Tyramine / phenolic aldehyde double-bio-based epoxy resin monomer and preparation method thereof

Abstract

The invention provides a tyramine / phenolic aldehyde double-bio-based epoxy resin monomer and a preparation method thereof. Tyramine and phenolic aldehyde which are biological sources are used as raw materials, and TMVE, TMIE and TM42E bio-based bisphenol is prepared through a simple aldol condensation reaction. The corresponding bio-based epoxy resin monomer can be prepared by performing epoxidation reaction on the TMVE, TMIE and TM42E bio-based bisphenol, and the epoxy resin monomer has an alpha and beta unsaturated ketone structure, can also be crosslinked with amine, and is a novel epoxy resin monomer structure. The bio-based epoxy resin material is obtained by crosslinking and curing the bio-based epoxy resin monomer and dipolyamine. The bio-based epoxy resin material is low in toxicity, good in biocompatibility and relatively high in yield.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to an epoxy resin monomer based on bio-based tyramine and bio-based phenolic formaldehyde and a preparation method thereof. Background Art

[0002] Epoxy resin is a typical thermosetting resin with excellent mechanical properties, good thermal stability and easy processing. It is widely used in coatings, adhesives, composite materials and other fields. Since the 1940s, petroleum-based bisphenol A diglycidyl ether (DGEBA) has been the leading product in the epoxy resin industry, with a market share of more than 90%. However, the overuse of fossil fuel reservoirs and the increase in greenhouse gas emissions have caused serious environmental problems. At the same time, factors such as the carcinogenicity, mutagenicity, reproductive toxicity and endocrine disruption of DGEBA are being closely watched. Developing a bio-based epoxy resin monomer and applying the monomer to the epoxy resin industry is the focus of researchers.

[0003] The main biological sources of bio-based epoxy resin monomers currently studied are still based on benzene ring aromatic systems, such as epoxy resin monomers based on structures such as cardanol, resveratrol, vanillin and lignin. In addition, there are also some epoxy monomers based on chain or non-aromatic cyclic biomass structures (such as sorbitol and isosorbide as skeleton structures). At present, epoxy resin monomers based on bio-based sources are gradually being developed, but there are basically no reports on the construction of new epoxy resin monomers based on di-bio-based tyramine and phenolic formaldehyde. Summary of the invention

[0004] In order to make up for the deficiencies of the prior art, the present invention provides a method for preparing a tyramine / phenolic bis-bio-based epoxy resin monomer, the preparation steps of which are as follows:

[0005] S1, according to the prior art scheme, preparing 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid;

[0006] S2, in an alkaline environment, the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid reacts with bio-based phenolic aldehyde under the catalysis of L-proline to produce tyramine / phenolic aldehyde bis-bio-based bisphenol;

[0007] S3, mixing the tyramine / phenolic bis-bio-based bisphenol prepared in S2 with epichlorohydrin, an alkaline solution and a phase transfer catalyst to react and prepare three tyramine / phenolic bis-bio-based epoxy resin monomers;

[0008] The alkaline environment in S2 is a mixture of triethylamine and toluene as a reaction system;

[0009] The volume ratio of triethylamine and toluene in S2 should be 1:(1.5-2);

[0010] The molar ratio of the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid to the bio-based phenolic aldehyde in S2 is 1:(1-2);

[0011] The molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to triethylamine in S2 is 1:(9-10);

[0012] S2 The reaction temperature is 25 to 125°C; the reaction time is 18 to 21 hours;

[0013] S2 The bio-based phenolic aldehyde is vanillin, isovanillin or 4-hydroxy-2-methoxybenzaldehyde;

[0014] S3 The alkaline solution is potassium carbonate solution, sodium carbonate solution, sodium hydroxide solution or potassium hydroxide solution;

[0015] S3 The phase transfer catalyst includes but is not limited to tetrabutylammonium bromide, tetrabutylammonium chloride or tetrabutylammonium iodide;

[0016] The molar ratio of tyramine / phenolic bis-bio-based bisphenol to epichlorohydrin and phase transfer catalyst in S3 is 1:(15-25):(0.15-0.25);

[0017] S3: the molar ratio of epichlorohydrin to potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide in the alkaline solution is 1:1;

[0018] S3 The reaction temperature is 60-80°C; the reaction time is 2-3h; the reaction is carried out under stirring at a rotation speed of 800-2000rpm.

[0019] Based on the above-mentioned preparation method of a tyramine / phenolic bis-bio-based epoxy resin monomer, the present invention provides a tyramine / phenolic bis-bio-based epoxy resin monomer. On the basis of the above-mentioned preparation steps, the bio-based phenolic aldehyde in S2 is vanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; the obtained tyramine / phenolic bis-bio-based epoxy resin monomer is named TMVE;

[0020] Alternatively, the bio-based phenolic aldehyde in S2 is isovanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; and the obtained tyramine / phenolic bis-bio-based epoxy resin monomer is named TMIE;

[0021] Alternatively, the bio-based phenolic formaldehyde described in S2 is 4-hydroxy-2-methoxybenzaldehyde; the alkaline solution described in S3 is sodium hydroxide solution; the phase transfer catalyst described in S3 is tetrabutylammonium bromide; and the obtained tyramine / phenolic formaldehyde dual bio-based epoxy resin monomer is named TM24E.

[0022] The present invention provides a method for preparing a tyramine / phenolic bi-bio-based epoxy resin, the preparation steps of which are as follows:

[0023] S1, according to the prior art scheme, preparing 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid;

[0024] S2, in an alkaline environment, the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid reacts with bio-based phenolic aldehyde under the catalysis of L-proline to produce tyramine / phenolic aldehyde bis-bio-based bisphenol;

[0025] S3, mixing the tyramine / phenolic bis-bio-based bisphenol prepared in S2 with epichlorohydrin, an alkaline solution and a phase transfer catalyst to react and prepare a tyramine / phenolic bis-bio-based epoxy resin monomer;

[0026] S4, in a nitrogen or inert gas environment, mixing the tyramine / phenolic bis-bio-based epoxy resin monomer obtained in S3 with a diamine curing agent, heating the mixture to completely melt it, and performing a temperature treatment and a curing treatment after cooling, and obtaining a tyramine / phenolic bis-bio-based epoxy resin after natural cooling;

[0027] The alkaline environment described in S2 is to mix triethylamine and toluene as a reaction system; the volume ratio of triethylamine and toluene described in S2 should be 1:(1.5-2); the molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to the bio-based phenolic aldehyde described in S2 is 1:(1-2); the molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to triethylamine described in S2 is 1:(9-10); the reaction temperature described in S2 is 25-125°C; the reaction time is 18-21h; the bio-based phenolic aldehyde described in S2 is vanillin, isovillin or 4-hydroxy-2-methoxybenzaldehyde;

[0028] S3 The alkaline solution is potassium carbonate solution, sodium carbonate solution, sodium hydroxide solution or potassium hydroxide solution; S3 The phase transfer catalyst includes but is not limited to tetrabutylammonium bromide, tetrabutylammonium chloride or tetrabutylammonium iodide; S3 The molar ratio of tyramine / phenolic bis-bio-based bisphenol to epichlorohydrin and phase transfer catalyst is 1:(15-25):(0.15-0.25); S3 The molar ratio of epichlorohydrin to potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide in the alkaline solution is 1:1; S3 The reaction temperature is 60-80°C; The reaction time is 2-3h; The reaction is carried out under stirring at a speed of 800-2000rpm;

[0029] S4: the tyramine / phenolic bis-bio-based epoxy resin monomer and the diamine curing agent are added in the following ratio: for every 1 mmol of amine in the added diamine curing agent, 1 mmol of epoxy group in the tyramine / phenolic bis-bio-based epoxy resin monomer is required to be added accordingly;

[0030] The diamine curing agent in S4 is Priamine 1074, and each 1g of diamine Priamine 1074 contains 3.7mmol of amine;

[0031] The curing temperature of S4 is 100-140° C., and the curing time is 6-8 hours.

[0032] Based on the preparation method of a tyramine / phenolic bis-bio-based epoxy resin provided above, the present invention provides a tyramine / phenolic bis-bio-based epoxy resin. On the basis of the above preparation steps, the bio-based phenolic resin in S2 is vanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; the dimeramine curing agent in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine; the obtained tyramine / phenolic bis-bio-based epoxy resin monomer is named TMVE-based epoxy resin;

[0033] Alternatively, the bio-based phenolic aldehyde in S2 is isovanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; the dimeramine curing agent in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine; the obtained tyramine / phenolic bis-bio-based epoxy resin is named TMIE-based epoxy resin;

[0034] Alternatively, the bio-based phenolic formaldehyde described in S2 is 4-hydroxy-2-methoxybenzaldehyde; the alkaline solution described in S3 is sodium hydroxide solution; the phase transfer catalyst described in S3 is tetrabutylammonium bromide; the dimeramine curing agent described in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine; the obtained tyramine / phenolic formaldehyde dual bio-based epoxy resin is named TM42E-based epoxy resin.

[0035] Beneficial Effects

[0036] (1) The present invention uses biologically derived tyramine and phenolic formaldehyde as raw materials to prepare TMVE, TMIE, and TM42E bio-based bisphenols through a simple aldol condensation reaction.

[0037] (2) The present invention can prepare the corresponding bio-based epoxy resin monomer by epoxidation reaction of the TMVE, TMIE, and TM42E bio-based bisphenols. The epoxy resin monomer has an α, β unsaturated ketone structure and can also be cross-linked with amines. It is a new epoxy resin monomer structure.

[0038] (3) The present invention cross-links and solidifies the bio-based epoxy resin monomer with diamine to obtain a bio-based epoxy resin material. The bio-based epoxy resin material has low toxicity, good biocompatibility and high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Embodiments of the present invention are described in detail with reference to the accompanying drawings, in which:

[0040] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of epoxy resin monomer TMVE;

[0041] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of epoxy resin monomer TMIE;

[0042] Figure 3 This is the hydrogen NMR spectrum of epoxy resin monomer TM42E;

[0043] Figure 4 is the carbon NMR spectrum of epoxy resin monomer TMVE;

[0044] Figure 5 is the carbon NMR spectrum of epoxy resin monomer TMIE;

[0045] Figure 6 is the carbon NMR spectrum of epoxy resin monomer TM42E;

[0046] Figure 7 This is the high-resolution mass spectrum of the epoxy resin monomer TMVE;

[0047] Figure 8This is the high-resolution mass spectrum of epoxy resin monomer TMIE;

[0048] Fig. 9 This is the high-resolution mass spectrum of epoxy resin monomer TM42E;

[0049] Fig.10 is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 8;

[0050] Fig.11 is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 9;

[0051] Fig.12 is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 10;

[0052] Fig.13 This is a thermogravimetric graph of the epoxy resin polymer of Example 8;

[0053] Fig.14 This is a thermogravimetric curve of the epoxy resin polymer of Example 9;

[0054] Fig.15 This is a thermogravimetric curve of the epoxy resin polymer of Example 10;

[0055] Fig.16 The structure diagrams of three tyramine / phenolic bi-bio-based epoxy resin monomers provided by the present invention. DETAILED DESCRIPTION

[0056] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0057] 1. Determination of the amine value of amines in the embodiments of the present invention

[0058] Amine value, in English, refers to a chemical property that indicates its functionality. Amine curing agents widely used in the preparation of epoxy resins often use amine value to indicate their functionality. In the preparation of epoxy resins, amine value is the amount of acid required to titrate 1g of alkaline amine, expressed in milligrams of equivalent potassium hydroxide. The amine value of amines in the embodiments of the present invention is provided by the raw material supplier after testing.

[0059] The amine used in the embodiment of the present invention is Priamine 1074

[0060] According to the purchase information (brand name COROA), it is indicated that 3.7 mmol of amine is contained in every 1 g of Priamine 1074. According to the relative molecular mass of diepoxy provided by the present invention, about 3.7 mmol of epoxy groups are contained in every 1.26 g of the tyramine / phenolic bis-bio-based epoxy resin monomer prepared in the example.

[0061] 2. Synthesis technology roadmap

[0062] 2.1 Preparation of tyramine / phenolic bio-based epoxy resin monomers TMVE, TMIE, and TM42E

[0063] The present invention provides three tyramine / phenolic bi-bio-based epoxy resin monomers as shown in the following figure, which are: (E)-3-(3-methoxy-4-(oxiran-2-ylmethoxy)phenyl)-N-(4-(oxiran-2-ylmethoxy)phenethyl)acrylamide (hereinafter referred to as TMVE), (E)-3-(4-methoxy-3-(oxiran-2-ylmethoxy)phenyl)-N-(4-(oxiran-2-ylmethoxy)phenethyl)acrylamide (hereinafter referred to as TMIE), (E)-3-(2-methoxy-4-(oxiran-2-ylmethoxy)phenyl)-N-(4-(oxiran-2-ylmethoxy)phenethyl)acrylamide (hereinafter referred to as TM42E);

[0064]

[0065] The preparation method of TMVE, TMIE and TM42E is as follows:

[0066] S1: According to the prior art, under an inert environment, cycloisopropyl malonate and tyramine react in an alkaline solution to prepare the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid (hereinafter referred to as TMA); the alkaline solution is a mixed solution of alkali and water; wherein the alkali is triethylamine, and the mass ratio of triethylamine to water is 1:(6-8).

[0067] S2: Under alkaline conditions, the compound TMA reacts with three different bio-based phenolic aldehydes under the catalysis of L-proline to produce three tyramine / phenolic bis-bio-based bisphenols;

[0068] S3: In an atmospheric environment, three tyramine / phenolic bis-bio-based bisphenols react with epichlorohydrin, an alkaline solution and a phase transfer catalyst to prepare three tyramine / phenolic bis-bio-based epoxy resin monomers TMVE, TMIE and TM42E;

[0069] The preparation route of the preparation method is:

[0070]

[0071] 2.2 Preparation of TMVE-based, TMIE-based, and TM42E-based tyramine / phenolic bis-bio-based epoxy resins

[0072] The invention provides a preparation method of TMVE-based, TMIE-based and TM42E-based tyramine / phenolic bis-bio-based epoxy resins: three tyramine / phenolic bis-bio-based epoxy resin monomers TMVE, TMIE and TM42E are mixed with a diamine curing agent, heated to completely melt, uniformly injected into a mold, and then continued to heat and cure to obtain the tyramine / phenolic bis-bio-based epoxy resin.

[0073] The diamine curing agent is Priamine 1074.

[0074] According to the calculation based on the amine value, the molar ratio of the epoxy groups in the three tyramine / phenolic bis-bio-based epoxy resin monomers to the amino groups in Priamine 1074 is (0.8-1.2):1.

[0075] The curing temperature is 100 to 140° C. and the curing time is 6 to 8 hours.

[0076] The diamine curing agent is Priamine 1074, and the structural formula is:

[0077]

[0078] The TMVE-based, TMIE-based, TM42E-based tyramine / phenolic bis-bio-based epoxy resin is a binary polymer composed of a, b, c (the tyramine / phenolic bis-bio-based epoxy resin monomers TMVE, TMIE, TM42E) and Priamine 1074 (hereinafter referred to as P):

[0079]

[0080] As shown in formula I, II, and III, the structural schematic diagram of the TMVE-based, TMIE-based, and TM42E-based tyramine / phenolic bis-bio-based epoxy resins is as follows:

[0081] Among them, m≥2, n≥2;

[0082]

[0083] 3. Specific embodiments

[0085] Example 1 Preparation of Compound TMA

[0086] Compound TMA was prepared according to the prior art protocol

[0087] The Schlenk bottle was dehydrated and deoxygenated, and then cycloisopropyl malonate (20 g, 139 mmol, 1 equiv.), triethylamine (19.4 mL, 139 mmol, 1 equiv.) and 150 mL of water were added to the 500 mL Schlenk bottle in sequence, and stirred at room temperature for 30 minutes. Tyramine (19.1 g, 139 mmol, 1.0 equiv.) was added and refluxed for 90 minutes. After the reaction was completed, it was cooled to room temperature, 10% KOH was added to the mixture to adjust the pH>7, 10% HCl was added to the extracted aqueous phase, the pH was adjusted to <7, and the organic phase was extracted. The organic phase was collected and rotary evaporated to obtain white solid TMA.

[0088] 1 H NMR (400MHz, DMSO-d6) δ12.49(s,1H),9.16(s,1H),8.09(s,1H),7.00(d,J=8.4Hz, 2H),6.67(d,J=8.4Hz,2H),3.25–3.18(m,2H),3.11(s,2H),2.59(t,J=7.4Hz,2H).

[0089] Example 2 Preparation of Compound TMV

[0090] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (16.7 mL, 120 mmol, 10 equiv.) and 30 mL of toluene were added to a 250 mL Schlenk bottle in sequence and stirred at 25°C for 30 minutes. Then p-hydroxybenzaldehyde (2.20 g, 18 mmol, 1.5 equiv.) and L-proline (1.10 g, 9.6 mmol, 0.8 equiv.) were added, and the mixture was reacted at 50°C for 12 h, and then refluxed for 6-8 h after 12 h. After the reaction was completed, the mixture was cooled to room temperature, 10% HCl was added to the mixture to adjust the pH to <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TMV was obtained after drying.

[0091] 1 H NMR (400MHz, DMSO-d6) δ9.42(s,1H),9.18(s,1H),7.98(t,J=5.6Hz,1H),7.30(d,J=15.7Hz,1H),7.11(s,1H),6.99(dd,J=14.3,8 .3Hz,3H),6.78(d,J=8.1Hz,1H),6.69(d,J=1.9Hz,2H),6.43(d,J=15.7Hz,1H),3.80(s,3H),3.32(m,2H),2.64(t,J=7.4Hz,2H).

[0092] Example 3 Preparation of Compound TMI

[0093] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (16.7 mL, 120 mmol, 10 equiv.) and 30 mL of toluene were added to a 250 mL Schlenk bottle in sequence and stirred at 25°C for 30 minutes. 3-Hydroxy-4-methoxybenzaldehyde (2.74 g, 18 mmol, 1.5 equiv.) and L-proline (1.10 g, 9.6 mmol, 0.8 equiv.) were then added, and the mixture was reacted at 50°C for 12 h, and then refluxed for 6-8 h. After the reaction was completed, the mixture was cooled to room temperature, 10% HCl was added to the mixture to adjust the pH to <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TMI was obtained after drying.

[0094] 1 H NMR(400MHz, DMSO-d6)δ9.16(s,2H),8.04(t,J=5.6Hz,1H),7.26(d,J=15.7Hz,1H),7.03–6.93(m,5H) ,6.68(d,J=8.4Hz,2H),6.38(d,J=15.7Hz,1H),3.79(s,3H),3.34–3.29(m,2H),2.65(t,J=7.4Hz,2H).

[0095] Example 4 Preparation of Compound TM42

[0096] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (16.7 mL, 120 mmol, 10 equiv.) and 30 mL of toluene were added to a 250 mL Schlenk bottle in sequence and stirred at 25°C for 30 minutes. 4-Hydroxy-2-methoxybenzaldehyde (2.74 g, 18 mmol, 1.5 equiv.) and L-proline (1.10 g, 9.6 mmol, 0.8 equiv.) were then added, and the mixture was reacted at 50°C for 12 h, and then refluxed for 6-8 h. After the reaction was completed, the mixture was cooled to room temperature, 10% HCl was added to the mixture to adjust the pH to <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TM42 was obtained after drying.

[0097] 1H NMR (400MHz, DMSO-d6) δ9.93(s,1H),9.19(s,1H),7.99(t,J=5.4Hz,1H),7.55(d,J=15.8Hz,1H),7.32(d,J=8.4Hz,1H),7 .01(d,J=8.2Hz,2H),6.69(d,J=8.2Hz,2H),6.47–6.38(m,3H),3.79(s,3H),3.32(d,J=6.8Hz,2H),2.64(t,J=7.3Hz,2H).

[0098] Example 5 Preparation of Compound TMVE

[0099] Add compound TMV (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium bromide (0.11 g, 0.34 mmol, 0.085 equiv.) and epichlorohydrin (8.3 mL, 106.4 mmol, 26.6 equiv.) to a 100 mL round-bottom flask. Set the oil bath temperature to 80 ° C and react for 3 hours. After three hours, take out the round-bottom flask, cool to room temperature, add a 30% NaOH aqueous solution in an ice bath, and react for another 1 hour at 25 ° C. After the reaction is completed, extract the organic phase. Collect the organic phase and rotary evaporate to obtain p-hydroxybenzaldehyde diepoxide.

[0100] 1 H NMR(400MHz,Chloroform-d)δ7.54(d,J=15.5Hz,1H),7.14(d,J=8.6Hz,2H),7.02(d,J=12.3Hz,2H), 6.89(d,J=12.9Hz,3H), 6.19(d,J=15.5Hz,1H), 5.57(d,J=5.7Hz,1H), 4.29(dd,J=11.4,3.3Hz,1H), 4.22(dd,J=11.1,3.1Hz,1H),4.04(dd,J=11.4,5.6Hz,1H),3.97–3.92(m,1H),3.89(s,3H),3.62(q, J=6.7Hz,2H),3.41–3.33(m,2H),2.91(d,J=9.0Hz,2H),2.83(t,J=6.8Hz,2H),2.76(d,J=7.2Hz,2H).

[0101] Example 6 Preparation of Compound TMIE

[0102] Add compound TMI (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium bromide (0.11 g, 0.34 mmol, 0.085 equiv.) and epichlorohydrin (8.3 mL, 106.4 mmol, 26.6 equiv.) to a 100 mL round-bottom flask. Set the oil bath temperature to 80 ° C and react for 3 hours. After three hours, take out the round-bottom flask, cool to room temperature, add a 30% NaOH aqueous solution in an ice bath, and react for another 1 hour at 25 ° C. After the reaction is completed, extract the organic phase. Collect the organic phase and rotary evaporate to obtain diepoxy.

[0103] 1 H NMR(400MHz,Chloroform-d)δ7.52(d,J=15.5Hz,1H),7.10(t,J=8.8Hz,4H),6.87(dd,J =8.4,4.2Hz,3H),6.18(d,J=15.5Hz,1H),5.60(s,1H),4.29(dd,J=11.4,3.2Hz,1H),4.2 3–4.19(m,1H),4.01(dd,J=11.4,5.7Hz,1H),3.94(dd,J=11.1,5.7Hz,1H),3.88(s,3H) ,3.61(d,J=6.3Hz,2H),3.39–3.33(m,2H),2.90(s,2H),2.85–2.80(m,2H),2.75(s,2H).

[0104] Example 7 Preparation of Compound TM42E

[0105] Compound TM42 (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium bromide (0.11 g, 0.34 mmol, 0.085 equiv.) and epichlorohydrin (8.3 mL, 106.4 mmol, 26.6 equiv.) were added to a 100 mL round-bottom flask in sequence. The oil bath temperature was set to 80 °C and the reaction was continued for 3 h. After three hours, the round-bottom flask was removed and cooled to room temperature. A 30% aqueous solution of NaOH was added in an ice bath and the reaction was continued for another 1 h at 25 °C. After the reaction was completed, the organic phase was extracted. The organic phase was collected and rotary evaporated to obtain diepoxy.

[0106] 1H NMR (400MHz, Chloroform-d) δ7.76 (d, J = 15.7Hz, 1H), 7.36 (d, J = 8.4Hz, 1H), 7.13 (d, J = 8. 4Hz,2H),6.87(d,J=8.4Hz,2H),6.55–6.43(m,2H),6.37(d,J=15.7Hz,1H),5.65(s,1H),4 .23(ddd,J=22.7,11.0,2.9Hz,2H),3.95(dq,J=8.6,2.8Hz,2H),3.84(s,3H),3.60(q,J=6 .6Hz,2H),3.38–3.29(m,2H),2.99–2.89(m,2H),2.82(t,J=6.8Hz,2H),2.78–2.72(m,2H).

[0107] Example 8 Preparation of TMVE-based epoxy resin

[0108] Under nitrogen atmosphere, add 1.26g TMVE and 1g curing agent Pramine 1074 at 25℃, heat to 135℃ and stir rapidly for 30min to make the materials fully melted and mixed evenly. Remove the nitrogen atmosphere, remove the bubbles in the mixture by vacuum decompression and let it stand; pour the above materials evenly on the metal template, slowly heat to 120℃ and cure for 2h, cool naturally to obtain epoxy resin polymer material. Thermogravimetric data analysis under nitrogen, such as Fig.13 As shown, the initial decomposition temperature is 252°C, the maximum decomposition temperature is 398°C, and the obtained material has good heat resistance. (m is 0.037 mol, n is 0.0037 mol).

[0109] Polymer infrared data attribute: 1072cm -1 Vibration of carbon-oxygen bond in ether bond COC; 1605cm -1 Vibration of carbon-oxygen bond in carbonyl C=O; 3278cm -1 The broad absorption peak at is the NH bond vibration in the amide bond.

[0110] Example 9 Preparation of TMIE-based epoxy resin

[0111] In a nitrogen atmosphere, add 1.26g TMIE and 1g curing agent Pramine 1074 at 25℃, heat to 135℃ and stir rapidly for 30min to ensure that the materials are fully melted and mixed evenly. Remove the nitrogen atmosphere, remove the bubbles in the mixture by vacuum decompression, and let it stand; pour the above materials evenly on the metal template, slowly heat to 120℃ and cure for 2h, and cool naturally to obtain epoxy resin polymer material. Fig.14As shown, the initial decomposition temperature is 272°C, the maximum decomposition temperature is 383°C, and the obtained material has good heat resistance. (m is 0.037 mol, n is 0.0037 mol).

[0112] Polymer infrared data attribute: 1023cm -1 Vibration of carbon-oxygen bond in ether bond COC; 1622 cm -1 Vibration of carbon-oxygen bond in carbonyl C=O; 3282cm -1 The broad absorption peak at is the NH bond vibration in the amide bond.

[0113] Example 10 Preparation of TM24E-based epoxy resin

[0114] In a nitrogen atmosphere, add 1.26g TM42E and 1g curing agent Pramine 1074 at 25℃, heat to 135℃ and stir rapidly for 30min to make sure the materials are fully melted and mixed evenly. Remove the nitrogen atmosphere, remove the bubbles in the mixture by vacuum decompression and let it stand; pour the above materials evenly on the metal template, slowly heat to 120℃ and cure for 2h, and cool naturally to obtain epoxy resin polymer material. Fig.15 As shown, the initial decomposition temperature is 214°C, the maximum decomposition temperature is 343°C, and the obtained material has good heat resistance. (m is 0.037 mol, n is 0.0037 mol).

[0115] Polymer infrared data attribute: 1099cm -1 Vibration of carbon-oxygen bond in ether bond COC; 1604cm -1 Vibration of carbon-oxygen bond in carbonyl C=O; 3269cm -1 The broad absorption peak at is the NH bond vibration in the amide bond.

[0116] Example 11 Preparation of Compound TMA

[0117] To a 500mL Schlenk bottle, add cycloisopropyl malonate (20g, 139mmol, 1equiv.), triethylamine (38.8mL, 278mmol, 2equiv.) and 200mL of water in sequence, and stir at room temperature for 30 minutes. Then add tyramine (19.1g, 139mmol, 1.0equiv.) and reflux for 120 minutes. After the reaction is completed, cool to room temperature, add 10% KOH to the mixture, adjust the pH>7, extract the aqueous phase, add 15% HCl, adjust the pH<7, and extract the organic phase. Collect the organic phase and rotary evaporate to obtain white solid TMA.

[0118] Example 12 Preparation of Compound TMV

[0119] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (16.7 mL, 120 mmol, 10 equiv.) and 50 mL of toluene were added to a 250 mL Schlenk bottle in sequence and stirred at 35°C for 1 hour. Then p-hydroxybenzaldehyde (2.20 g, 18 mmol, 1.5 equiv.) and L-proline (1.38 g, 12 mmol, 1 equiv.) were added, and the mixture was reacted at 70°C for 12 hours, and then refluxed for 8 hours after 12 hours. After the reaction was completed, the mixture was cooled to room temperature, 15% HCl was added to adjust the pH <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TMV was obtained after drying.

[0120] Example 13 Preparation of Compound TMI

[0121] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (20.0 mL, 144 mmol, 12 equiv.) and 50 mL of toluene were added into a 250 mL Schlenk bottle in sequence and stirred at 25°C for 30 minutes. Then 3-hydroxy-4-methoxybenzaldehyde (2.74 g, 18 mmol, 1.5 equiv.) and L-proline (1.38 g, 12 mmol, 1 equiv.) were added, and the mixture was reacted at 70°C for 12 hours, and then refluxed for 8 hours after 12 hours. After the reaction was completed, the mixture was cooled to room temperature, 15% HCl was added to adjust the pH <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TMI was obtained after drying.

[0122] Example 14 Preparation of Compound TM42

[0123] TMA (2.68 g, 12 mmol, 1 equiv.), triethylamine (20.0 mL, 144 mmol, 12 equiv.) and 50 mL of toluene were added to a 250 mL Schlenk bottle in sequence and stirred at 25°C for 30 minutes. Then 4-hydroxy-2-methoxybenzaldehyde (2.74 g, 18 mmol, 1.5 equiv.) and L-proline (1.38 g, 12 mmol, 1 equiv.) were added, and the mixture was reacted at 70°C for 12 hours, and then refluxed for 8 hours after 12 hours. After the reaction was completed, the mixture was cooled to room temperature, 15% HCl was added to adjust the pH to <7, and the organic phase was extracted. The organic solvent was removed by rotary evaporation, and the corresponding compound TM42 was obtained after drying.

[0124] Example 15 Preparation of Compound TMVE

[0125] Add compound TMV (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium chloride (0.11 g, 0.4 mmol, 0.1 equiv.) and epichlorohydrin (8.7 mL, 112 mmol, 28 equiv.) to a 100 mL round-bottom flask. Set the oil bath temperature to 90 ° C and react for 3.5 hours. After four hours, take out the round-bottom flask, cool to room temperature, add a 25% NaOH aqueous solution in an ice bath, and react at 30 ° C for another 1 hour. After the reaction is completed, extract the organic phase. Collect the organic phase and rotary evaporate to obtain p-hydroxybenzaldehyde diepoxide.

[0126] Example 16 Preparation of Compound TMIE

[0127] Add compound TMI (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium chloride (0.11 g, 0.4 mmol, 0.1 equiv.) and epichlorohydrin (8.7 mL, 112 mmol, 28 equiv.) to a 100 mL round-bottom flask. Set the oil bath temperature to 90 ° C and react for 3.5 hours. After four hours, take out the round-bottom flask, cool to room temperature, add a 25% NaOH aqueous solution in an ice bath, and react at 30 ° C for another 1 hour. After the reaction is completed, extract the organic phase. Collect the organic phase and rotary evaporate to obtain diepoxy.

[0128] Example 17 Preparation of Compound TM42E

[0129] Compound TM42 (1.13 g, 4 mmol, 1.0 equiv.), tetrabutylammonium iodide (0.15 g, 0.4 mmol, 0.1 equiv.) and epichlorohydrin (8.7 mL, 112 mmol, 28 equiv.) were added to a 100 mL round-bottom flask in sequence. The oil bath temperature was set to 90 °C and the reaction was continued for 3.5 h. After four hours, the round-bottom flask was removed and cooled to room temperature. A 25% aqueous solution of NaOH was added in an ice bath and the reaction was continued at 30 °C for another 1 h. After the reaction was completed, the organic phase was extracted. The organic phase was collected and rotary evaporated to obtain diepoxy.

[0130] Example 18 Preparation of TMVE-based epoxy resin

[0131] A certain amount of tyramine / phenolic bi-bio-based epoxy resin TMVE was weighed into a reaction bottle. 1.26g TMVE and 1g curing agent Pramine 1074 were added at 25°C under a nitrogen atmosphere. The temperature was raised to 130°C and stirred rapidly for 30 minutes to ensure that the materials were fully melted and mixed evenly. The nitrogen atmosphere was removed, and the bubbles in the mixture were removed by vacuum decompression and then allowed to stand; the above materials were evenly poured on a metal template, and the temperature was slowly raised to 140°C for curing for 2 hours, and then naturally cooled to obtain an epoxy resin polymer material.

[0132] Example 19 Preparation of TMIE-based epoxy resin

[0133] A certain amount of tyramine / phenolic bi-bio-based epoxy resin TMIE was weighed into a reaction bottle, and 1.26g TMIE and 1g curing agent Pramine 1074 were added at 25°C under a nitrogen atmosphere, and the temperature was raised to 130°C while rapidly stirring for 30 minutes to ensure that the materials were fully melted and mixed evenly. The nitrogen atmosphere was removed, and the bubbles in the mixture were removed by vacuum decompression and then allowed to stand; the above materials were evenly poured on a metal template, and the temperature was slowly raised to 140°C for curing for 2 hours, and then naturally cooled to obtain an epoxy resin polymer material.

[0134] Example 20 Preparation of TM24E-based epoxy resin

[0135] A certain amount of tyramine / phenolic bi-bio-based epoxy resin TM42E was weighed into a reaction bottle. 1.26g TM42E and 1g curing agent Pramine 1074 were added at 25°C under a nitrogen atmosphere. The temperature was raised to 130°C and stirred rapidly for 30 minutes to ensure that the materials were fully melted and mixed evenly. The nitrogen atmosphere was removed, and the bubbles in the mixture were removed by vacuum decompression and then allowed to stand; the above materials were evenly poured on a metal template, and the temperature was slowly raised to 140°C for curing for 2 hours, and then naturally cooled to obtain an epoxy resin polymer material.

[0136] The above is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A method for preparing a tyramine / phenolic bis-bio-based epoxy resin monomer, characterized in that: The preparation steps are: S1, according to the prior art scheme, preparing 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid; S2, in an alkaline environment, the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid reacts with bio-based phenolic aldehyde under the catalysis of L-proline to produce tyramine / phenolic aldehyde bis-bio-based bisphenol; S3, mixing the tyramine / phenolic bis-bio-based bisphenol prepared in S2 with epichlorohydrin, an alkaline solution and a phase transfer catalyst, and reacting to prepare a tyramine / phenolic bis-bio-based epoxy resin monomer.

2. The preparation method according to claim 1, characterized in that The alkaline environment in S2 is a mixture of triethylamine and toluene as a reaction system; The volume ratio of triethylamine and toluene in S2 should be 1:(1.5-2); The molar ratio of the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid to the bio-based phenolic aldehyde in S2 is 1:(1-2); The molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to triethylamine in S2 is 1:(9-10); The reaction temperature in S2 is 25 to 125°C; the reaction time is 18 to 21 hours.

3. The preparation method according to claim 1, characterized in that: The bio-based phenolic aldehyde described in S2 is vanillin, isovanillin or 4-hydroxy-2-methoxybenzaldehyde.

4. The preparation method according to claim 1, characterized in that: S3 The alkaline solution is potassium carbonate solution, sodium carbonate solution, sodium hydroxide solution or potassium hydroxide solution; S3 The phase transfer catalyst includes but is not limited to tetrabutylammonium bromide, tetrabutylammonium chloride or tetrabutylammonium iodide.

5. The preparation method according to claim 1, characterized in that: The molar ratio of tyramine / phenolic bis-bio-based bisphenol to epichlorohydrin and phase transfer catalyst in S3 is 1:(15-25):(0.15-0.25); S3: the molar ratio of epichlorohydrin to potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide in the alkaline solution is 1:1; S3 The reaction temperature is 60-80°C; the reaction time is 2-3h; the reaction is carried out under stirring at a rotation speed of 800-2000rpm.

6. A method for preparing a tyramine / phenolic bis-bio-based epoxy resin, characterized in that: The preparation steps are: S1, according to the prior art scheme, preparing 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid; S2, in an alkaline environment, the compound 3-((4-hydroxyphenylethyl)amino)-3-oxopropionic acid reacts with bio-based phenolic aldehyde under the catalysis of L-proline to produce tyramine / phenolic aldehyde bis-bio-based bisphenol; S3, mixing the tyramine / phenolic bis-bio-based bisphenol prepared in S2 with epichlorohydrin, an alkaline solution and a phase transfer catalyst to react and prepare a tyramine / phenolic bis-bio-based epoxy resin monomer; S4, in a nitrogen or inert gas environment, mixing the tyramine / phenolic bis-bio-based epoxy resin monomer obtained in S3 with a diamine curing agent, heating the mixture to completely melt it, and performing a temperature treatment and a curing treatment after cooling, and obtaining a tyramine / phenolic bis-bio-based epoxy resin after natural cooling; The alkaline environment described in S2 is to mix triethylamine and toluene as a reaction system; the volume ratio of triethylamine and toluene described in S2 should be 1:(1.5-2); the molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to the bio-based phenolic aldehyde described in S2 is 1:(1-2); the molar ratio of the compound 3-((4-hydroxyphenethyl)amino)-3-oxopropionic acid to triethylamine described in S2 is 1:(9-10); the reaction temperature described in S2 is 25-125°C; the reaction time is 18-21h; the bio-based phenolic aldehyde described in S2 is vanillin, isovillin or 4-hydroxy-2-methoxybenzaldehyde; S3 The alkaline solution is potassium carbonate solution, sodium carbonate solution, sodium hydroxide solution or potassium hydroxide solution; S3 The phase transfer catalyst includes but is not limited to tetrabutylammonium bromide, tetrabutylammonium chloride or tetrabutylammonium iodide; S3 The molar ratio of tyramine / phenolic bis-bio-based bisphenol to epichlorohydrin and phase transfer catalyst is 1:(15-25):(0.15-0.25); S3 The molar ratio of epichlorohydrin to potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide in the alkaline solution is 1:1; S3 The reaction temperature is 60-80°C; The reaction time is 2-3h; The reaction is carried out under stirring at a rotation speed of 800-2000rpm.

7. The preparation method according to claim 6, characterized in that: S4 The tyramine / phenolic bis-bio-based epoxy resin monomer and the diamine curing agent are added in the following proportions: For every 1 mmol of amine in the added diamine curing agent, 1 mmol of epoxy group in the tyramine / phenolic bis-bio-based epoxy resin monomer is required to be added accordingly.

8. The preparation method according to claim 6, characterized in that: The diamine curing agent in S4 is Priamine 1074, and each 1g of diamine Priamine 1074 contains 3.7mmol of amine; The curing temperature of S4 is 100-140° C., and the curing time is 6-8 hours.

9. A tyramine / phenolic bis-bio-based epoxy resin monomer obtained by the preparation method according to claims 1 to 5, characterized in that: The bio-based phenolic aldehyde described in S2 is vanillin; the alkaline solution described in S3 is sodium hydroxide solution; the phase transfer catalyst described in S3 is tetrabutylammonium bromide; Alternatively, the bio-based phenolic aldehyde in S2 is isovanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; Alternatively, the bio-based phenolic aldehyde described in S2 is 4-hydroxy-2-methoxybenzaldehyde; the alkaline solution described in S3 is sodium hydroxide solution; and the phase transfer catalyst described in S3 is tetrabutylammonium bromide.

10. A tyramine / phenolic bis-bio-based epoxy resin obtained by the preparation method according to claims 6 to 8, characterized in that: The bio-based phenolic aldehyde described in S2 is vanillin; the alkaline solution described in S3 is sodium hydroxide solution; the phase transfer catalyst described in S3 is tetrabutylammonium bromide; the dimeramine curing agent described in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine; Alternatively, the bio-based phenolic aldehyde in S2 is isovanillin; the alkaline solution in S3 is sodium hydroxide solution; the phase transfer catalyst in S3 is tetrabutylammonium bromide; the dimeramine curing agent in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine; Alternatively, the bio-based phenolic formaldehyde described in S2 is 4-hydroxy-2-methoxybenzaldehyde; the alkaline solution described in S3 is sodium hydroxide solution; the phase transfer catalyst described in S3 is tetrabutylammonium bromide; and the dimeramine curing agent described in S4 is Priamine 1074, and each 1g of dimeramine Priamine 1074 contains 3.7mmol of amine.

Images