Daidzein-based alkene monomers, daidzein-based thermosetting resins, and methods for making the same

Abstract

Soybean genistein base alkene monomer, soybean genistein base thermosetting resin and preparation method thereof belong to the field of biomass polymer material preparation, soybean genistein, bromine propylene and phase transfer catalyst are added into a reaction system, then alkali and solvent are added, after mixing uniformly, reaction is carried out at room temperature, after reaction is completed, soybean genistein base alkene monomer is obtained through filtration and purification. Then, soybean genistein base alkene monomer and thiol curing agent are mixed according to a certain proportion, 4-dimethylaminopyridine is added and mixed uniformly, heating, degassing, pouring into a mold, and after ultraviolet light curing process, soybean genistein base thermosetting resin is obtained. The soybean genistein base thermosetting resin can be obtained by thiol-alkene click chemistry reaction of soybean genistein base alkene monomer and thiol, respectively, and the mechanical properties of the biomass thermosetting resin can be controlled. The soybean genistein base thermosetting resin has very low dielectric constant, and has wide application prospect in the field of electronic packaging materials.

Description

Technical Field

[0001] This invention belongs to the field of biomass polymer material preparation, specifically relating to daidzein-based olefin monomers, daidzein-based thermosetting resins, and their preparation methods. Background Technology

[0002] The rapid development of the electronics industry has led to the widespread application of large-scale integrated circuits and electronic devices in industrial production and daily life, resulting in increasing attention being paid to electronic packaging materials with excellent dielectric properties. While traditional polymeric electronic packaging materials (such as epoxy resin) possess good mechanical properties and ease of processing, their raw materials are primarily derived from fossil resources. The increasing scarcity of petroleum resources, global warming, and environmental pollution limit the further development of traditional electronic packaging materials. Therefore, the development of various bio-based polymeric materials with excellent dielectric properties for electronic packaging is urgently needed.

[0003] Currently, there are some reports on the preparation of bio-based thermosetting resins based on thiol-olefin click chemistry. For example, Guo et al. (Composites Part B: Engineering, 2022, 242:110074) prepared phosphorus-containing bio-based monomers using magnolol as a raw material, and then used thiols containing three and four thiol groups to carry out thiol-olefin click chemistry reactions with magnolol monomers to prepare bio-based thermosetting resins with excellent flame retardant properties, but the mechanical strength and toughness of this resin are significantly insufficient. Zhang et al. (Chemical Engineering Journal, 2022, 439:135740) introduced porous materials into the resin matrix to prepare a novel eugenol-functionalized cage-like polyhedral oligosilane. Benefiting from its good solubility and reactivity with BD-type bismaleimide resin, the composite material exhibits excellent dielectric properties when this substance is added at 4 wt%, with the dielectric constant (k) and dielectric loss (tanδ) decreasing from 3.33 and 0.013 to 2.88 and 0.010 at 1 MHz. However, the dielectric properties of this resin are improved by adding inorganic fillers, and the dielectric properties of general biomass resins still need to be improved.

[0004] Therefore, designing and synthesizing a bio-based organic photocurable material with excellent mechanical and dielectric properties is a completely new challenge. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a daidzein-based olefin monomer, a daidzein-based thermosetting resin and its preparation method. The prepared daidzein-based thermosetting resin has the advantages of adjustable mechanical properties and extremely low dielectric constant.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention proposes a daidzeinyl olefin monomer, the chemical structural formula of which is as follows:

[0008]

[0009] This invention also proposes a method for preparing this daidzein-based olefin monomer, which involves adding daidzein, allyl bromide, and a phase transfer catalyst to a reaction system, then adding an alkali and a solvent, mixing thoroughly, and reacting at room temperature for 2-12 hours. After the reaction is completed, the daidzein-based olefin monomer is obtained by filtration and purification. The molar ratio of daidzein to allyl bromide is 1:2-10.

[0010] As a preferred embodiment of the present invention, in the method for preparing this daidzeinyl olefin monomer:

[0011] The phase transfer catalyst is selected from one or a combination of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, and benzyltrimethylammonium chloride, and the amount of phase transfer catalyst added is 1-5 wt% of the total mass of all raw materials except the solvent. The alkali is selected from potassium carbonate, and the amount added is 1-5 times that of bromopropylene; the solvent is selected from N,N-dimethylformamide.

[0012] This invention also proposes a daidzein-based thermosetting resin, which is prepared by a click chemical reaction of the daidzein-based olefin monomer and a thiol curing agent. Specifically, the daidzein-based olefin monomer and the thiol curing agent are mixed, then 4-dimethylaminopyridine is added and mixed evenly. The mixture is heated, degassed, poured into a mold, and cured under ultraviolet light to obtain the daidzein-based thermosetting resin.

[0013] As a preferred embodiment of the present invention, in the preparation method of this daidzein-based thermosetting resin:

[0014] The thiol curing agent is selected from one or a combination of bis(3-mercaptopropionic acid) ethylene glycol, trihydroxypropane tri(3-mercaptopropionate), pentaerythritol tetra-mercaptopropionate, and 2,3,6,7,10,11-triphenylhexathiol.

[0015] The soybean aglycone olefin monomer and the thiol curing agent are mixed at a molar ratio of double bond units to mercapto units of 1:1.

[0016] The amount of 4-dimethylaminopyridine added is 1-5 wt% of the total mass of all raw materials.

[0017] In the specific preparation process, the mixture is placed in an oven and heated to 180°C for 20 minutes. After heating, the mixture is thoroughly mixed and poured into a mold. Then, it is cured in a UV curing machine at 180 mW / cm². 2 450mW / cm 2 Each power unit was cured for 2 hours.

[0018] Compared with the prior art, the superior effects of the present invention are as follows:

[0019] 1) The daidzein-based thermosetting resin of the present invention is prepared from biomass resources, which meets the policy requirements of green sustainable development and carbon emission reduction.

[0020] 2) The daidzein-based thermosetting resin of the present invention can be obtained by carrying out mercapto-olefin click chemical reactions between daidzein-based olefin monomers and trithiols and tetrathiols, respectively, to obtain a thermosetting resin with adjustable mechanical properties.

[0021] 3) The soybean aglycone-based thermosetting resin of the present invention has an extremely low dielectric constant and has broad application prospects in the field of electronic packaging materials. Attached Figure Description

[0022] Figure 1 The 1H NMR spectrum of the resin monomer DDAB prepared in Example 1 of this invention ( 1 HNMR).

[0023] Figure 2 The carbon NMR spectrum of the resin monomer DDAB prepared in Example 1 of this invention ( 13 CNMR.

[0024] Figure 3 Thermogravimetric analysis (TGA) curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention under a nitrogen atmosphere.

[0025] Figure 4 The derivative thermogravimetric (DTG) curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention under a nitrogen atmosphere.

[0026] Figure 5 Storage modulus-temperature curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention.

[0027] Figure 6 Mechanical loss-temperature curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention.

[0028] Figure 7The heat release rate curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention are shown.

[0029] Figure 8 The stress-strain curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention were obtained by tensile property testing.

[0030] Figure 9 The dielectric constant curves of the thermosetting resins DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7 of this invention were obtained by dielectric property testing. Detailed Implementation

[0031] The following description, in conjunction with embodiments and accompanying drawings, provides a more detailed account of the daidzein-based olefin monomer, daidzein-based thermosetting resin, and their preparation method of the present invention.

[0032] Example 1

[0033] 0.04 mol daidzein, 0.08 mol allyl bromide, 30 g anhydrous potassium carbonate, and 1 wt% tetrabutylammonium bromide (mass percentage indicates its proportion to the total mass of all raw materials excluding solvent, the same below) were dissolved in 400 mL N,N-dimethylformamide. A magnetic rotor was added and the mixture was stirred, and the reaction was carried out at room temperature for 12 h. After the reaction was complete, the mixture was filtered to remove the precipitate, and then the solvent was removed by vacuum distillation. Column chromatography (pure dichloromethane) yielded a white solid as the product, the daidzein-based olefin monomer DDAB (yield: 81%).

[0034] Figure 1 and Figure 2 The DDAB monomers prepared in Example 1 are respectively 1 H NMR and 13 The C NMR spectrum is analyzed in detail below:

[0035] 1 H NMR (400MHz, CDCl3, ppm): δ=4.57 (d, 4H), δ=5.38 (m, 4H), δ=6.60 (m, 2H), δ= 6.82 (s, 1H), δ = 6.97 (t, 3H), δ = 7.46 (d, 2H), δ = 7.88 (s, 1H), δ = 8.18 (d, 1H).

[0036] 13C NMR (100MHz, CDCl3, ppm): δ=69.28 (d, 2C), δ=100.99 (s, C), δ=114.74 (d, C), δ=118.47 (t, 3C), δ=124.37 (s, C), δ=124.78 ( s, C), δ = 127.78 (s, C), δ = 130.06 (s, 2C), δ = 133.19 (d, 2C), δ = 152.12 (sC), δ = 157.82 (d, C) δ = 162.84 (s, C), δ = 175.81 (s, C)

[0037] The structural formula of daidzein used in this invention is:

[0038]

[0039] Combination 1 H NMR and 13 According to the C NMR spectral data, the structural formula of the DDAB monomer prepared in this invention is:

[0040]

[0041] Example 2

[0042] 0.04 mol daidzein, 0.08 mol allyl bromide, 30 g anhydrous potassium carbonate, and 1 wt% tetrabutylammonium chloride were dissolved in 400 mL of N,N-dimethylformamide. The mixture was stirred with a magnetic rotor and reacted at room temperature for 12 h. After the reaction was complete, the mixture was filtered to remove the precipitate, and then the solvent was removed by vacuum distillation. Column chromatography (using pure dichloromethane) yielded a white solid as the daidzein-based olefin monomer DDAB (yield: 79%).

[0043] Example 3

[0044] 0.04 mol daidzein, 0.08 mol allyl bromide, 30 g anhydrous potassium carbonate, and 1 wt% benzyltriethylammonium chloride were dissolved in 400 mL of N,N-dimethylformamide. The mixture was stirred with a magnetic rotor and reacted at room temperature for 12 h. After the reaction was complete, the mixture was filtered to remove the precipitate, and then the solvent was removed by vacuum distillation. Column chromatography (using pure dichloromethane) yielded a white solid as the daidzein-based olefin monomer DDAB (yield: 81%).

[0045] Example 4

[0046] 0.04 mol daidzein, 0.08 mol allyl bromide, 30 g anhydrous potassium carbonate, and 1 wt% hexadecyltrimethylammonium bromide were dissolved in 400 mL of N,N-dimethylformamide. The mixture was stirred with a magnetic rotor and reacted at room temperature for 12 h. After the reaction was complete, the mixture was filtered to remove the precipitate, and then the solvent was removed by vacuum distillation. Column chromatography (using pure dichloromethane) yielded a white solid as the daidzein-based olefin monomer DDAB (yield: 80%).

[0047] Example 5

[0048] 0.004 mol of DDAB monomer, 0.004 mol of bis(3-mercaptopropionic acid) ethylene glycol, and 2 wt% of 4-dimethylaminopyridine (mass percentage indicates its proportion to the total mass of all raw materials, the same below) were placed in a polytetrafluoroethylene container. The container was then placed in an oven and heated to 180°C for 20 minutes. After heating, the mixture was thoroughly mixed and poured into a mold. The mixture was then cured in a UV curing machine at 180 mW / cm². 2 450mW / cm 2 The resin was cured for 2 hours at each power source and then cooled to obtain the product, daidzein-based thermosetting resin DDAB / 2SH.

[0049] Example 6

[0050] 0.003 mol of DDAB monomer, 0.002 mol of trihydroxypropane tris(3-mercaptopropionate), and 2 wt% 4-dimethylaminopyridine were placed in a polytetrafluoroethylene container. The container was then placed in an oven and heated to 180°C for 20 minutes. After heating, the mixture was thoroughly mixed and poured into a mold. The mixture was then cured in a UV curing machine at 180 mW / cm². 2 450mW / cm 2 The resin was cured for 2 hours at each power source and then cooled to obtain the product, daidzein-based thermosetting resin DDAB / 3SH.

[0051] The structural formula of the daidzein-based thermosetting resin DDAB / 3SH is:

[0052]

[0053] Example 7

[0054] 0.004 mol of DDAB monomer, 0.002 mol of pentaerythritol tetra-mercaptopropionate, and 2 wt% 4-dimethylaminopyridine were placed in a polytetrafluoroethylene container. The container was then placed in an oven and heated to 180°C for 20 minutes. After heating, the mixture was thoroughly mixed and poured into a mold. The mixture was then cured in a UV curing machine at 180 mW / cm². 2 450mW / cm 2The resin was cured for 2 hours at each power source and then cooled to obtain the product, daidzein-based thermosetting resin DDAB / 4SH.

[0055] The structural formula of the daidzein-based thermosetting resin DDAB / 4SH is:

[0056]

[0057] Example 8

[0058] 0.003 mol of DDAB monomer, 0.001 mol of 2,3,6,7,10,11-triphenylhexathiol, and 2 wt% 4-dimethylaminopyridine were placed in a polytetrafluoroethylene container. The container was then placed in an oven and heated to 180°C for 20 minutes. After heating, the mixture was thoroughly mixed and poured into a mold. The mixture was then cured in a UV curing machine at 180 mW / cm². 2 450mW / cm 2 The resin was cured for 2 hours at each power source and then cooled to obtain the product, daidzein-based thermosetting resin DDAB / 6SH.

[0059] Thermogravimetric analysis, dynamic thermomechanical analysis, micro combustion calorimetry, tensile property testing, and dielectric property testing were performed on the DDAB / 3SH and DDAB / 4SH prepared in Examples 6 and 7, respectively. Relevant curves and data are shown below. Figures 3 to 9 See Table 1.

[0060] Table 1

[0061]

[0062]

[0063] The test results are as follows:

[0064] from Figure 3 Thermogravimetric curve and Figure 4 The derivative thermogravimetric curve shows that the decomposition temperature (T) of DDAB / 3SH is... -5％ T max The decomposition temperatures (T) of DDAB / 4SH are 343℃ and 387℃, respectively. -5％ T max The temperatures were 347℃ and 390℃, respectively. At 800℃, the carbon residues of DDAB / 3SH and DDAB / 4SH were 16.4% and 22.0%, respectively, indicating that DDAB / 3SH and DDAB / 4SH have good thermal stability and carbonization properties.

[0065] from Figure 5 Storage modulus-temperature curve and Figure 6The mechanical loss-temperature curves show that the storage modulus of DDAB / 3SH at -40℃ is 2118 MPa, and that of DDAB / 4SH at -40℃ is 1853 MPa. The glass transition temperature (T) of DDAB / 3SH... g The glass transition temperature (T) of DDAB / 4SH is 32.9℃. g The temperature was 54.4℃, indicating that DDAB / 3SH has superior thermodynamic properties.

[0066] from Figure 7 The heat release rate curves show that the peak heat release rate (PHRR) of DDAB / 3SH is 356.9 W / g, and the peak heat release rate (PHRR) of DDAB / 4SH is 307.1 W / g, indicating that the soybean aglycone-based thermosetting resin has excellent flame retardant properties.

[0067] from Figure 8 As can be seen from the stress-strain curves, the tensile strength of DDAB / 4SH is significantly higher than that of DDAB / 3SH. However, DDAB / 3SH has an extremely high elongation at break, indicating that the mechanical properties of DDAB / 3SH have also been significantly improved, and it has good application potential in fields such as electronic packaging and circuit protection.

[0068] from Figure 9 The results show that the lowest dielectric constant of DDAB / 3SH is 2.58, and the lowest dielectric constant of DDAB / 4SH is 2.70, indicating that soybean aglycone-based thermosetting resins have excellent dielectric properties and have great application potential in the field of electronic packaging.

[0069] The above results fully demonstrate that the daidzein-based thermosetting resin prepared by this invention has excellent mechanical properties, flame retardant properties and dielectric properties, and has broad application prospects in high-tech fields such as electronic packaging and circuit protection.

[0070] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A daidzein-based thermosetting resin, characterized in that, It is prepared by click chemistry reaction of soybean aglycone olefin monomer and thiol curing agent; The chemical structural formula of the daidzeinyl olefin monomer is as follows: The thiol curing agent is selected from one or a combination of bis(3-mercaptopropionic acid) ethylene glycol, trihydroxypropane tri(3-mercaptopropionate), pentaerythritol tetra-mercaptopropionate, and 2,3,6,7,10,11-triphenylhexathiol.

2. A method for preparing the daidzein-based thermosetting resin as described in claim 1, characterized in that, The daidzein-based olefin monomer and thiol curing agent are mixed, and then 4-dimethylaminopyridine is added and mixed evenly. The mixture is heated, degassed, poured into a mold, and cured by ultraviolet light to obtain daidzein-based thermosetting resin.

3. The method as described in claim 2, characterized in that, The soybean aglycone olefin monomer and the thiol curing agent are mixed at a molar ratio of double bond units to mercapto units of 1:

1.

4. The method as described in claim 2, characterized in that, The amount of 4-dimethylaminopyridine added is 1-5 wt% of the total mass of all raw materials.

5. The method as described in claim 2, characterized in that, Place the mixture in an oven and heat to 180°C for 20 minutes. After heating, mix the mixture thoroughly and pour it into a mold. Then, cure the mixture in a UV curing machine at 180 mW / cm². 2 450 mW / cm 2 Each power unit was cured for 2 hours.

6. The method according to any one of claims 2-5, characterized in that, The preparation method of the daidzein-based olefin monomer is as follows: daidzein, allyl bromide, and phase transfer catalyst are added to the reaction system, followed by the addition of alkali and solvent. After mixing evenly, the mixture is reacted at room temperature for 2-12 h. After the reaction is completed, the daidzein-based olefin monomer is obtained by filtration and purification. The molar ratio of daidzein to allyl bromide is 1:2-10.

7. The method as described in claim 6, characterized in that, The phase transfer catalyst is selected from one or a combination of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide and benzyltrimethylammonium chloride, and the amount of phase transfer catalyst added is 1-5 wt% of the total mass of all raw materials except solvent.

8. The method as described in claim 6, characterized in that, The alkali is selected from potassium carbonate, and the amount added is 1-5 times that of bromopropylene; the solvent is selected from N,N-dimethylformamide.

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