azo initiators, organic peroxide initiators, inorganic peroxide initiators, and redox initiation systems, but is not limited thereto.

[0083] Furthermore, the azo initiator includes any one or a combination of two or more initiators such as azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate, but is not limited thereto.

[0084] Furthermore, the organic peroxide initiator includes any one or a combination of two or more initiators such as benzoyl peroxide, dodecyl peroxide, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, but is not limited thereto.

[0085] Furthermore, the redox initiation system can be selected from systems such as hydrogen peroxide / Na2SO3, benzoyl peroxide / N,N-dimethylaniline, etc., but is not limited to these.

[0086] In some preferred embodiments, the total molar ratio of the polymerization initiator to the comonomer is 0.00001 to 0.05:1, preferably 0.0001 to 0.01:1.

[0087] In some preferred embodiments, the temperature of the pre-reaction is 0–100°C, preferably 80–90°C.

[0088] Furthermore, the pre-reaction time is 10–30 min, preferably 10–15 min.

[0089] Furthermore, the high-temperature curing treatment is carried out at a temperature of 60–160°C for 2–24 hours.

[0090] Based on the reaction phenomena, the material pre-reaction is most ideal when the pre-reaction temperature is 80-90℃ and the pre-reaction time is 10-30 minutes, and the liquid is in a viscous state with a certain molecular weight.

[0091] In the preparation method of the present invention, the curing process preferably employs a stepped temperature increase curing method for the high-temperature curing treatment. Specifically, the preparation method includes: first curing the homogeneous mixed reaction system at 60–80°C for 4–12 hours, then curing it at 80–120°C for 1.5–2.5 hours, and finally curing it at 120–160°C for 1.5–2.5 hours. Test results show that the sample achieves the most complete curing through the optimized curing procedure.

[0092] Another aspect of the present invention provides a hemiacetal-based thermosetting resin material prepared by the aforementioned method.

[0093] In some embodiments, the hemiacetal-based thermosetting resin material is prepared by in-situ polymerization dynamic crosslinking technology using a comonomer of formula (I) and a vinyl ether crosslinking agent of formula (II); and at least one comonomer has an R5 of -COOH; the linear polymer backbone contained in the obtained hemiacetal-based thermosetting resin material forms a network structure by being connected by hemiacetal bonds -COOC(CH3)O-.

[0094]

[0095] Where k≥0, l≥1; the R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 These are mutually independent and can be the same or different. The terms R1, R2, R3, R4, R5, R6, R7, R8, R9, and R... 10 As defined above in this invention.

[0096] In some preferred embodiments, the hemiacetal-based thermosetting resin material is prepared by in-situ polymerization-dynamic crosslinking technology using a comonomer and a vinyl ether crosslinking agent of formula (II); at least one comonomer is selected from acrylic monomers of formula (III) and styrene monomers of formula (IV), and at least one comonomer has an R 12 For COOH (when L1 is selected from single bonds, then R) 12(For H).

[0097]

[0098] Where k≥0, l≥1; R6, R7, R8, R9, R 10 R 11 R 12 L1 and L2 are independent of each other and can be the same or different. R6, R7, R8, R9, and R... 10 R 11 R 12 L1 and L2 are as defined above in this invention.

[0099] In some embodiments, the hemiacetal-based thermosetting resin material has a structure as shown in formula (A) and / or formula (B):

[0100]

[0101] Where co represents copolymerization; p or q represents the degree of polymerization of the comonomer, with p and q ranging from 1 to 1000; y represents the type of comonomer, with y ranging from 0 to 10, k ≥ 0, and l ≥ 1.

[0102] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 These are mutually independent and can be the same or different. The terms R1, R2, R3, R4, R5, R6, R7, R8, R9, and R... 10 As defined above in this invention.

[0103] In some more preferred embodiments, the hemiacetal-based thermosetting resin material has a structure as shown in any of formulas (1) to (18):

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] Wherein, co represents copolymerization; m and n are the degrees of polymerization of the comonomer, with m and n ranging from 1 to 1000, and z from 1 to 25.

[0110] Another aspect of the present invention provides the application of the aforementioned hemiacetal-based thermosetting resin material in the preparation of continuously processable cross-linked polymer materials.

[0111] Furthermore, another aspect of the present invention provides a method for preparing a continuously processable cross-linked polymer material, comprising:

[0112] Provided the hemiacetal-based thermosetting resin material;

[0113] The hemiacetal-based thermosetting resin material was pulverized and then subjected to twin-screw extrusion at a temperature higher than the glass transition temperature and lower than the decomposition temperature to obtain a cross-linked polymer material.

[0114] Specifically, the present invention also provides a method for reprocessing a reprocessable hemiacetal-based thermosetting resin material, comprising: crushing the hemiacetal-based thermosetting resin material sample obtained above into particles, and performing twin-screw extrusion at a temperature higher than the glass transition temperature and lower than the decomposition temperature, so as to reprocess it into a sample with a complete shape.

[0115] In summary, this invention, by introducing dynamic hemiacetal bonds, endows thermosetting materials with the advantage of being recyclable. Simultaneously, the cross-linked structure improves the material's mechanical, thermal, and solvent resistance properties, and also enables reprocessing. The in-situ polymerization and dynamic cross-linking process of the polymer network in this invention is simple to operate, reduces the process flow, and can be mass-produced using existing chemical equipment, offering advantages such as ease of implementation, green operation, high efficiency, and high yield. Furthermore, this invention achieves the technical effect of reprocessing polymer materials under conditions below decomposition temperature and high pressure during the preparation of polymer materials, demonstrating broad application prospects.

[0116] The technical solution of the present invention will be further explained and described below with reference to several embodiments and accompanying drawings. Those skilled in the art will readily understand that the embodiments are merely illustrative of the invention and should not be considered as specific limitations thereof.

[0117] In the following examples, the infrared spectra of the prepared polymers were measured at room temperature using a micro-infrared spectrometer (model: Cary 660+620) from Agilent Technologies, USA. The absorption mode was used for the measurements.

[0118] Example 1

[0119]

[0120] Take 18.0216g (0.18mol) methyl methacrylate, 1.72g (0.02mol) methacrylic acid, 1.9629g (0.01mol) 1,4-cyclohexanedivinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (1).

[0121] The product was tested and found to have an elongation at break of 5.7%, a tensile strength of 55 MPa, a Young's modulus of 1900 MPa, and an FTIR of 1900 MPa. Figure 1 As shown, this material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0122] Example 2

[0123]

[0124] Take 18.0216g (0.18mol) of methyl methacrylate, 1.72g (0.02mol) of methacrylic acid, 1.582g (0.01mol) of diethylene glycol divinyl ether, and 0.001mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (2).

[0125] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0126] Example 3

[0127]

[0128] Take 18.0216g (0.18mol) of methyl methacrylate, 1.72g (0.02mol) of methacrylic acid, 2.02g (0.01mol) of triethylene glycol divinyl ether, and 0.001mol of azobisisobutyronitrile. Mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours. That is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (3).

[0129] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0130] Example 4

[0131]

[0132] Take 18.75g (0.18mol) styrene, 1.72g (0.02mol) methacrylic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (4).

[0133] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0134] Example 5

[0135]

[0136] Take 18.75g (0.18mol) styrene, 1.72g (0.02mol) methacrylic acid, 1.582g (0.01mol) diethylene glycol divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (5).

[0137] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0138] Example 6

[0139]

[0140] Take 18.75g (0.18mol) styrene, 1.72g (0.02mol) methacrylic acid, 2.02g (0.01mol) triethylene glycol divinyl ether, and 0.001mol azobisisobutyronitrile, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (3).

[0141] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0142] Example 7

[0143]

[0144] Take 20.55g (0.18mol) ethyl methacrylate, 1.4412g (0.02mol) acrylic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (7).

[0145] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0146] Example 8

[0147]

[0148] Take 20.55g (0.18mol) ethyl methacrylate, 1.4412g (0.02mol) acrylic acid, 1.582g (0.01mol) diethylene glycol divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (8).

[0149] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0150] Example 9

[0151]

[0152] Take 20.55g (0.18mol) ethyl methacrylate, 1.4412g (0.02mol) acrylic acid, 2.02g (0.01mol) triethylene glycol divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (9).

[0153] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0154] Example 10

[0155]

[0156] Take 18.75g (0.18mol) styrene, 1.4412g (0.02mol) acrylic acid, 1.582g (0.01mol) diethylene glycol divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (10).

[0157] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0158] Example 11

[0159]

[0160] Take 18.75g (0.18mol) styrene, 1.72g (0.02mol) methacrylic acid, 0.05mol tetravinyl ether, 0.0006mol dodecyl peroxide and 0.0003mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (11).

[0161] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0162] Example 12

[0163] Take 19.0228g (0.19mol) of methyl methacrylate, 0.8609g (0.01mol) of methacrylic acid, 0.98145g (0.005mol) of 1,4-cyclohexanedivinyl ether, and 0.001mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing.

[0164] The material has an elongation at break of 5.6%, a tensile strength of 57 MPa, and a Young's modulus of 1960 MPa. This material can be hot-pressed for 10 minutes at 160°C and 10 MPa using a flat vulcanizing apparatus to recreate the complete network structure, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion processing using a twin-screw extruder at 200°C, with equally excellent performance.

[0165] Example 13

[0166] Take 17.0204g (0.17mol) of methyl methacrylate, 2.5827g (0.03mol) of methacrylic acid, 2.94435g (0.015mol) of 1,4-cyclohexanedivinyl ether, and 0.01mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing.

[0167] The material has an elongation at break of 5.83%, a tensile strength of 53 MPa, and a Young's modulus of 1864 MPa. This material can be hot-pressed for 10 minutes at 160°C and 10 MPa using a flat vulcanizing apparatus to recreate the complete network structure, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0168] Example 14

[0169] Take 16.0192 g (0.16 mol) of methyl methacrylate, 3.4436 g (0.04 mol) of methacrylic acid, 3.9258 g (0.02 mol) of 1,4-cyclohexanedivinyl ether, and 0.000002 mol of benzoyl peroxide, mix and stir evenly, pre-react at 90°C for 15 min, pour the viscous prepolymer into a mold, polymerize at 60°C for 12 hours, post-treat at 80°C for 4 hours, cure at 120°C for 2 hours, and cure at 160°C for 2 hours, that is, the product is obtained by step temperature curing.

[0170] The material has an elongation at break of 5.49%, a tensile strength of 52 MPa, and a Young's modulus of 1773 MPa. This material can be hot-pressed for 10 minutes at 160°C and 10 MPa using a flat vulcanizing apparatus to recreate the complete network structure, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion processing using a twin-screw extruder at 200°C, with equally excellent performance.

[0171] Example 15

[0172] Take 18.0216g (0.18mol) of methyl methacrylate, 1.72g (0.02mol) of methacrylic acid, 1.9629g (0.01mol) of 1,4-cyclohexanedivinyl ether, and 0.0048446g (0.00002mol) of benzoyl peroxide, mix and stir evenly, pre-react at 60℃ for 30min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 1.5 hours, and cure at 160℃ for 2.5 hours, that is, the product is obtained by step temperature curing.

[0173] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0174] Example 16

[0175] Take 18.0216g (0.18mol) of methyl methacrylate, 1.72g (0.02mol) of methacrylic acid, 1.9629g (0.01mol) of 1,4-cyclohexane divinyl ether, and 0.48446g (0.002mol) of benzoyl peroxide, mix and stir evenly, pre-react at 100℃ for 10min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing.

[0176] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0177] Example 17

[0178] The difference between this embodiment and Example 1 is that the ratio of the sum of the moles of methyl methacrylate and methacrylic acid to the moles of 1,4-cyclohexanedivinyl ether is 5:1, while the other conditions are basically the same.

[0179] The performance of the final product was found to be basically consistent with that of Example 1 after testing.

[0180] Example 18

[0181] The difference between this embodiment and Example 1 is that the ratio of the sum of the moles of methyl methacrylate and methacrylic acid to the moles of 1,4-cyclohexanedivinyl ether is 2:1, while the other conditions are basically the same.

[0182] The performance of the final product was found to be basically consistent with that of Example 1 after testing.

[0183] Example 19

[0184] The difference between this embodiment and Example 1 is that the ratio of the sum of the moles of methyl methacrylate and methacrylic acid to the moles of 1,4-cyclohexanedivinyl ether is 100:1, while the other conditions are basically the same.

[0185] The performance of the final product was found to be basically consistent with that of Example 1 after testing.

[0186] Example 20

[0187]

[0188] Take 25.9416g (0.18mol) polyethylene glycol monomethyl ether methacrylate, 1.72g (0.02mol) methacrylic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, i.e., stepwise temperature rise curing to obtain the product. The structural schematic diagram of the product is shown in formula (12).

[0189] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0190] Example 21

[0191]

[0192] Take 90g (0.18mol) polyethylene glycol methyl ether methacrylate (Mn = ~500), 1.72g (0.02mol) methacrylic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (13).

[0193] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0194] Example 22

[0195]

[0196] Take 25.7724g (0.18mol) of dimethylaminoethyl acrylate, 1.72g (0.02mol) of methacrylic acid, 1.9629g (0.01mol) of 1,4-cyclohexanedivinyl ether, and 0.001mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (14).

[0197] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0198] Example 23

[0199]

[0200] Take 34.7472g (0.18mol) of ethyl 2-bromomethacrylate, 1.72g (0.02mol) of methacrylic acid, 1.9629g (0.01mol) of 1,4-cyclohexanedivinyl ether, and 0.001mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (15).

[0201] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0202] Example 24

[0203]

[0204] Take 20.55g (0.18mol) ethyl methacrylate, 3.8048g (0.02mol) 2-methyl-2-(4-vinylphenyl)propionic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (16).

[0205] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0206] Example 25

[0207]

[0208] Take 23.0706g (0.18mol) of ethyl 2-ethyl acrylate, 1.72g (0.02mol) of methacrylic acid, 1.9629g (0.01mol) of 1,4-cyclohexane divinyl ether, and 0.001mol of benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 15min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 8 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (17).

[0209] Example 26

[0210]

[0211] Take 15.49602g (0.18mol) methacrylic acid, 1.9629g (0.01mol) 1,4-cyclohexane divinyl ether, and 0.001mol benzoyl peroxide, mix and stir evenly, pre-react at 85℃ for 12min, pour the viscous prepolymer into a mold, polymerize at 60℃ for 12 hours, post-treat at 80℃ for 4 hours, cure at 120℃ for 2 hours, and cure at 160℃ for 2 hours, that is, the product is obtained by step temperature curing. The structural diagram of the product is shown in formula (18).

[0212] The material can be hot-pressed for 10 minutes at 160°C and 10MPa using a flat vulcanizing apparatus to obtain the complete network structure again, exhibiting excellent performance. Furthermore, the same network structure can be repeatedly obtained after extrusion reprocessing at 200°C using a twin-screw extruder, with equally excellent performance.

[0213] The above is a detailed description of the present invention in conjunction with the embodiments. However, the implementation of the present invention is not limited to the above embodiments. Any changes, substitutions, combinations and simplifications made under the core guiding idea of ​​the present invention are included within the protection scope of the present invention.

[0214] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments. For example, trimethylpropane trivinyl ether and multifunctional vinyl ether resins were used as vinyl ether crosslinking agents, and methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate, tetrahydrofuran methyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl acrylate, lauryl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate were used as comonomers, and relatively ideal results were obtained in all cases.

[0215] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.

Claims

1. A method for preparing a hemiacetal-based thermosetting resin material, characterized in that, include: At least one comonomer as shown in formula (I), at least one vinyl ether crosslinking agent and polymerization initiator are uniformly mixed to form a uniform mixed reaction system. After pre-reaction, the mixture is then cured at high temperature to obtain a hemiacetal-based thermosetting resin material. The terminal group of at least one comonomer is -COOH. The molar ratio of the polymerization initiator to the comonomer is 0.00001 to 0.05:1; the molar ratio of the comonomer to the vinyl ether crosslinking agent is 2 to 100:

1. The pre-reaction temperature is 0~100℃, and the pre-reaction time is 10~30min; the high-temperature curing treatment is carried out by step heating, specifically including: curing the uniformly mixed reaction system first at 60~80℃ for 4~12 h, then at 80~120℃ for 1.5~2.5 h, and finally at 120~160℃ for 1.5~2.5 h; The comonomer has a structure as shown in formula (Ⅰ): ； (Ⅰ)； Among them, R1 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R a replace; R2 is selected from C 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R b replace; R3 is selected from H and C. 1- C 15 alkyl or C 1- C 15 heteroalkyl groups, and the C 1- C 15 alkyl or C 1- C 15 The heteroalkyl group is optionally surrounded by 1, 2 or 3 R c replace; The R a R b R c Selected independently from C 1- C 10 alkyl, C 2- C 10 alkenyl, C 1- C 10 heteroalkyl or C 2- C 10 heteroene group; R4 is selected from or ; Wherein, L1 is selected from -C2H4-, -C3H6-, -C4H8-, -C6H 12 -、-C 12 H 24 - or -C2H4-O-C2H4-, wherein L2 is selected from -CH2-O-C2H4-, -CH2-O-C3H6-, -CH2-O-C4H8-, -CH2-O-C5H 10 -,-CH2-O-C6H 12 -、-CH2-O-C7H 14 -,-CH2-O-C8H 16 -、-CH2-O-C9H 18 -, -CH2-OC 10 H 20 -, -CH2-OC 11 H 22 -, -CH2-OC 12 H 24 -, -CH2-OC 13 H 26 -or-CH2-O-C2H4-O-C2H4-; R5 is selected from H or COOH; The vinyl ether crosslinking agent is selected from any one or a combination of two or more of diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane divinyl ether, trimethylpropane trivinyl ether, tetravinyl ether, and multifunctional vinyl ether resins.

2. The preparation method according to claim 1, characterized in that: The comonomer is an acrylic acid monomer.

3. The preparation method according to claim 2, characterized in that: The comonomer includes methacrylic acid monomers, acrylic acid monomers, or acrylate monomers as shown in formula (III), or styrene monomers as shown in formula (IV), and at least one comonomer has an R 12 It is COOH; ； (Ⅲ) (Ⅳ)； L1 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 Heteroalkylene groups, where L2 is selected from single bonds, C 1- C 15 alkylene or C 1- C 15 heteroalkyl groups; R 11 Selected from H or C 1- C3 alkyl group; R 12 Selected from H or COOH.

4. The preparation method according to claim 3, characterized in that: The methacrylic acid monomer, acrylic acid monomer, or acrylate monomer shown in formula (III) is selected from any one or a combination of two or more of the following: acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate, tetrahydrofuran methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl acrylate, lauryl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate.

5. The preparation method according to claim 3, characterized in that: The styrene monomers represented by formula (Ⅳ) are selected from any one or a combination of two or more of styrene, 2-bromostyrene, and 4-chlorostyrene.

6. The preparation method according to claim 1, characterized in that: The molar ratio of the comonomer to the vinyl ether crosslinking agent is 5~20:

1.

7. The preparation method according to claim 1, characterized in that: The polymerization initiator is selected from any one or a combination of two or more of the following: azo initiators, organic peroxide initiators, inorganic peroxide initiators, and redox initiation systems.

8. The preparation method according to claim 7, characterized in that: The azo initiator is selected from any one or a combination of two or more of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate.

9. The preparation method according to claim 7, characterized in that: The organic peroxide initiator is selected from any one or a combination of two or more of benzoyl peroxide, dodecyl peroxide, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.

10. The preparation method according to claim 1, characterized in that: The molar ratio of the polymerization initiator to the comonomer is 0.0001 to 0.01:

1.

11. The preparation method according to claim 1, characterized in that: The pre-reaction temperature is 80~90℃, and the pre-reaction time is 10~15 min.

12. A hemiacetal-based thermosetting resin material prepared by the preparation method according to any one of claims 1-11; The linear polymer skeleton of the hemiacetal-based thermosetting resin material has a network structure formed by hemiacetal bonds -COOC(CH3)O-. The hemiacetal-based thermosetting resin material has a structure as shown in any of formulas (1) to (18): ； Equation (1); ； Equation (2); ； Equation (3); ； Equation (4); ； Equation (5); ； Equation (6); ； Equation (7); ； Equation (8); ； Equation (9); ； Equation (10); ； Equation (11); ； Equation (12); ； Equation (13); ； Equation (14); ； Equation (15); ； Equation (16); ； Equation (17); ； Equation (18); in, The "co" mentioned above represents copolymerization; m and n are the degrees of polymerization of the comonomer, with values ​​ranging from 1 to 1000, and z from 1 to 25.

13. The hemiacetal-based thermosetting resin material according to claim 12, characterized in that: The hemiacetal-based thermosetting resin material has a Young's modulus of 1700~2000MPa, a tensile strength of 48~62MPa, and an elongation at break of 4%~10%.

14. The use of the hemiacetal-based thermosetting resin material of claim 12 or 13 in the preparation of continuously processable cross-linked polymer materials.

15. A method for preparing a continuously processable cross-linked polymer material, characterized in that, include: Provide a hemiacetal-based thermosetting resin material as described in claim 12 or 13; The hemiacetal-based thermosetting resin material was pulverized and then subjected to twin-screw extrusion at a temperature higher than the glass transition temperature and lower than the decomposition temperature to obtain a cross-linked polymer material.

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