A magnolol / glycosyl furan bibi-based epoxy resin monomer and its preparation method and application

Abstract

The present invention discloses a magnolol / glycosyl furan bis-bio-based epoxy resin monomer and a preparation method and application thereof, wherein the magnolol / glycosyl furan bis-bio-based epoxy resin monomer is shown in Formula MF. The novel structural polymer material in the present invention has a high glass transition temperature and a wide applicable temperature range; its high storage modulus (>3GPa) shows that the polymer material has high rigidity properties, which is a great advantage over traditional petroleum-based epoxy resin materials; its average heat release rate value is low, indicating that the resin has good flame retardant properties, less combustion heat release, and can reduce the risk of fire.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and specifically relates to a magnolol / glycosyl furan bibi-based epoxy resin monomer and a preparation method and application thereof. Background Art

[0002] Epoxy resin (EP) has excellent electrical insulation properties, wear resistance, chemical stability, and the material is easy to produce and process. It is widely used in electrical and electronic insulation materials, aerospace and other fields; however, traditional epoxy resins are generally easy to burn. Although some materials have good mechanical properties, their thermal properties and flame retardant properties are not ideal, which greatly limits their application. Therefore, the existing technology usually enhances the flame retardant properties of epoxy resins through molecular modification and additive compounding, improves the current shortcomings of epoxy resins, and reduces safety risks. In this way, thermosetting flame retardant resins are gradually coming into people's field of vision and attracting the attention of scholars.

[0003] Thermosetting resin is a resin that can form a highly cross-linked network polymer after polymerization. It is widely used in the field of engineering technology research due to its excellent mechanical properties, thermal properties and corrosion resistance. In the context of the decreasing petrochemical resources, the search for renewable and recyclable biomass epoxy resin has become a current research hotspot.

[0004] Biomass such as lignin and natural phenolic compounds are rich in unsaturated double bonds or hydroxyl groups with good reaction activity, and can be obtained through epoxidation reaction to obtain epoxy compounds. As renewable resources, lignin and natural phenolic compounds are rich in raw material sources, low in cost, and have the advantages of being degradable, renewable, and environmentally friendly. The continuous emergence and research of biomass epoxy resins have enriched the use options of epoxy resins, reduced dependence on petroleum products, and reduced harm to the environment.

[0005] Magnolol is a renewable biomass raw material extracted from the bark of Magnolia officinalis. It belongs to a biphenol compound with high rigidity. This type of structure can improve the heat resistance of epoxy resin materials and reduce the free volume to achieve the purpose of improving toughness. In this paper, we used magnolol as a raw material to synthesize a new type of epoxy resin. The synthesis steps are simple, the reaction conditions are mild, and the raw materials are widely available and easy to obtain. The polymer material polymerized from the epoxy resin monomer has good thermal properties and a higher decomposition temperature, which has many advantages over the traditional bisphenol A epoxy resin. Summary of the invention

[0006] Purpose of the invention: The technical problem to be solved by the present invention is to provide a magnolol / glycosyl furan bibio-based epoxy resin monomer in view of the deficiencies in the prior art.

[0007] The technical problem that the present invention needs to solve is to provide a method for preparing the above-mentioned magnolol / glycosyl furan bibio-based epoxy resin monomer.

[0008] The technical problem that the present invention needs to solve is to provide a magnolol / glycosyl furan bibio-based epoxy resin.

[0009] The technical problem that the present invention needs to solve is to provide a method for preparing the above-mentioned magnolol / glycosyl furan bibio-based epoxy resin.

[0010] The technical problem that the present invention needs to solve is to provide the application of the above-mentioned magnolol / glycosyl furan bibio-based epoxy resin.

[0011] In order to solve the above-mentioned first technical problem, the present invention discloses a magnolol / glycosyl furan bis bio-based epoxy resin monomer MF;

[0012]

[0013] In order to solve the second technical problem, the present invention discloses a method for preparing the magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF, such as Figure 1 As shown, the following steps are included:

[0014] (1) Etherification reaction: In an alkaline solution, under the action of a catalyst, magnolol and 5-chloromethylfurfural are stirred in an air atmosphere to carry out a first reaction to obtain compound c;

[0015] (2) Reduction reaction: In a protic solvent, the obtained compound c undergoes a second reaction with a reducing agent to obtain compound d;

[0016] (3) Epoxidation reaction: Under an inert environment, the obtained compound d, epichlorohydrin, an alkaline solution and a phase transfer catalyst are subjected to a third reaction to obtain magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF;

[0017]

[0018] In step (1), the alkaline solution is a mixed solution of an alkali and an organic solvent in a mass ratio of 1:2 to 20; wherein the alkali includes but is not limited to any one or a combination of sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate and sodium carbonate; and the organic solvent includes but is not limited to any one or a combination of dichloromethane, ethyl acetate, acetonitrile, acetone, tetrahydrofuran and dioxane.

[0019] In step (1), the 5-chloromethylfurfural can be prepared according to the prior art, or according to the following method: 5-hydroxymethylfurfural is mixed and dissolved with a solvent, concentrated hydrochloric acid is added, and the mixture is reacted for 12 hours at 25° C. under stirring conditions to obtain 5-chloromethylfurfural; wherein the solvent is any one or a combination of dichloromethane, ethyl acetate, acetonitrile, acetone, tetrahydrofuran and dioxane; the mass volume ratio of 5-hydroxymethylfurfural to solvent is 1 g: 4 to 10 mL; the concentration of the concentrated hydrochloric acid is 12 mol / L; the molar ratio of hydrochloric acid to 5-hydroxymethylfurfural is 1.5 to 3: 1; and the reaction is carried out under stirring at a rotation speed of 800 to 2000 rpm.

[0020] In step (1), the molar ratio of magnolol to 5-chloromethylfurfural is 1:2.05-3.

[0021] In step (1), the catalyst includes but is not limited to sodium iodide; the amount of the catalyst used is 5% to 15% of the molar amount of magnolol.

[0022] In step (1), the reaction temperature is 60 to 100° C., preferably 80° C.; the reaction time is 8 to 16 hours.

[0023] In step (1), after the reaction is completed, the reaction solution is diluted with an appropriate amount of water to completely dissolve the salt generated by the reaction, and then extracted with an organic solvent, dried over anhydrous sodium sulfate, filtered, and the filtrate is decompressed to remove the solvent. After column separation and purification, a light yellow viscous liquid is obtained, which is compound c.

[0024] In step (2), the protic solvent is any one or a combination of methanol, ethanol and water.

[0025] In step (2), the concentration of compound c is 0.05 to 0.15 g / mL.

[0026] In step (2), the reducing agent is any one of sodium borohydride, lithium aluminum hydride, aluminum triisopropoxide and hydrogen; and the molar ratio of compound c to the reducing agent is 1:0.5-2.5.

[0027] In step (2), the reaction temperature is -5 to 5°C, preferably 0°C; and the reaction time is 12 to 18 hours.

[0028] In step (2), after the reaction is completed, an appropriate amount of distilled water is added to quench the reaction, and the magnolol disubstituted furan hydroxy compound is purified to obtain compound d.

[0029] In step (3), the inert environment is preferably nitrogen protection, and the nitrogen inlet flow rate is 50 to 200 mL / min.

[0030] In step (3), the phase transfer catalyst includes but is not limited to one of tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium chloride or a mixture of several of them.

[0031] In step (3), compound d is dissolved in an organic solvent and then added to epichlorohydrin, an alkaline solution and a phase transfer catalyst; wherein the organic solvent includes but is not limited to any one or a combination of dichloromethane, ethyl acetate, acetonitrile, acetone, tetrahydrofuran and dioxane; and the alkaline solution is any one or a combination of potassium carbonate solution, sodium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.

[0032] In step (3), the molar ratio of the compound d to epichlorohydrin, the base in the alkaline solution and the phase transfer catalyst is 1:15-25:15-25:0.15-0.3.

[0033] In step (3), the reaction is carried out under stirring at a rotation speed of 800 to 2000 rpm.

[0034] In step (3), the reaction temperature is 40 to 60° C., preferably 50° C.; and the reaction time is 2 to 8 hours.

[0035] In step (3), after the reaction is completed, the reaction solution is extracted after dilution with water, dried, filtered, and the filtrate is decompressed to remove the solvent, and the magnolol / glycosyl furan bibio-based epoxy resin monomer MF is purified.

[0036] Wherein, the desiccant used in the post-treatment of each synthesis step in the above process is anhydrous sodium sulfate.

[0037] In order to solve the third technical problem mentioned above, the present invention discloses a magnolol / glycosyl furan bibi-based epoxy resin, which is a binary polymer composed of A and B, or a binary polymer composed of A and C;

[0038] Among them, the structural units of A, B, and C are:

[0039]

[0040] Wherein, the binary polymer composed of A and B has a repeating structural unit shown in formula I, and the binary polymer composed of A and C has a repeating structural unit shown in formula II;

[0041]

[0042] Among them, m≥2, n≥2; m=2n.

[0043] The initial decomposition temperature of the magnolol / glycosyl furan bis-bio-based epoxy resin in a nitrogen atmosphere is 310-370° C., preferably 314-363° C. The maximum decomposition temperature of the magnolol / glycosyl furan bis-bio-based epoxy resin in a nitrogen atmosphere is 420-490° C., preferably 420-480° C., preferably 420-470° C., preferably 420-460° C., preferably 425-457° C.

[0044] The initial decomposition temperature of the magnolol / glycosyl furan bis bio-based epoxy resin in air atmosphere is 280-330°C, preferably 290-320°C, and preferably 293-316°C.

[0045] The maximum decomposition temperature of the magnolol / glycosyl furan bis bio-based epoxy resin in air atmosphere is 480-670°C, preferably 480-650°C, preferably 490-650°C, preferably 490-645°C, preferably 500-643°C.

[0046] The residual carbon content of the magnolol / glycosyl furan bis bio-based epoxy resin at 750° C. in an air atmosphere is 1% to 11%, preferably 2% to 10%, and preferably 2.5% to 9.5%. The storage modulus of the magnolol / glycosyl furan bis bio-based epoxy resin is 3 to 9 GPa, preferably 3 to 6 GPa, preferably 3.5 to 5.5 GPa, and preferably 3.96 to 5.04 GPa.

[0047] Wherein, the phase transition temperature of the magnolol / glycosyl furan bis bio-based epoxy resin is 200-250°C, preferably 200-240°C, preferably 200-230°C, preferably 200-225°C, and preferably 202-223°C.

[0048] The average heat release rate of the magnolol / glycosyl furan bis-bio-based epoxy resin is 50 to 100 W / g, preferably 55 to 95 W / g, preferably 60 to 95 W / g, and preferably 64 to 93 W / g.

[0049] In order to solve the fourth technical problem mentioned above, the present invention discloses a method for preparing the above-mentioned magnolol / glycosyl furan bis-bio-based epoxy resin, comprising mixing magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF and aromatic sulfone diamine curing agent, stirring and heating to completely melt, uniformly injection molding, and continuing to heat and cure under the protection of inert gas to obtain magnolol / glycosyl furan bis-bio-based epoxy resin.

[0050] The aromatic sulfone diamine curing agent includes but is not limited to 4,4'-diaminodiphenyl sulfone (44DDS) and / or 3,3'-diaminodiphenyl sulfone (33DDS).

[0051]

[0052] The molar ratio of the epoxy group in the magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF to the amino group in the aromatic sulfone diamine curing agent is 0.8 to 1.5:1, preferably 0.8 to 1.2:1.

[0053] Wherein, the melting temperature is 120-180°C; the solidification temperature is 200-230°C; and the solidification time is 2-5h.

[0054] In order to solve the fifth technical problem mentioned above, the present invention discloses the use of the above-mentioned magnolol / glycosyl furan bibio-based epoxy resin as or in the preparation of a heat-resistant material, which has a higher Tg value, indicating that it can work at a very high temperature.

[0055] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0056] (1) The present invention provides a structure of a novel bi-biobased epoxy resin monomer of magnolol / glycosylfuran and a method for preparing the same. The preparation process is highly green and is a novel bi-biobased composite epoxy monomer material.

[0057] (2) The magnolol and glycosyl 5-hydroxymethylfurfural in the present invention can be obtained by bio-preparation by converting or separating magnolia officinalis and biomass such as corn, wheat or straw, so the biological added value of the monomers is very high.

[0058] (2) The present invention constructs a polymer material of a new structure based on a synthesized new monomer structure. The polymer material is synthesized from bio-based raw materials and has not only excellent thermal stability but also good biosafety.

[0059] (4) The new structural polymer material in the present invention has a higher glass transition temperature and can be used in a wide temperature range; its high storage modulus (>3GPa) shows that the polymer material has high stiffness properties, which is a great advantage over traditional petroleum-based epoxy resin materials; its average heat release rate value is low, indicating that the resin has good flame retardant properties, releases less combustion heat, and can reduce the risk of fire. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0061] Figure 1 This is the reaction path of the present invention.

[0062] Figure 2This is the hydrogen nuclear magnetic resonance spectrum of epoxy resin monomer MF.

[0063] Figure 3 This is the carbon NMR spectrum of epoxy resin monomer MF.

[0064] Figure 4 This is the high-resolution mass spectrum of epoxy resin monomer MF.

[0065] Figure 5 This is the Fourier infrared spectrum of epoxy resin monomer MF.

[0066] Figure 6 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 5.

[0067] Figure 7 This is the Fourier transform infrared spectrum of the epoxy resin polymer in Example 6.

[0068] Figure 8 This is the TGA diagram of epoxy resin monomer MF.

[0069] Fig. 9 This is the TGA diagram of epoxy resin monomer Meng-guan HF.

[0070] Fig.10 This is the TGA chart of the epoxy resin polymer in Example 5 under nitrogen.

[0071] Fig.11 This is the TGA chart of the epoxy resin polymer in Example 5 under air.

[0072] Fig.12 This is the TGA chart of the epoxy resin polymer in Example 6 under nitrogen.

[0073] Fig.13 This is the TGA chart of the epoxy resin polymer in Example 6 under air.

[0074] Fig.14 DMA (Tan-Delta) graph of the epoxy resin polymers of Examples 5 and 6.

[0075] Fig.15 DMA (storage modulus) graph of the epoxy resin polymers of Examples 5 and 6.

[0076] Fig.16 The DSC graphs of the epoxy resin polymers of Examples 5 and 6 are shown in FIG.

[0077] Fig.17 This is the MCC diagram of the epoxy resin polymers of Example 5 and Example 6.

[0078] Fig.18 This is the MCC diagram of Meng-gaun HF system epoxy resin polymer. DETAILED DESCRIPTION

[0079] 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.

[0080] The structure of Meng-guan HF described in the following examples is as follows:

[0081]

[0082] Example 1 Preparation of 5-chloromethyl-2-furancarboxaldehyde b

[0083] 5-Hydroxymethylfurfural (31.5 g, 250 mmol) was added to a 500 mL round-bottom flask, and dichloromethane (150 mL) was added. 12 mol / L concentrated hydrochloric acid (40 mL) was slowly added dropwise under strong stirring (1000 rpm). After the addition was completed, the reaction was stirred at room temperature overnight, and the reaction progress was monitored by thin layer chromatography. After the reaction was completed, an appropriate amount of water was added to dilute the reaction solution, and the organic phase and the aqueous phase were separated. The aqueous phase was extracted with dichloromethane (90 mL) for 3 times, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography using pure dichloromethane as an eluent to obtain high-purity 5-chloromethylfurfural b (32.7 g) with a yield of 90.8%.

[0084] 1 H NMR (400 MHz, CDCl 3 )δ9.63(s,1H),7.25(d,J=3.6Hz,1H),6.63(d,J=3.6Hz,1H),4.65(s,2H).

[0085] Example 2 Preparation of Compound C

[0086] 5-Chloromethylfurfural b (14.3 g, 100 mmol) obtained by the reaction in Example 1 was weighed and dissolved in 60 ml of acetonitrile and placed in a constant pressure low liquid funnel for later use; magnolol (11 g, 41.3 mmol) was added to a 500 ml round-bottom flask, and 50 ml of acetonitrile was added to completely dissolve it. Potassium carbonate (13.7 g, 100 mmol) was added at room temperature with stirring (800 rpm) and stirred for 30 min; then the 5-chloromethylfurfural acetonitrile solution described above was added dropwise, and sodium iodide (0.5 g, 3. 3mmol), the temperature of the reaction system was raised to 80°C, and the reaction progress was monitored by thin layer chromatography; after reacting for 16h, 50mL of distilled water was added to dilute the reaction solution, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotation, and the crude product was purified by column chromatography with a petroleum ether-ethyl acetate (PE / EA:6 / 1-PE / EA:3 / 1) system gradient elution to obtain compound c (15.1g, 31.3mmol) with a yield of 76%, which was a creamy yellow block solid that could be ground into powder and was slightly hard.

[0087] 1 H NMR (400 MHz, CDCl 3 )δ9.55(s,2H),7.15-7.08(m,6H),6.93(d,J=8.3Hz,2H),6.31(d,J=3.5Hz,2H),5.96(ddt,J=16.8,10.0,6.7Hz,2H),5.14 -5.04(m,4H),5.02(s,4H),3.36(d,J=6.7Hz,4H).

[0088] Example 3 Preparation of Compound d

[0089] Compound c (15.1 g, 31.3 mmol) was added to a 500 mL round-bottom flask, and 200 mL of methanol was added to completely dissolve it. If necessary, sonication was used to assist dissolution. Sodium borohydride (2.4 g, 63.4 mmol) was added four times at 0°C, and the reaction was stirred overnight. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, 50 mL of distilled water was added to quench the reaction. The reaction solution was extracted with ethyl acetate (120 mL) three times, dried over anhydrous sodium sulfate, and then the solvent was removed by rotary evaporation. Petroleum ether-ethyl acetate (PE / EA:2 / 1-PE / EA:1 / 1) system was used as an eluent for elution and purification to obtain compound d (12 g, 24.7 mmol) with a yield of 78.8% as a white solid powder.

[0090] 1 H NMR (400 MHz, CDCl 3)δ7.14-7.05(m,4H),6.96(d,J=8.5Hz,2H),6.14(dd,J=15.6,3.1Hz,4H),5.96(ddt,J=16 .8,10.0,6.7Hz,2H),5.14-5.00(m,4H),4.86(s,4H),4.50(s,4H),3.35(d,J=6.7Hz,4H).

[0091] Example 4 Preparation of magnolol / glycosyl furan bis bio-based epoxy resin monomer MF

[0092] At room temperature, epichlorohydrin (45.7 g, 494 mmol), tetrabutylammonium bromide (1.6 g, 4.96 mmol) and a sodium hydroxide aqueous solution (40%, 30 mL) containing NaOH (20 g, 0.5 mol) were added to a 500 mL round-bottom flask and mixed rapidly; N 2 , slowly drop a tetrahydrofuran solution (50 mL) containing compound d (12 g, 24.7 mmol), raise the temperature of the reaction system to 50 ° C, and stir the reaction for 4 hours. After the reaction is completed, add an appropriate amount of distilled water to dilute the reaction solution, extract with ethyl acetate, dry with anhydrous sodium sulfate and spin-dry the solvent, elute and purify with petroleum ether-ethyl acetate (PE / EA:4 / 1-PE / EA:2 / 1) system as eluent, and obtain magnolol / glycosyl furan bibi-based epoxy resin monomer (9.51 g, 16 mmol) with a yield of 64.4%. It is a light yellow transparent liquid with a relatively viscous texture. NMR mass spectrometry is shown as Figures 2 to 4 As shown, infrared Figure 5 As shown, TGA test Figure 8 As shown, the initial decomposition temperature (T d5 ) is 296.3℃, while Meng-guan HF( Fig. 9 The initial decomposition temperature (T d5 ) is 260.5℃, indicating that MF monomer has better thermal stability.

[0093] 1 H NMR (400 MHz, CDCl 3)δ7.08(d,J=7.1Hz,4H),6.96(d,J=8.9Hz,2H),6.22(d,J=3.1Hz,2H),6.13(d,J=3.1H z,2H),5.95(ddt,J=16.8,10.0,6.7Hz,2H),5.05(dd,J=22.4,5.5Hz,4H),4.88(s,4H), 4.44(q,J=12.9Hz,4H),3.79-3.63(m,2H),3.37(dd,J=9.6,4.0Hz,2H),3.34(d,J=6.7H z, 4H), 3.10 (qd, J = 5.9, 3.0Hz, 2H), 2.74 (t, J = 4.6Hz, 2H), 2.55 (dd, J = 5.0, 2.7Hz, 2H).

[0094] 13 C NMR (101 MHz, CDCl 3 )δ154.36,151.51,151.29,137.78,132.63,131.94,128.62,128.33,115 .57,113.75,110.45,109.78,70.56,65.12,63.82,50.70,44.28,39.45.

[0095] HRMS(ESI-TOF)m / z Calcd for C 36 H 38 NaO 8 [M+Na] + :621.2459,found:621.2459.

[0096] Comparative Example 1

[0097] Weigh the magnolol / glycosyl furan bi-bio-based epoxy resin Meng-guan HF (8.0 g) in the reaction bottle, add the curing agent 4,4'-diaminodiphenyl sulfone (1.7 g) at 25°C under a nitrogen atmosphere, heat to 150°C and stir rapidly for 30 minutes 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, move it into a curing box with a nitrogen atmosphere, slowly heat to 220°C for curing for 2 hours, and cool naturally under a nitrogen atmosphere to obtain an epoxy resin polymer material.

[0098] Comparative Example 2

[0099] Weigh the magnolol / glycosyl furan bi-bio-based epoxy resin Meng-guan HF (8.0 g) in the reaction bottle, add the curing agent 3,3'-diaminodiphenyl sulfone (1.7 g) at 25°C under a nitrogen atmosphere, heat to 150°C and stir rapidly for 30 minutes to ensure that the materials are fully dissolved 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, move it into a curing box with a nitrogen atmosphere, slowly heat to 220°C for curing for 2 hours, and cool naturally under a nitrogen atmosphere to obtain an epoxy resin polymer material.

[0100] Example 5

[0101] Weigh magnolol / glycosyl furan bibi-based epoxy resin MF (8.0 g) in a reaction bottle, add curing agent 4,4'-diaminodiphenyl sulfone (1.7 g) at 25°C under a nitrogen atmosphere, heat to 150°C and stir rapidly for 30 minutes 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, move it into a curing box with a nitrogen atmosphere, slowly heat to 210°C and cure for 2 hours, and cool naturally under a nitrogen atmosphere to obtain an epoxy resin polymer material.

[0102] By judging its infrared data, such as Figure 6 As shown, the infrared peaks of ethylene oxide in the original epoxy substrate (855 and 928 cm -1 The disappearance of the stretching vibration of equal intensity indicates that the epoxy group and the amine group of the epoxy resin have been completely polymerized; and the infrared peak of the C=C double bond in the olefin in the original epoxy substrate (1637cm -1 The uniform stretching vibration) disappeared, indicating that the vinyl groups in the system have completely self-polymerized (m is 8.05×10 21 , n is 4.025×10 21 ). Polymer infrared data attribute: 1102cm -1 Vibration of carbon-oxygen bond in ether bond COC; 1401cm -1 Characteristic peaks of CN bonds; 1636, 1592, 1508 cm -1 Characteristic peak of benzene ring; 3144cm -1 The left and right peaks are the stretching vibrations of the =CH bond on the furan ring; 3420cm -1 The broad absorption peak at is caused by the ring opening of ethylene oxide leading to the appearance of OH groups.

[0103] Thermogravimetric data analysis under nitrogen, such as Fig.10 As shown in the figure, the initial decomposition temperature is 314℃ and the maximum decomposition temperature is 457℃. The obtained material has good heat resistance. Thermogravimetric data analysis under air shows that Fig.11As shown, the initial decomposition temperature is 293.6°C, the maximum decomposition temperature is 500.7 / 640.7°C, the residual carbon content is 9.22% at 750°C, and the obtained material has good heat resistance.

[0104] The epoxy resin obtained in Example 5 was analyzed by dynamic mechanical analyzer (DMA). Figure 14-15 The curve data shows that the polymer has a high storage modulus (E>3GPa), which is 3.96GPa (25°C), indicating that the curing system of MF and 4,4'-diaminodiphenyl sulfone has a polymer structure with a high storage modulus. The peak of its dynamic mechanical loss data appears at 204.3°C, indicating that its glass transition temperature is high and its thermal properties are good. By comparing this data with the data of the Meng-guanHF / 44DDS sample of the same system, the storage modulus of the sample of this embodiment at 25°C is significantly greater than that of Meng-guan HF / 44DDS (Comparative Example 1, 3.07GPa), which has certain advantages.

[0105] The thermal curing behavior of the epoxy resin obtained in Example 5 was studied by differential scanning calorimetry (DSC). Fig.16 It is shown in the figure that the polymer has a high phase transition temperature, and its Tg data is 202.3℃, indicating that the resin has a good working temperature range.

[0106] The flame retardancy of the epoxy resin obtained in Example 5 was tested by microscale combustion calorimetry (MCC). The heat release rate (HRR) and temperature curve are shown in Figure 2. Fig.17 As shown in the figure, the average heat release rate of the polymer is 64.5 W / g. Compared with 498.8 W / g of the traditional resin DGEBA in the same curing system, the average heat release rate of the resin obtained in Example 5 is significantly lower; moreover, compared with the MCC data of Meng-gaun HF / 44DDS in the same system ( Fig.18 ), the average heat release rate of Meng-gaun HF / 44DDS is 137.5W / g, indicating that the resin has good flame retardant properties, releases less heat during combustion, and can reduce the risk of fire.

[0107] Example 6

[0108] Weigh magnolol / glycosyl furan bibio-based epoxy resin MF (8.0 g) in a reaction bottle, add curing agent 3,3'-diaminodiphenyl sulfone (1.7 g) at 25°C under a nitrogen atmosphere, heat to 150°C and stir rapidly for 30 minutes to ensure that the materials are fully dissolved 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, move it into a curing box with a nitrogen atmosphere, slowly heat to 210°C and cure for 2 hours, and cool naturally under a nitrogen atmosphere to obtain an epoxy resin polymer material.

[0109] Judging from infrared data, Figure 7 As shown, the infrared peaks of ethylene oxide in the original epoxy substrate (855 and 928 cm -1 The disappearance of the stretching vibration of equal intensity indicates that the epoxy group and the amine group of the epoxy resin have been completely polymerized; and the infrared peak of the C=C double bond in the olefin in the original epoxy substrate (1637cm -1 The uniform stretching vibration) disappeared, indicating that the vinyl groups in the system have completely self-polymerized (m is 8.05×10 21 , n is 4.025×10 21 ). Polymer infrared data attribute: 1104cm -1 Vibration of carbon-oxygen bond in ether bond COC; 1403cm -1 Characteristic peaks of CN bonds; 1597, 1562, 1494 cm -1 It is the characteristic peak of benzene ring; 2918cm -1 The left and right peaks are the stretching vibrations of saturated CH bonds on the aliphatic chain; 3405cm -1 The broad absorption peak at is caused by the ring opening of ethylene oxide leading to the appearance of OH groups.

[0110] Thermogravimetric data analysis under nitrogen, such as Fig.12 As shown in the figure, the initial decomposition temperature is 363℃ and the maximum decomposition temperature is 425℃. The obtained material has good heat resistance. Thermogravimetric data analysis under air shows that Fig.13 As shown, the initial decomposition temperature is 316°C, the maximum decomposition temperature is 565°C, and the residual carbon content is 2.59% at 750°C. The obtained material has good heat resistance.

[0111] The epoxy resin obtained in Example 6 was analyzed by dynamic mechanical analyzer (DMA). Figure 14-15 , the curve data shows that the polymer has a higher storage modulus of 5.04GPa (25°C) compared with Example 5, indicating that the curing system of MF and 3,3'-diaminodiphenyl sulfone has a polymer structure with a higher storage modulus. The peak of its dynamic mechanical loss data appears at 218.6°C, indicating that its glass transition temperature is high and its thermal properties are good. By comparing this data with the data of the Meng-guan HF / 44DDS sample of the same system, the storage modulus of the sample of this embodiment at 25°C is significantly greater than the data of Meng-guan HF / 44DDS (3.07GPa), which has certain advantages.

[0112] The thermal curing behavior of the epoxy resin obtained in Example 6 was studied by differential scanning calorimetry (DSC). Fig.16It is shown in the data that the polymer has a very high phase transition temperature, and its Tg data is as high as 222.7°C, which also shows that the resin has a high application temperature range.

[0113] The flame retardancy of the epoxy resin obtained in Example 6 was tested by microscale combustion calorimetry (MCC). The heat release rate (HRR) and temperature curve are shown in Figure 2. Fig.17 As shown in Figure 1, the average heat release rate of the polymer is 92.6 W / g. Compared with 553 W / g of the traditional resin DGEBA in the same curing system, the average heat release rate of the resin obtained in Example 6 is significantly lower, and compared with the MCC data of Meng-guan HF / 33DDS in the same system ( Fig.18 ), the average heat release rate of Meng-guan HF / 33DDS is 117.5W / g, indicating that the resin has good flame retardant properties, releases less heat during combustion, and can reduce the risk of fire.

[0114] The present invention provides a magnolol / glycosyl furan bibi-based epoxy resin monomer and its preparation method and application ideas and methods. There are many methods and ways to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the scope of protection of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A magnolol / glycosyl furan bi bio-based epoxy resin monomer MF; 2. The method for preparing the magnolol / glycosyl furan bis bio-based epoxy resin monomer MF according to claim 1, It is characterized in that The following steps are involved: (1) Under the action of a catalyst, magnolol and 5-chloromethylfurfural undergo a first reaction to obtain compound c; (2) the obtained compound c is subjected to a second reaction with a reducing agent to obtain a compound d; (3) the obtained compound d, epichlorohydrin, alkaline solution and phase transfer catalyst are subjected to a third reaction to prepare magnolol / glycosyl furan bis bio-based epoxy resin monomer MF; In step (1), the catalyst is sodium iodide; In step (2), the reducing agent is any one of sodium borohydride, lithium aluminum hydride, aluminum triisopropoxide and hydrogen; In step (3), the phase transfer catalyst is one of tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium chloride or a mixture thereof; 3. A magnolol / glycosyl furan bibi-based epoxy resin, It is characterized in that Composed of a binary polymer consisting of A and B, or a binary polymer consisting of A and C; Among them, the structural units of A, B, and C are: Wherein, the binary polymer composed of A and B has a repeating structural unit shown in formula I, and the binary polymer composed of A and C has a repeating structural unit shown in formula II; Among them, m≥2, n≥2.

4. The magnolol / glycosyl furan bis bio-based epoxy resin according to claim 3, It is characterized in that The initial decomposition temperature of the magnolol / glycosyl furan bis-bio-based epoxy resin in a nitrogen atmosphere is 310-370°C, and the maximum decomposition temperature is 420-490°C; the initial decomposition temperature of the magnolol / glycosyl furan bis-bio-based epoxy resin in an air atmosphere is 280-330°C, and the maximum decomposition temperature is 480-670°C, and the residual carbon content at 750°C is 1%-11%.

5. The magnolol / glycosyl furan bis bio-based epoxy resin according to claim 3, It is characterized in that The storage modulus of the magnolol / glycosyl furan bibio-based epoxy resin is 3 to 9 GPa.

6. The magnolol / glycosyl furan bis bio-based epoxy resin according to claim 3, It is characterized in that The phase transition temperature of the magnolol / glycosyl furan bibio-based epoxy resin is 200-250°C.

7. The magnolol / glycosyl furan bis bio-based epoxy resin according to claim 3, It is characterized in that The average heat release rate of the magnolol / glycosyl furan bis bio-based epoxy resin is 50-100 W / g.

8. The method for preparing the magnolol / glycosyl furan bis bio-based epoxy resin according to any one of claims 3 to 7, It is characterized in that Mixing magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF and aromatic sulfone diamine curing agent, melting, injection molding, and curing to obtain magnolol / glycosyl furan bis-bio-based epoxy resin; 9. The preparation method according to claim 8, It is characterized in that The molar ratio of the epoxy group in the magnolol / glycosyl furan bis-bio-based epoxy resin monomer MF to the amino group in the aromatic sulfone diamine curing agent is 0.8-1.5:1; the melting temperature is 120-180°C; and the curing temperature is 200-230°C.

10. Use of the magnolol / glycosyl furan bis bio-based epoxy resin according to any one of claims 3 to 7 as or in the preparation of heat-resistant materials.

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