Bio-based MS resin and preparation method thereof

Abstract

The invention belongs to the technical field of polymer synthetic materials, and particularly relates to bio-based MS resin and a preparation method thereof. The bio-based MS resin is a free radical copolymer of a methyl methacrylate monomer and a styrene monomer; the methyl methacrylate monomers comprise bio-based methyl methacrylate, isobornyl methacrylate and 3-pinane methacrylate, and the methyl methacrylate monomers comprise methyl methacrylate, isobornyl methacrylate and 3-pinane methacrylate; the styrene monomers comprise styrene and caffeic acid derivatives; based on 100% of the mass of the bio-based MS resin, the methacrylate monomer accounts for 30%; the molar ratio of caffeic acid derivatives to styrene in the styrene monomers is 1: (1-9). The synthesized bio-based MS resin has the characteristics of greenness and reproducibility, compared with petroleum-based MS resin, the performance of the MS resin can be regulated and controlled by designing a protecting group of a bio-based caffeic acid derivative so as to expand the application range of the MS resin, a specific functional group can be introduced to prepare a functional, advanced and high-performance polymer material, and the MS resin has a good market prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer synthetic materials, and in particular relates to a bio-based MS resin and a preparation method thereof. Background Art

[0002] Methyl methacrylate-styrene copolymer (MS), a traditional thermoplastic material, boasts advantages such as high light transmittance, excellent electrical insulation, easy coloring, and excellent processability. It is widely used in various fields, including construction, packaging, pharmaceuticals, and electronic components. Methyl methacrylate-styrene copolymer (MS) resin is produced through the free radical polymerization of methyl methacrylate and styrene monomers. However, methyl methacrylate monomer is a petroleum-based resource, and styrene monomer is traditionally produced by dehydrogenating petrochemical ethylbenzene. Its production is highly dependent on petroleum resources, which are non-renewable.

[0003] In recent years, extensive research has been conducted on biomass resources. Bio-based polymers, produced from renewable resources, are promising candidates to overcome the negative impacts of petroleum resource shortages. Bio-based polymers refer to novel polymer materials manufactured from renewable biomass raw materials through biological, chemical, and physical methods.

[0004] In summary, how to develop a class of bio-based MS resins to effectively alleviate the shortage of petroleum resources, reduce the environmental burden, and at the same time retain the excellent processing performance and mechanical properties of styrene polymers is a technical problem that needs to be solved urgently. Summary of the Invention

[0005] To address the high dependence of existing MS resins on petroleum resources, effectively alleviate petroleum resource shortages, and reduce environmental impact, the present invention provides a bio-based MS resin and its preparation method. This invention utilizes free radical copolymerization of bio-based methyl methacrylate, isobornyl methacrylate, or 3-pinane methacrylate with bio-based caffeic acid derivative monomers, styrene, and methyl methacrylate to produce a bio-based MS resin that partially replaces petroleum-based styrene and methyl methacrylate. This bio-based MS resin material exhibits a high glass transition temperature, excellent mechanical properties, high toughness while maintaining high strength, and is made from environmentally friendly and sustainable raw materials.

[0006] In the first aspect, the present invention provides a type of bio-based MS resin, which is a free radical copolymer of methyl methacrylate monomers and styrene monomers; the methyl methacrylate monomers include isobornyl methacrylate, 3-pinane methacrylate, and bio-based methyl methacrylate; the styrene monomers include styrene and caffeic acid derivatives; the caffeic acid derivatives are selected from 3,4-dihydroxystyrene derivatives protected by siloxy groups, acetoxy groups, methoxymethyl ether groups, methoxybenzyl groups, and dimethylaminosulfonyl groups, and the functional group substituents on the benzene ring are directly connected to the phenolic hydroxyl group of the caffeic acid derivative, and are located at the para and meta positions of the double bond, and the functional groups are selected from one of the functional groups with structures of (-O-Si(CH3)2-(CH3)3), (-O-CO-CH3), (-O-OC5H9), (-O-C7H6-OCH3) or (-O-SO2-N-(CH3)2).

[0007] Furthermore, the number average molecular weight of the bio-based MS resin is in the range of 10×10 4 -40×10 4 g / mol.

[0008] Furthermore, based on the mass of the bio-based MS resin being 100%, the methacrylate monomer accounts for 20%-40%, and the styrene monomer (petroleum-based / bio-based) accounts for 60%-80%.

[0009] Furthermore, based on the molar number of the methacrylate monomer as 100%, the molar ratio of the bio-based methyl methacrylate to isobornyl methacrylate or 3-pinane methacrylate is not less than 1:2.

[0010] Furthermore, based on the molar number of the styrene monomer as 100%, the molar ratio of the caffeic acid derivative to styrene is 1:1-9.

[0011] Furthermore, the caffeic acid derivative is selected from at least one of 3,4-bis(tert-butyldimethylsilyloxy)styrene, 3,4-bis(acetoxy)styrene, 3,4-bis(methoxymethyl ether)styrene, 3,4-bis(methoxybenzyl)styrene, and 3,4-bis(dimethylaminosulfonyl)styrene, and the molecular formulas are:

[0012]

[0013] In a second aspect, the present invention provides a method for preparing a bio-based MS resin, comprising the following steps:

[0014] S1. Under nitrogen or argon protection, methyl methacrylate monomer, styrene monomer, ethylbenzene solvent and free radical initiator are stirred and dissolved to form a first organic phase solution, and added to a polymerization reactor;

[0015] S2. Heating the first organic phase solution to the initiation temperature of the free radical initiator (70° C.-135° C.) to perform a free radical polymerization reaction, wherein the polymerization reaction is performed for more than 8 hours until the monomer is completely converted to obtain a crude product containing bio-based MS resin;

[0016] S3. The crude product obtained in step S2 is subjected to a post-processing process to obtain the bio-based MS resin material.

[0017] Furthermore, the caffeic acid derivative is preferably selected from one of 3,4-bis(tert-butyldimethylsilyloxy)styrene, 3,4-bis(acetoxy)styrene, 3,4-bis(methoxymethylether)styrene, 3,4-bis(methoxybenzyl)styrene and 3,4-bis(dimethylaminosulfonyl)styrene.

[0018] Furthermore, the amount of ethylbenzene used accounts for 10%-20% of the total mass of the reaction monomers.

[0019] The free radical initiator is selected from peroxide thermal decomposition initiator and azobisnitrile thermal decomposition initiator.

[0020] Furthermore, the organic solvent is at least one selected from non-polar aromatic hydrocarbons, including but not limited to benzene, toluene and ethylbenzene.

[0021] Furthermore, the peroxide thermal decomposition initiator is selected from diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl hydroperoxide, dialkane peroxide, preferably at least one selected from dibenzoyl peroxide, di-o-methylbenzoyl peroxide, acetylisobutyryl peroxide, diisolactone peroxydicarbonate, di-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl perbenzoate, tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, 1,1-di(tert-butylperoxide)cyclohexane, diisopropylbenzene peroxide, and 3,6,9-trimethyl-3,6,9-triethyl-1,4,7-triperoxane.

[0022] Furthermore, the azo thermal decomposition initiator is selected from one or a mixture of azobisisobutyronitrile, dimethyl azobisisobutyrate, azoisobutylcyanamide, and azobisisoheptanenitrile. The initiator for free radical polymerization can be at least one of the above initiators.

[0023] Furthermore, the post-treatment process is as follows: the crude product is first dissolved in an organic solvent, poured into a poor solvent such as ethanol for precipitation, and the precipitate is filtered, washed, and vacuum-dried.

[0024] The beneficial effects of the present invention are:

[0025] The present invention uses biomass-derived methyl methacrylate, isobornyl methacrylate or 3-pinane methacrylate, and caffeic acid derivatives as monomers. These monomers are renewable green resources that are very friendly to reducing petrochemical energy consumption and the ecological environment. They are used to partially replace traditional petroleum-based methyl methacrylate monomers and styrene monomers, respectively, and synthesize a type of bio-based MS resin through a one-pot free radical copolymerization. On the one hand, it breaks through the bottleneck of low strength and low heat deformation temperature of traditional methyl methacrylate-styrene resin. Compared with conventional MS resin, the bio-based copolymer developed by the present invention has a higher T g This bio-based caffeic acid derivative significantly outperforms traditional MS resins in core performance indicators such as strength, toughness, and performance, making it a promising alternative to petroleum-based MS resins with promising implementation value and market prospects. Furthermore, thanks to the catechol functional groups inherent in bio-based caffeic acid derivatives, their properties can be manipulated by designing protective groups, expanding their application range. For example, the introduction of 3,4-bis(acetoxy)styrene significantly improved the strength and glass transition temperature of traditional MS resins, while the introduction of 3,4-bis(tert-butyldimethylsilyloxy)styrene significantly enhanced the toughness and thermal stability of traditional MS resins, even achieving high toughness at a low feed ratio (1:9 ratio of styrene (bio-based / petroleum-based) monomers). This precise screening of protective groups in bio-based caffeic acid derivatives provides a feasible solution for overcoming the bottlenecks of traditional petroleum-based styrene polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 GPC curves of the bio-based MS materials prepared in Examples 3-6;

[0027] Figure 2 DSC curves of the bio-based MS materials prepared in Examples 3-6;

[0028] Figure 3 Thermogravimetric curves of the bio-based MS materials prepared in Examples 3-6;

[0029] Figure 4 : The stress-strain curves of the bio-based MS materials prepared in Examples 3-6;

[0030] Figure 1-4 Wherein a is the copolymer obtained in Example 3, b is the copolymer obtained in Example 4, c is the copolymer obtained in Example 5, and d is the copolymer obtained in Example 6. DETAILED DESCRIPTION

[0031] In order to more clearly understand the above-mentioned objectives, features and advantages of the present invention, the scheme of the present invention will be further described below. It should be noted that, in the absence of conflict, the embodiments of the present invention and the features therein can be combined with each other.

[0032] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein; it is obvious that the embodiments in the specification are only part of the embodiments of the present invention, rather than all the embodiments.

[0033] The preferred embodiments of the present invention will be described in detail below with reference to the examples. It should be understood that the following examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. Those skilled in the art may make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.

[0034] Unless otherwise specified, the experimental methods and calculation methods used in the following examples are conventional methods.

[0035] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0036] In the examples of the present invention, the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymers were analyzed by gel permeation chromatography, the glass transition temperature and thermal stability of the copolymers were analyzed by differential scanning calorimetry and thermogravimetric analysis, and the mechanical properties were measured using a universal tensile tester according to ASTM D412.

[0037] Example 1 (Synthesis of 3,4-bis(tert-butyldimethylsilyloxy)styrene)

[0038] Caffeic acid (25.6 g) was dissolved in DMF (199 mL). Triethylamine (59.0 mL) was added to the solution, and the mixture was then heated to 100°C with stirring. After 1 hour, the reaction mixture was cooled to room temperature, and tert-butyldimethylsilyl chloride (in toluene) was slowly added at 0°C. The reaction mixture was stirred at room temperature. After 24 hours, ice water was added to the mixture to stop the reaction. Extraction was performed with n-hexane, and the organic layer was washed with aqueous HCl, aqueous NaHCO3, and aqueous NaCl. The organic layer was concentrated by rotary evaporation. The residue was purified by silica gel column chromatography and then concentrated to obtain a colorless liquid. The liquid was dried in a vacuum oven to constant weight to obtain purified 3,4-di(tert-butyldimethylsilyloxy)styrene with a yield of 93.04% and a purity of 99.59%.

[0039] Example 2 (Synthesis of 3,4-bis(acetoxy)styrene)

[0040] Caffeic acid (25.0 g) was dissolved in DMF (194 mL). Triethylamine (58.0 mL) was added to the solution, and the mixture was heated to 100°C with stirring. After 1 hour, the reaction mixture was cooled to room temperature, and acetic anhydride (26.4 mL) was slowly added at 0°C. The reaction mixture was stirred at room temperature. After 2 hours, aqueous HCl was added to the mixture to stop the reaction. Extraction was performed with diethyl ether, and the organic layer was washed with aqueous HCl, aqueous NaHCO3, and aqueous NaCl. The organic layer was concentrated by rotary evaporation. The residue was purified by silica gel column chromatography and then concentrated to obtain a colorless viscous liquid. The liquid was dried in a vacuum drying oven to constant weight to obtain purified 3,4-di(acetoxy)styrene with a yield of 74.28% and a purity of 98.96%.

[0041] Example 3 (Synthesis of Isobornyl Methacrylate / Methyl Methacrylate / Styrene / 3,4-Di(tert-Butyldimethylsilyloxy)Styrene Copolymer Resin)

[0042] First, the air in the experimental device was replaced with argon, and the argon atmosphere was maintained during the experiment. The calculated masses of each component (15 parts of isobornyl methacrylate, 15 parts of bio-based methyl methacrylate, 63 parts of styrene, 7 parts of 3,4-di(tert-butyldimethylsilyloxy)styrene, and 20% of the total mass of monomers) were added to a 250 mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was then placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 22.3×10 4 g / mol, the molecular weight distribution is 1.73, the glass transition temperature of the copolymer is 99.4°C, the fastest thermal weight loss temperature is 409.5°C, the tensile strength is 37.2 MPa and the elongation at break is 39.5%.

[0043] Example 4 (Synthesis of Isobornyl Methacrylate / Methyl Methacrylate / Styrene / 3,4-Di(Acetoxy)Styrene Copolymer Resin)

[0044] First, replace the air in the experimental device with argon, and maintain the argon atmosphere during the experiment. The calculated masses of each component (15 parts of isobornyl methacrylate, 15 parts of bio-based methyl methacrylate, 35 parts of styrene, 35 parts of 3,4-di(acetoxy)styrene, and 20% of the total mass of monomers) were added to a 250mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 18.1×10 4 g / mol, the molecular weight distribution is 2.46, the glass transition temperature of the copolymer is 110.7°C, the fastest thermal weight loss temperature is 395.2°C, the tensile strength is 50.7 MPa and the elongation at break is 13.3%.

[0045] Example 5 (Synthesis of 3-pinane methacrylate / methyl methacrylate / styrene / 3,4-bis(tert-butyldimethylsilyloxy)styrene copolymer resin)

[0046] First, the air in the experimental device was replaced with argon, and the argon atmosphere was maintained during the experiment. The calculated masses of the components (15 parts of 3-pinane methacrylate, 15 parts of bio-based methyl methacrylate, 63 parts of styrene, 7 parts of 3,4-di(tert-butyldimethylsilyloxy)styrene, and 20% of the total mass of the monomers) were added to a 250 mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was then placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 24.4×10 4 g / mol, the molecular weight distribution is 1.75, the glass transition temperature of the copolymer is 107.0°C, the fastest thermal weight loss temperature is 416.5°C, the tensile strength is 40.4 MPa and the elongation at break is 15.8%.

[0047] Example 6 (Synthesis of 3-pinane methacrylate / methyl methacrylate / styrene / 3,4-bis(acetoxy)styrene copolymer resin)

[0048] First, replace the air in the experimental apparatus with argon, and maintain the argon atmosphere during the experiment. The calculated masses of each component (15 parts of 3-pinene methacrylate, 15 parts of bio-based methyl methacrylate, 35 parts of styrene, 35 parts of 3,4-di(acetoxy)styrene, and 20% of the total mass of monomers) were added to a 250mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was then placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 10.3×10 4 g / mol, the molecular weight distribution is 2.96, the glass transition temperature of the copolymer is 111.4°C, the fastest thermal weight loss temperature is 397.8°C, the tensile strength is 56.5 MPa and the elongation at break is 6.0%.

[0049] Comparative Example 1 (Synthesis of Isobornyl Methacrylate / Methyl Methacrylate / Styrene Copolymer Resin)

[0050] First, replace the air in the experimental device with argon, and maintain the argon atmosphere during the experiment. The calculated masses of each component (15 parts of isobornyl methacrylate, 15 parts of bio-based methyl methacrylate, 70 parts of styrene, and 20% of the total mass of ethylbenzene) were added to a 250mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was then placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 9.8×10 4 g / mol, the molecular weight distribution is 2.31, the glass transition temperature of the copolymer is 96.7°C, the fastest thermal weight loss temperature is 392.8°C, the tensile strength is 40.6 MPa and the elongation at break is 5.5%.

[0051] Comparative Example 2

[0052] First, replace the air in the experimental device with argon, and maintain the argon atmosphere during the experiment. The calculated masses of each component (15 parts of 3-pinene methacrylate, 15 parts of bio-based methyl methacrylate, 70 parts of styrene and 20% of the total mass of ethylbenzene) were added to a 250mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 9.9×10 4 g / mol, the molecular weight distribution is 2.41, the glass transition temperature of the copolymer is 106.3°C, the fastest thermal weight loss temperature is 394.4°C, the tensile strength is 41.5 MPa and the elongation at break is 3.8%.

[0053] Comparative Example 3 (Synthesis of Methyl Methacrylate / Styrene Copolymer Resin)

[0054] First, replace the air in the experimental device with argon, and maintain the argon atmosphere during the experiment. The calculated masses of each component (30 parts of bio-based methyl methacrylate, 70 parts of styrene, and 20% of the total mass of ethylbenzene) were added to a 250mL three-necked flask in sequence, placed in an oil bath and heated, and reacted at 85°C for 4 hours using mechanical stirring. The temperature was then raised and the reaction was continued at 135°C for 4 hours to allow the polymerization reaction to proceed fully. The polymer obtained by the reaction was dissolved in dichloromethane and precipitated in ethanol. The precipitated polymer was cut into pieces, dissolved again in dichloromethane, and precipitated in ethanol for a total of three precipitations to fully remove the unreacted monomers in the polymer. The polymer was placed in a 50°C vacuum drying oven and dried to remove the ethanol in the polymer. The product structure analysis results are as follows: the number average molecular weight is 8.8×10 4 g / mol, the molecular weight distribution is 2.66, the glass transition temperature of the copolymer is 91.5°C, the fastest thermal weight loss temperature is 372.7°C, the tensile strength is 40.9 MPa and the elongation at break is 2.0%.

[0055] While the above description of specific embodiments of the present invention is provided in conjunction with the accompanying drawings, this description is not intended to limit the scope of the present invention, but rather to facilitate understanding by those skilled in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments described herein, but is intended to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A bio-based MS resin, characterized in that: The bio-based MS resin is a free radical copolymer of methyl methacrylate monomers and styrene monomers; the methyl methacrylate monomers include bio-based methyl methacrylate, isobornyl methacrylate, and 3-pinane methacrylate; the styrene monomers include styrene and caffeic acid derivatives; the caffeic acid derivatives are selected from 3,4-dihydroxystyrene derivatives protected by siloxy groups, acetoxy groups, methoxymethyl ether groups, methoxybenzyl groups, and dimethylaminosulfonyl groups, the functional group substituents on the benzene ring are directly connected to the phenolic hydroxyl group of the caffeic acid derivative, and are located at the para and meta positions of the double bond, and the functional groups are selected from one of the functional groups with structures of (-O-Si(CH3)2-(CH3)3), (-O-CO-CH3), (-O-OC5H9), (-O-C7H6-OCH3) or (-O-SO2-N-(CH3)2); The number average molecular weight of the bio-based MS resin is in the range of 10×10 4 -40×10 4 g / mol.

2. The bio-based MS resin according to claim 1, characterized in that Taking the mass of the bio-based MS resin as 100%, the methacrylate monomer accounts for 20%-40%, and the styrene monomer accounts for 60%-80%.

3. The bio-based MS resin according to claim 1, characterized in that Based on the molar number of the methacrylate monomer as 100%, the molar ratio of the bio-based methyl methacrylate to isobornyl methacrylate or 3-pinane methacrylate is not less than 1:

2.

4. The bio-based MS resin according to claim 1, characterized in that Based on the molar number of the styrene monomer as 100%, the molar ratio of the caffeic acid derivative to styrene is 1:1-9.

5. The bio-based MS resin according to claim 1, characterized in that The caffeic acid derivative is selected from one of 3,4-bis(tert-butyldimethylsilyloxy)styrene, 3,4-bis(acetoxy)styrene, 3,4-bis(methoxymethyl ether)styrene, 3,4-bis(methoxybenzyl)styrene and 3,4-bis(dimethylaminosulfonyl)styrene.

6. A method for preparing a bio-based MS resin according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Under nitrogen or argon protection, methyl methacrylate monomer, styrene monomer, ethylbenzene solvent and free radical initiator are stirred and dissolved to form a first organic phase solution, and added to a polymerization reactor; S2. heating the first organic phase solution to 70° C.-135° C. to carry out a free radical polymerization reaction for a polymerization time of not less than 8 hours to obtain a crude product containing a bio-based MS resin; S3. The crude product obtained in step S2 is subjected to a post-processing process to obtain the bio-based MS resin.

7. The preparation method according to claim 6, characterized in that The caffeic acid derivative is selected from one of 3,4-bis(tert-butyldimethylsilyloxy)styrene, 3,4-bis(acetoxy)styrene, 3,4-bis(methoxymethyl ether)styrene, 3,4-bis(methoxybenzyl)styrene and 3,4-bis(dimethylaminosulfonyl)styrene.

8. The preparation method according to claim 6, characterized in that The amount of ethylbenzene used accounts for 10%-20% of the total mass of the reaction monomers.

9. The preparation method according to claim 6, characterized in that The organic solvent is selected from at least one of benzene, toluene, and ethylbenzene; and the free radical initiator is selected from one of a peroxide thermal decomposition initiator and an azobisnitrile thermal decomposition initiator.

10. The preparation method according to claim 6, characterized in that The post-processing process is as follows: the crude product is first dissolved in an organic solvent, poured into a poor solvent for precipitation, and the precipitate is filtered, washed, and vacuum-dried.

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