Low-volatility and low-curing heat release liquid acrylate thermoplastic resin and preparation method thereof

Abstract

A preparation method of the low-volatility and low-curing heat release liquid acrylate thermoplastic resin comprises the following steps: firstly, taking a methacrylate monomer and a high ultraviolet absorption monomer as main raw materials, and performing ultraviolet radiation under heating and stirring conditions to obtain a photo-thermal activated and modified liquid acrylate resin prepolymer; and adding an oxygen polymerization inhibitor and an acrylic monomer, and heating and stirring to obtain the low-volatility and low-curing heat release liquid acrylate thermoplastic resin. According to the invention, the methacrylate monomer and the high ultraviolet absorption monomer are introduced, and ultraviolet light is combined with heating to activate prepolymerization means, so that uniform and controllable polymerization of the resin can be realized in subsequent normal-temperature curing, the manufacturability of the liquid acrylate resin is improved, the volatility and curing heat release of the resin are reduced, and the curing period is effectively shortened; and a new thought can be provided for preparation of high-performance plastic resin.

Description

Technical Field

[0001] The invention belongs to the technical field of functional materials, and in particular relates to a low-volatile, low-curing exothermic liquid acrylic ester thermoplastic resin and a preparation method thereof. Background Art

[0002] Liquid acrylic thermoplastic resins are widely used in resin-based composite materials, coatings, adhesives and other fields due to their excellent mechanical properties, weather resistance, chemical stability, recyclability, processability and weldability. With the rapid development of the above fields, the demand for liquid acrylic resins has increased significantly, showing huge market potential.

[0003] However, the current preparation and molding technology of liquid acrylic resins is still not mature enough, and the shortcomings of the existing resin system, such as high volatility and easy explosion, seriously hinder its further development and application. In view of the above problems, under the premise of ensuring the original excellent performance of liquid acrylic resins, it is a key technical problem that needs to be solved urgently to reduce the volatility and reaction heat of liquid acrylic resins through new technical means, and prepare liquid acrylic thermoplastic resins with low volatility and low curing heat. Summary of the invention

[0004] The main purpose of the present invention is to provide a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin in view of the problems and shortcomings of the prior art, introduce a high ultraviolet absorption monomer to perform ultraviolet light-heat prepolymerization treatment on the resin, and achieve uniform and controllable prepolymerization of the resin, which can significantly reduce the volatility and curing exothermicity of the liquid acrylic resin and greatly improve the processability of the liquid acrylic resin; and the preparation method involved is relatively simple, has low energy consumption, and is suitable for popularization and application.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin comprises the following steps:

[0007] 1) Preparation of photothermal activated modified acrylic resin prepolymer;

[0008] The methacrylate monomer and the high ultraviolet absorption monomer are mixed, stirred evenly at room temperature under an inert atmosphere, and then irradiated with ultraviolet light under heating and stirring conditions to obtain a light-activated modified liquid acrylic resin prepolymer;

[0009] 2) Preparation of low volatility, low curing exothermic liquid acrylic resin;

[0010] Add oxygen inhibitor and acrylic monomer to the obtained light-activated modified liquid acrylic resin prepolymer, stir evenly at room temperature, then heat and stir, and cool to obtain the low-volatile, low-curing exothermic liquid acrylic thermoplastic resin.

[0011] In the above scheme, the methacrylate monomer can be selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, ethyl methacrylate and the like.

[0012] In the above scheme, the high ultraviolet absorption monomer can be selected from one or more of isobornyl methacrylate, butyl methacrylate, phenyl methacrylate and the like.

[0013] In the above scheme, the amount of the high ultraviolet absorption monomer is 5-20wt% of the mass of the methacrylate monomer; preferably 10-15wt%.

[0014] In the above scheme, the inert atmosphere can be nitrogen or the like.

[0015] In the above scheme, the stirring time in step 1) is 10 to 30 minutes.

[0016] In the above scheme, the temperature used for the heating and stirring treatment in step 1) is 50-80° C., and the stirring rate is 100-300 r / min.

[0017] In the above scheme, the wavelength of ultraviolet irradiation in step 1) is 200-390nm, the power is 200-400W, and the time is 2-8h.

[0018] Preferably, the heating temperature in step 1) is 50-65° C.; the wavelength of ultraviolet irradiation is 220-365 nm, the power is 300-400 W, and the time is 2-4 h; and the stirring rate is 200-300 r / min.

[0019] In the above scheme, the oxygen inhibitor can be selected from one or more of pentaerythritol tetrakis(3-mercaptopropionate), p-hydroxyanisole, methylhydroquinone and the like.

[0020] In the above scheme, the amount of the oxygen inhibitor used is 0.1-0.4 wt% of the mass of the light-activated modified liquid acrylic resin prepolymer; preferably 0.3-0.4 wt%.

[0021] In the above scheme, the acrylic monomer can be selected from one or more of acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate and the like.

[0022] In the above scheme, the amount of the acrylic monomer used is 10-30% of the mass of the light-activated modified liquid acrylic resin prepolymer; preferably 20-25wt%.

[0023] In the above scheme, the stirring time at room temperature in step 2) is 10 to 30 minutes.

[0024] In the above scheme, the temperature used for the heating and stirring treatment in step 2) is 40-60° C., the stirring rate is 200-300 r / min, and the time is 0.5-2 h.

[0025] The low-volatile, low-curing exothermic liquid acrylic resin prepared according to the above scheme has a prepolymer volatilization rate as low as 0.149-0.182 g / cm at 60°C. 2 ·h, when thermally initiated at room temperature, the highest exothermic temperature of curing is 76.15~85.75℃, which is lower than the boiling point of the resin monomer and can effectively avoid the occurrence of violent polymerization.

[0026] The present invention also provides a molding method for the above-mentioned low-volatile, low-curing exothermic liquid acrylic ester thermoplastic resin, comprising the following steps: adding a curing agent and an accelerator to the low-volatile, low-curing exothermic liquid acrylic ester thermoplastic resin, stirring at room temperature, vacuum degassing, pouring, and curing at room temperature to obtain an acrylic ester thermoplastic resin molded product.

[0027] Furthermore, the curing agent is an organic peroxide initiator, and specifically one or more of benzoyl peroxide, diisopropylbenzene peroxide, tert-butyl perbenzoate, etc. can be selected.

[0028] Furthermore, the accelerator may be one or more selected from N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, triethanolamine, and the like.

[0029] In the above scheme, the amount of the curing agent is 0.1-0.4wt% of the mass of the liquid acrylic ester thermoplastic resin, preferably 0.2-0.3wt%; the amount of the accelerator is 0.03-0.085wt% of the mass of the liquid acrylic ester thermoplastic resin, preferably 0.043-0.06wt%.

[0030] In the above scheme, the room temperature condition is 25-30°C, and the stirring time is 20-30 minutes.

[0031] In the above scheme, the vacuum degree used in the vacuum degassing is -0.04 to -0.08 MPa, and the maintenance time is 5 to 20 minutes.

[0032] Preferably, the vacuum degree is -0.06 to -0.08 MPa, and the vacuum is maintained for 5 to 10 minutes.

[0033] In the above scheme, the room temperature curing adopts a temperature of 20 to 35° C. and a time of 3 to 5 hours.

[0034] Preferably, the room temperature curing adopts a temperature of 25 to 30° C. and a time of 3 to 4 hours.

[0035] The principle of the present invention is:

[0036] The invention adds highly ultraviolet-absorbing monomers such as isobornyl methacrylate, butyl methacrylate and phenyl methacrylate, utilizes ultraviolet light combined with external temperature to activate the unsaturated bonds to break, generates a large number of active free radicals, converts the monomers into macromolecular oligomers, and realizes uniform and controllable polymerization of the resin in subsequent room-temperature curing, effectively improves the processability of the liquid acrylic resin, reduces the volatility and curing heat release of the resin, and effectively shortens the curing cycle, thereby realizing the efficient preparation of the liquid acrylic resin with low volatility and low curing heat release.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1) The present invention first uses methacrylate monomers and high ultraviolet absorption monomers as main raw materials, and irradiates them with ultraviolet light under heating and stirring conditions to obtain a light- and heat-activated modified liquid acrylic resin prepolymer, which can effectively reduce the volatilization rate and curing exothermic temperature of the obtained resin system, avoid problems such as violent polymerization, and can greatly improve the processability of the liquid acrylic resin, effectively broadening its application field;

[0039] 2) The low-volatile, low-curing exothermic liquid acrylic thermoplastic resin of the present invention can achieve uniform and controllable polymerization of the resin in the subsequent room-temperature curing, and can effectively shorten the curing cycle; and is conducive to improving the toughness of the obtained cured resin product, which can provide a new idea for the preparation of high-performance acrylic thermoplastic resins;

[0040] 3) The preparation method of the present invention is relatively simple, easy to operate, and has mild reaction conditions, and is suitable for popularization and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a comparison chart of the volatilization rates of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin described in Comparative Example 1 at 60° C.;

[0042] Figure 2 The XPS spectra of C1s of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin described in Comparative Example 1;

[0043] Figure 3 The morphology of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin described in Comparative Example 1 after curing;

[0044] Figure 4The curing exothermic curves of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin described in Comparative Example 1 are shown.

[0045] Figure 5 The mechanical properties of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin described in Comparative Example 1. DETAILED DESCRIPTION

[0046] In order to more clearly and thoroughly illustrate the advantages of the present invention, the present invention is further described in detail through the following specific implementation cases and accompanying drawings. The specific embodiments described herein are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. After reading the present invention, the various equivalent forms of modifications to the present invention by those skilled in the art are all within the scope of the claims attached to this application.

[0047] In the following embodiments, the preparation method of the liquid acrylic thermoplastic resin comprises the following steps:

[0048] 1) Preparation of photothermal activated modified acrylic resin prepolymer:

[0049] 100g of methacrylate monomer is added into a three-necked flask, and then 5-20wt% (the percentage of the mass of methacrylate monomer, the same below) of high ultraviolet absorption monomer is added, nitrogen atmosphere is introduced into the flask, and the mixture is stirred for 10-30min at room temperature, and then placed under an ultraviolet lamp (wavelength 200-390nm, power 200-400W), and stirred (100-300r / min) and irradiated for 2-8h under a heating environment of 50-80°C to obtain a light-activated modified liquid acrylic resin prepolymer; the methacrylate monomer is a mixture of one or more monomers selected from methyl methacrylate, hydroxyethyl methacrylate, and ethyl methacrylate; and the high ultraviolet absorption monomer is a mixture of one or more selected from isobornyl methacrylate, butyl methacrylate, and phenyl methacrylate;

[0050] 2) Preparation of low volatility, low curing exothermic liquid acrylic resin:

[0051] 0.1-0.4wt% (the percentage of the prepolymer mass, the same below) of oxygen inhibitor and 10-30wt% (the percentage of the prepolymer mass, the same below) of acrylic monomer are added to the light-activated modified liquid acrylic resin prepolymer prepared in step 1, and the mixture is first stirred at room temperature for 10-30min, and then placed in a 40-60°C water bath and stirred (200-300r / min) for 0.5-2h to fully mix the components, and then cooled to room temperature to obtain a low-volatile, low-curing exothermic liquid acrylic resin; the oxygen inhibitor is one or a mixture of tetrakis(3-mercaptopropionic acid) pentaerythritol ester, p-hydroxyanisole, and methylhydroquinone; and the acrylic monomer is one or a mixture of acrylic acid, methacrylic acid, methyl acrylate, and butyl acrylate.

[0052] The room temperature curing molding step of the liquid acrylic resin comprises:

[0053] Add 0.1-0.4wt% (the percentage of the mass of the acrylic resin, the same below) of benzoyl peroxide (BPO) and 0.03-0.085wt% (the percentage of the mass of the acrylic resin, the same below) of N,N-dimethylaniline to the obtained liquid acrylic resin, stir for 20-30min at 25-30°C, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.04-0.08MPa, maintain for 5-20min to remove bubbles in the resin, then pour it into a mold or compound it with a fiber-reinforced material, place it in an oven at 20-35°C for curing for 3-5h, demould, and obtain a resin casting or a fiber-reinforced acrylic resin composite material.

[0054] Example 1

[0055] A method for preparing a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin comprises:

[0056] 1) Preparation of photothermal activated modified acrylic resin prepolymer:

[0057] 100 g of methyl methacrylate was added into a three-necked flask, and then 10 wt % (percentage of the mass of the methacrylate monomer) of isobornyl methacrylate was added, and a nitrogen atmosphere was introduced into the flask, and the flask was stirred for 20 min at room temperature, and then placed under an ultraviolet lamp (using a wavelength of 295 nm and 365 nm for common use, and a power of 300 W), and irradiated for 4 h at a stirring rate of 200 r / min under a heating environment of 60° C., to obtain a light-activated modified liquid acrylic resin prepolymer;

[0058] 2) Preparation of low volatility, low curing exothermic liquid acrylic resin:

[0059] To the obtained light-activated modified liquid acrylic resin prepolymer, 0.4 wt% of oxygen inhibitor pentaerythritol tetrakis(3-mercaptopropionate) and 25 wt% of acrylic acid were added respectively, and the components were first stirred at room temperature for 30 minutes to fully mix the components, and then placed in a 60°C water bath and stirred for 1 hour. After being allowed to cool to room temperature, a low-volatile, low-curing exothermic liquid acrylic resin was obtained.

[0060] Application Example 1

[0061] To the obtained liquid acrylic resin, add 0.2wt% of benzoyl peroxide and 0.043wt% of N,N-dimethylaniline respectively, and stir it at 25°C for 30 minutes. Place it in a vacuum equipment and evacuate the vacuum gauge pressure to -0.08MPa, maintain it for 10 minutes to remove bubbles in the resin. Then pour it into a mold, place it in a 25°C environment to cure for 4 hours, and demold it to obtain a resin casting.

[0062] Application Example 2

[0063] To the obtained liquid acrylic resin, 0.2wt% of benzoyl peroxide and 0.043wt% of N,N-dimethylaniline were added, and the mixture was stirred at 25°C for 30 minutes. The mixture was placed in a vacuum device and evacuated to a vacuum gauge pressure of -0.08MPa, which was maintained for 10 minutes to remove bubbles in the resin. Subsequently, the resin was placed on the glass fiber in a mass ratio of resin: glass fiber = 1:1 to impregnate the glass fiber, place the resin between two glass plates, and place the mixture in a 25°C environment for curing for 4 hours. The mixture was demolded to obtain a thermoplastic glass fiber prepreg.

[0064] Example 2

[0065] A method for preparing a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin comprises:

[0066] 1) Preparation of photothermal activated modified acrylic resin prepolymer:

[0067] 60g of methyl methacrylate and 40g of hydroxyethyl methacrylate were added to a three-necked flask, and then 10wt% of phenyl methacrylate was added, and a nitrogen atmosphere was introduced into the flask, and the flask was stirred at 30°C for 20min, and then placed under an ultraviolet lamp (using a wavelength of 295nm and 365nm, and a power of 300W), and irradiated at a stirring rate of 200r / min for 4h under a heating environment of 60°C to obtain a light-activated modified liquid acrylic resin prepolymer;

[0068] 2) Preparation of low volatility, low curing exothermic liquid acrylic resin:

[0069] To the obtained light-activated modified liquid acrylic resin prepolymer, 0.4 wt % of an oxygen inhibitor (a mixture of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and p-hydroxyanisole in a mass ratio of 7:3) and 25 wt % of an acrylic monomer (a mixture of acrylic acid and ethyl acrylate in a mass ratio of 8:2) were added respectively, and the mixture was stirred at room temperature for 30 min to allow the components to be fully mixed, and then placed in a 60° C. water bath and stirred for 1 h. After being allowed to cool to room temperature, a low-volatile, low-curing exothermic liquid acrylic resin was obtained.

[0070] Add 0.2wt% of benzoyl peroxide and 0.043wt% of N,N-dimethylaniline to the obtained liquid acrylic resin, stir it at 25°C for 30 minutes, place it in a vacuum equipment, evacuate the vacuum gauge pressure to -0.08MPa, maintain it for 10 minutes to remove bubbles in the resin, then pour it into a mold, place it in a 25°C environment to cure for 4 hours, and demold it to obtain a resin casting.

[0071] Example 3

[0072] A method for preparing a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin comprises:

[0073] 1) Preparation of photothermal activated modified acrylic resin prepolymer:

[0074] 100 g of methyl methacrylate was added into a three-necked flask, and then 10 wt % (based on the mass of the methacrylate monomer) of isobornyl methacrylate was added, a nitrogen atmosphere was introduced into the flask, and the mixture was stirred at room temperature for 20 min, and then placed under an ultraviolet lamp (wavelength 365 nm, power 300 W), and irradiated at a stirring rate of 200 r / min for 5 h at a heating environment of 60° C., to obtain a light-activated modified liquid acrylic resin prepolymer;

[0075] 2) Preparation of low volatility, low curing exothermic liquid acrylic resin:

[0076] To the obtained light-activated modified liquid acrylic resin prepolymer, 0.4 wt% of oxygen inhibitor pentaerythritol tetrakis(3-mercaptopropionate) and 25 wt% of acrylic acid were added respectively, and the components were first stirred at room temperature for 30 minutes to fully mix the components, and then placed in a 60°C water bath and stirred for 1 hour. After being allowed to cool to room temperature, a low-volatile, low-curing exothermic liquid acrylic resin was obtained.

[0077] Add 0.2wt% of benzoyl peroxide and 0.043wt% of N,N-dimethylaniline to the obtained liquid acrylic resin, stir it at 25°C for 30 minutes, place it in a vacuum equipment, evacuate the vacuum gauge pressure to -0.08MPa, maintain it for 10 minutes to remove bubbles in the resin, then pour it into a mold, place it in a 25°C environment to cure for 4 hours, and demold it to obtain a resin casting.

[0078] Comparative Example 1

[0079] A conventional liquid acrylic resin, the preparation method of which is substantially the same as that of Example 1, except that initiators benzoyl peroxide and N,N-dimethylaniline are directly added to the resin monomer mixed solution for curing, and the photothermal activation modification described in step 1) is not performed.

[0080] Comparison of the volatilization rates of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the conventional liquid acrylic resin obtained in Comparative Example 1 at 60°C Figure 1 As shown, the results show that the volatilization rate of the acrylic resin prepolymer treated with photothermal activation is significantly lower than that of the traditional liquid acrylic resin prepolymer, indicating that the resin prepolymer modified by photothermal activation can reduce the volatilization of small molecules in the subsequent curing process, which can not only improve the utilization rate of the monomer, but also effectively avoid the volume shrinkage and introduction of bubbles caused by the volatilization of the monomer during the curing process, and effectively ensure the curing effect.

[0081] The XPS spectra of C1s in the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the product obtained after curing the traditional liquid acrylic resin obtained in Comparative Example 1 are as follows: Figure 2 As shown in the figure, the binding energy of COC and C=O increases from 286eV and 288.9eV to 286.4eV and 289eV with the increase of light activation time, which increases by 0.4eV and 0.1eV respectively, indicating that the electron cloud density around the COC and C=O bonds decreases. Therefore, ultraviolet light can activate the copolymerization of isobornyl methacrylate with the acrylic resin matrix, so that the bulky side groups on isobornyl methacrylate are connected to the polymer main chain, thereby reducing the electron cloud density around the C atom.

[0082] The morphology of the product obtained after curing the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the traditional liquid acrylic resin obtained in Comparative Example 1 is as follows: Figure 3 As shown by Figure 3 It can be seen that the resin without photothermal activation has obvious implosion phenomenon, while the resin treated with photothermal activation does not have implosion phenomenon, which shows that photothermal activation can significantly improve the implosion phenomenon of resin curing.

[0083] The curing exothermic curves of the photothermally activated modified liquid thermoplastic resin prepolymer obtained in Example 1 and the conventional liquid acrylic resin in Comparative Example 1 are shown in FIG. Figure 4 It can be seen that when the resin without photothermal activation is thermally initiated and cured at room temperature, the maximum exothermic temperature is 117.8°C, and the curing process takes 5 to 6 hours to complete; the resin after photothermal activation treatment of the present invention is thermally initiated at room temperature under the action of the same amount of initiator, and the maximum exothermic temperature is 76.15°C, which is 41.65°C lower than that of the resin without photothermal activation. This temperature is lower than the boiling point of the resin monomer, which can effectively alleviate the potential self-acceleration effect that may occur in the polymerization process, greatly reduce the risk of implosion, and significantly shorten the required curing time.

[0084] The mechanical properties test results of the photothermally activated modified liquid thermoplastic resin obtained in Example 1 and the conventional liquid acrylic resin described in Comparative Example 1 are shown in FIG. Figure 5 It can be seen that the mechanical properties of the photothermal activated modified liquid thermoplastic resin have been significantly improved. Compared with the traditional liquid acrylic resin, its tensile strength has increased by 68.85%, the bending strength has increased by 59.97%, and the impact toughness has increased by 34.34%. The photothermal activated modified liquid thermoplastic resin of the present invention is cured more completely, which can reduce or eliminate the influence of the residual stress caused by the excessively high curing exothermic temperature on the mechanical properties during the curing process, thereby meeting the requirements of most application scenarios for the mechanical properties of resin products without the need for post-curing annealing treatment.

[0085] Comparative Example 2

[0086] A liquid acrylic resin, the preparation method of which is substantially the same as that of Example 1, except that 35 wt % of PMMA is first added to the resin monomer mixed solution for dissolution to increase its initial viscosity, and then the same initiators as in Example 1, benzoyl peroxide and N,N-dimethylaniline, are added for curing, without performing the heating-light activation modification described in step 1).

[0087] The volatilization rate of the pre-dissolved polymer resin obtained in Comparative Example 2 is 0.211-0.234 g / cm 2 h, the highest exothermic temperature of curing is 109.92℃, and violent polymerization is easy to occur during the curing process, which pollutes the environment and makes it difficult to control the quality of the product.

[0088] Comparative Example 3

[0089] A liquid acrylic resin, the preparation method of which is substantially the same as that of Example 1, except that in step 1), irradiation is performed under ultraviolet light and stirring conditions, and the simultaneous heating treatment described in step 1) is not performed.

[0090] The maximum curing exothermic temperature of the modified acrylic resin obtained in Comparative Example 3 is 99.72° C., which has a certain degree of risk of sudden polymerization, and the mechanical properties of the resulting resin casting are also lower than those of the photothermally activated modified liquid thermoplastic resin obtained in Example 1.

[0091] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0092] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a low-volatile, low-curing exothermic liquid acrylic thermoplastic resin, characterized in that: The steps include: 1) mixing a methacrylate monomer and a high ultraviolet absorption monomer, stirring them evenly at room temperature under an inert atmosphere, and then irradiating them with ultraviolet light under heating and stirring conditions to obtain a light-activated modified liquid acrylic resin prepolymer; 2) adding an oxygen inhibitor and an acrylic monomer to the obtained light-activated modified liquid acrylic resin prepolymer, stirring evenly at room temperature, then heating and stirring, and cooling to obtain the low-volatile, low-curing exothermic liquid acrylic thermoplastic resin.

2. The preparation method according to claim 1, characterized in that: The methacrylate monomer is one or more of methyl methacrylate, hydroxyethyl methacrylate, and ethyl methacrylate.

3. The preparation method according to claim 1, characterized in that: The high ultraviolet absorption monomer is one or more of isobornyl methacrylate, butyl methacrylate, and phenyl methacrylate.

4. The preparation method according to claim 1, characterized in that: The temperature used in step 1) of the heating and stirring treatment is 50-80°C.

5. The preparation method according to claim 1, characterized in that: Step 1) The ultraviolet irradiation adopts a wavelength of 200-390nm, a power of 200-400W, and a time of 2-8h.

6. The preparation method according to claim 1, characterized in that: The oxygen inhibitor is one or more of pentaerythritol tetrakis(3-mercaptopropionate), p-hydroxyanisole, and methylhydroquinone.

7. The preparation method according to claim 1, characterized in that: The acrylic monomer is one or more of acrylic acid, methacrylic acid, methyl acrylate and butyl acrylate.

8. The preparation method according to claim 1, characterized in that: The temperature of the heating and stirring treatment in step 2) is 40-60° C. and the time is 0.5-2 h.

9. The low-volatile, low-curing exothermic liquid acrylic resin prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The volatilization rate of its prepolymer at 60°C is as low as 0.149-0.182 g / cm 2 ·h, when thermally initiated at room temperature, the maximum exothermic temperature of its curing is 76.15~85.75℃.

10. The molding method of the low-volatile, low-curing exothermic liquid acrylic thermoplastic resin according to claim 9, characterized in that: The method comprises the following steps: adding a curing agent and an accelerator to a low-volatile, low-curing exothermic liquid acrylic ester thermoplastic resin, stirring at room temperature, vacuum degassing, pouring, and curing at room temperature to obtain an acrylic ester thermoplastic resin molded product.

Images