Organic silicon modified soybean flavone adhesive, preparation method therefor and use thereof

Abstract

Disclosed in the present invention is an organic silicon modified soybean flavone adhesive, mainly comprising the following components: hydroxy-carboxy terminated polydimethylsiloxane modified soybean flavone, a crosslinking agent, an organic metal catalyst and a first organic solvent, wherein hydroxy-carboxy terminated polydimethylsiloxane modified soybean flavone is mainly synthesized from hydroxy-carboxy terminated polydimethylsiloxane and epoxy soybean flavone by means of a ring-opening crosslinking reaction. When in use, the crosslinking agent and the organic metal catalyst are added into hydroxy-carboxy terminated polydimethylsiloxane modified soybean flavone, a certain amount of organic solvent is added such that the solid content in the system reaches 40%-50%, and the mixture is uniformly mixed. The organic silicon modified soybean flavone adhesive provided by the present invention has the advantages of high crosslinking density, high curing speed, good hydrophobicity and the like, and can be applied to preparation of wood-based panels.

Description

Silicone-modified soybean flavonoid adhesive and its preparation method and application Technical Field

[0001] The present invention belongs to the technical field of fine chemical industry, relates to an adhesive and a preparation method and application thereof, and specifically relates to an organosilicon-modified soybean flavone adhesive and a preparation method and application thereof. Background Art

[0002] At present, the formaldehyde-free adhesives used in the wood-based panel industry are mainly the following: (1) Polyvinyl acetate adhesives, which are made by emulsion polymerization of acetic acid and ethylene in water. They have high bonding strength, but have poor water resistance and cold resistance, poor creep resistance of the film, easy sliding of the adhesive layer, and poor storage stability. (2) Isocyanate adhesives, which have high bonding strength and good water resistance, but are expensive, highly active, have too fast reaction speed, and have high requirements for production process control. Materials will stick to pipes during transportation. (3) Soy protein adhesives, although they have good environmental performance and renewable raw materials, have poor bonding strength and water resistance, high hot pressing temperature, long hot pressing time, and are prone to bubbling. (4) Starch adhesives, which have the advantages of wide sources, low prices, renewable and biodegradable, but starch adhesives have many shortcomings during use, such as poor water resistance, poor fluidity, easy mildew, and poor storage stability.

[0003] Summary of the Invention

[0004] The main purpose of the present invention is to provide a silicone-modified soybean flavonoid adhesive to solve at least one of the above technical problems.

[0005] According to one aspect of the present invention, a silicone-modified soy flavonoid adhesive is provided, comprising the following components: hydroxycarboxyl-terminated polydimethylsiloxane-modified soy flavonoid, a crosslinking agent, an organometallic catalyst, and a first organic solvent. The silicone-modified soy flavonoid is synthesized primarily through a ring-opening crosslinking reaction between silicone-terminated polydimethylsiloxane and epoxy soy flavonoid. Under the action of the organometallic catalyst, the silicone-modified soy flavonoid crosslinks with the organosilicon crosslinker to form a three-dimensional network structure, effectively improving the viscosity and curing speed of the silicone-modified adhesive.

[0006] In some embodiments, the crosslinking agent may be selected from at least one of methyltrimethoxysilane, vinyltributylanoximesilane, and propyltriacetoxysilane.

[0007] In some embodiments, the organometallic catalyst may be selected from at least one of dibutyltin dilaurate, stannous isooctanoate, zinc isooctanoate, and bismuth isooctanoate.

[0008] When in use, a crosslinking agent and an organic metal catalyst are added to the terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and a certain amount of the first organic solvent is added to make the solid content of the system reach 40% to 50%, and mixed evenly to obtain the organic silicon modified soybean flavonoids adhesive working fluid.

[0009] In some embodiments, the first organic solvent may be selected from at least one of ethyl acetate, acetone, butanone, dimethyl sulfoxide, and dichloromethane.

[0010] In some embodiments, the amount of the cross-linking agent used can be 5% to 15% of the mass of the terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoid.

[0011] In some embodiments, the amount of the organometallic catalyst used may be 0.5% to 2% of the mass of the hydroxycarboxyl-terminated polydimethylsiloxane-modified soybean flavonoid.

[0012] The organosilicon-modified soybean flavonoid adhesive provided by the present invention has the advantages of high cross-linking density, good stability, fast curing speed, good hydrophobicity, etc., and can be used in the preparation of artificial boards.

[0013] When used in the preparation of artificial boards, the organic silicon modified soybean flavonoid adhesive working liquid is evenly applied on the veneer, closed and aged for 10 to 13 minutes under room temperature, and then molded to obtain the artificial board. The amount of glue applied can be 200g / m 3 ~240g / m 3 , the hot pressing pressure can be 0.9-1.1MPa, and the hot pressing temperature can be 120℃-140℃.

[0014] According to another aspect of the present invention, a method for preparing the above-mentioned organosilicon-modified soybean flavonoid adhesive is provided, comprising the following steps:

[0015] Mixing terminal hydroxycarboxyl polydimethylsiloxane, epoxy daidzein, a third phase transfer catalyst and a third organic solvent, and reacting them at a temperature of 75 to 85° C. for 1 to 3 hours to obtain terminal hydroxycarboxyl polydimethylsiloxane modified daidzein;

[0016] The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoid, the cross-linking agent, the organic metal catalyst and the first organic solvent are packaged independently to obtain the product.

[0017] The present invention firstly performs ring-opening crosslinking of the carboxyl group at the terminal of hydroxycarboxyl-terminated polydimethylsiloxane with the epoxy group in epoxy soy flavonoids to prepare hydroxycarboxyl-terminated polydimethylsiloxane-modified soy flavonoids; then independently packages the hydroxycarboxyl-terminated polydimethylsiloxane-modified soy flavonoids, a crosslinking agent, an organic metal catalyst, and a first organic solvent to prepare the organosilicon-modified soy flavonoids adhesive of the present invention.

[0018] In some embodiments, the molar ratio of the hydroxycarboxyl-terminated polydimethylsiloxane to the epoxy daidzein is 1:(0.5-1).

[0019] In some embodiments, the third phase transfer catalyst can be selected from at least one of triethylamine, trioctylmethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium bromide, triethylhexylammonium bromide, and triethyloctylammonium bromide.

[0020] In some embodiments, the amount of the third phase transfer catalyst may be 1% to 3% of the mass of the hydroxycarboxyl-terminated polydimethylsiloxane.

[0021] In some embodiments, the third organic solvent may be selected from at least one of ethyl acetate, acetone, butanone, dimethyl sulfoxide, and dichloromethane.

[0022] In some embodiments, the mass ratio of the third organic solvent to the total mass of the hydroxycarboxyl-terminated polydimethylsiloxane and the epoxy daidzein is 1:(1.0-1.5).

[0023] In some embodiments, the preparation method of epoxy daidzein may include the following steps:

[0024] Mixing soybean flavonoids, a modifier, and a second phase transfer catalyst, and reacting them at a temperature of 100 to 110° C. for 1 to 3 hours to obtain a reaction mixture;

[0025] The reaction mixture, sodium hydroxide aqueous solution and the second organic solvent are mixed and reacted at room temperature for 4 to 6 hours. The obtained reaction product is separated, purified and dried to obtain epoxydized soy flavonoids.

[0026] In some embodiments, the modifier may be selected from one of epichlorohydrin and epibromohydrin.

[0027] In some embodiments, the molar ratio of soybean flavonoids to the modifier is 1:(10-15).

[0028] In some embodiments, the second phase transfer catalyst can be selected from at least one of triethylamine, trioctylmethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium bromide, triethylhexylammonium bromide, and triethyloctylammonium bromide.

[0029] In some embodiments, the amount of the second phase transfer catalyst may be 5% to 8% of the mass of the daidzein.

[0030] In some embodiments, the mass ratio of daidzein to sodium hydroxide solution can be 1:(0.8-1.5). By using a certain concentration of sodium hydroxide solution as an alkaline treatment agent, the functional groups of the daidzein molecules can be exposed, which facilitates the smooth access of more epoxy groups during the reaction.

[0031] In some embodiments, the concentration of sodium hydroxide in the sodium hydroxide aqueous solution may be 45 wt % to 55 wt %.

[0032] In some embodiments, the second organic solvent is selected from at least one of ethyl acetate, acetone, butanone, dimethyl sulfoxide, and dichloromethane.

[0033] In some embodiments, the mass ratio of the second organic solvent to the total mass of daidzein and the modifier is (1.0-1.5):1.

[0034] In some embodiments, the preparation method of hydroxy-terminated polydimethylsiloxane may include the following steps:

[0035] The hydroxy-terminated polydimethylsiloxane, maleic anhydride and a first phase transfer catalyst are mixed and reacted at a temperature of 70 to 85° C. for 1 to 5 hours to obtain the hydroxy-terminated polydimethylsiloxane.

[0036] In some embodiments, the molar ratio of the hydroxyl-terminated polydimethylsiloxane to the maleic anhydride is 1:(1-1.2).

[0037] In some embodiments, the first phase transfer catalyst can be selected from at least one of triethylamine, trioctylmethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium bromide, triethylhexylammonium bromide, and triethyloctylammonium bromide.

[0038] In some embodiments, the amount of the first phase transfer catalyst used may be 1% to 3% of the total mass of the hydroxyl-terminated polydimethylsiloxane and the maleic anhydride.

[0039] The beneficial effects of the present invention include:

[0040] (1) The organosilicon-modified soybean flavonoid adhesive provided by the present invention does not contain formaldehyde, has a high bio-based content, and is environmentally friendly and safe;

[0041] (2) The organosilicon-modified soybean flavonoid adhesive provided by the present invention has good water resistance, fast curing speed, high cross-linking density, good wettability and high bonding strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG1 is a schematic diagram of the synthesis route of hydroxycarboxyl-terminated polydimethylsiloxane-modified soybean flavonoids of the present invention;

[0043] FIG2 is an infrared spectra of hydroxy-terminated polydimethylsiloxane, hydroxy-carboxyl-terminated polydimethylsiloxane synthesized in Example 1 of the present invention, and hydroxy-carboxyl-terminated polydimethylsiloxane-modified soybean flavonoids;

[0044] FIG3 is a rheological diagram of hydroxy-terminated polydimethylsiloxane (comparative example) and hydroxy-carboxyl-terminated polydimethylsiloxane prepared in Examples 1 to 6 of the present invention;

[0045] FIG4 is an infrared spectra of hydroxy-terminated polydimethylsiloxane (comparative example) and hydroxy-carboxyl-terminated polydimethylsiloxane prepared in Examples 1 to 6 of the present invention;

[0046] FIG5 is a TG curve (under nitrogen atmosphere) of the cured film obtained after curing the organosilicon-modified soybean flavonoid adhesive prepared in Examples 1 to 6 of the present invention;

[0047] FIG6 is a DTG curve (under nitrogen atmosphere) of the cured film obtained after curing the organosilicon-modified soybean flavonoid adhesive prepared in Examples 1 to 6 of the present invention;

[0048] FIG7 is a schematic diagram of plywood sample preparation and force loading direction in the bonding strength test;

[0049] FIG8 is a graph showing the bonding strength test results of the organosilicon-modified soybean flavonoid adhesives prepared in Examples 1 to 6 of the present invention;

[0050] FIG9 shows the water contact angle of the cured films obtained after curing of the organosilicon-modified soybean flavonoid adhesives prepared in Examples 1 to 6 of the present invention;

[0051] FIG10 is a fracture scanning electron micrograph of a cross section of a cured film obtained after curing the organosilicon-modified soybean flavonoid adhesive prepared in Examples 1 to 6 of the present invention. DETAILED DESCRIPTION

[0052] The present invention will be further described in detail below with reference to the following embodiments. The examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Unless otherwise specified, the raw materials and reagents used in the examples are commercially available conventional products. Experimental procedures in the examples where specific conditions are not specified are generally performed in accordance with conventional conditions in the art or the conditions recommended by the manufacturer.

[0053] Example 1 Preparation of silicone-modified soybean flavonoid adhesive

[0054] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0055] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 2.94 g (0.03 mol) of maleic anhydride, and 0.33 g of triethylamine to a three-necked flask and react at 75° C. for 1.5 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0056] (3) 5.43 g (0.015 mol) of epoxydized soybean flavonoids, 0.36 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxy-terminated carboxyl polydimethylsiloxane and reacted at 80° C. for 2 hours to obtain hydroxy-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0057] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, the crosslinking agent methyltrimethoxysilane, the organometallic catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organosilicon modified soybean flavonoids adhesive.

[0058] When in use, 1.5g of methyltrimethoxysilane and 0.4g of dibutyltin dilaurate can be added to 30g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 35g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0059] The schematic diagram of the synthesis route of the hydroxy-carboxyl-terminated polydimethylsiloxane-modified soybean flavonoids in this embodiment is shown in FIG1 .

[0060] Thermo-Nicolet Nexus 670 FT-IR spectrometer was used to record the FT-IR of the terminal hydroxyl polydimethylsiloxane, the terminal hydroxyl carboxyl polydimethylsiloxane synthesized in step (2), and the terminal hydroxyl carboxyl polydimethylsiloxane modified soybean flavonoid synthesized in step (3) at 4000-500 cm -1 Fourier transform infrared spectroscopy (FT-IR) analysis was performed within the range of 10 nm, with 32 scans. The results are shown in Figure 2.

[0061] Example 2 Preparation of silicone-modified soybean flavonoid adhesive

[0062] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0063] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 2.94 g (0.03 mol) of maleic anhydride, and 0.33 g of triethylamine to a three-necked flask and react at 80° C. for 3 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0064] (3) 8.25 g (0.0225 mol) of epoxydized soybean flavonoids, 0.36 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxy-terminated carboxyl polydimethylsiloxane and the mixture was fully reacted at 80° C. for 2 hours to obtain hydroxy-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0065] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, the crosslinking agent methyltrimethoxysilane, the organometallic catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organosilicon modified soybean flavonoids adhesive.

[0066] When in use, 3g of methyltrimethoxysilane and 0.4g of dibutyltin dilaurate can be added to 30g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 30g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0067] Example 3 Preparation of silicone-modified soybean flavonoid adhesive

[0068] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0069] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 2.94 g (0.03 mol) of maleic anhydride, and 0.33 g of triethylamine to a three-necked flask and react at 85° C. for 4.5 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0070] (3) 10.86 g (0.03 mol) of epoxydized soybean flavonoids, 0.36 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxy-terminated carboxyl polydimethylsiloxane and reacted at 80° C. for 2 hours to obtain hydroxy-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0071] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, the crosslinking agent methyltrimethoxysilane, the organometallic catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organosilicon modified soybean flavonoids adhesive.

[0072] When in use, 4.5g of methyltrimethoxysilane and 0.4g of dibutyltin dilaurate can be added to 30g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 30g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0073] Example 4 Preparation of silicone-modified soybean flavonoid adhesive

[0074] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0075] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 3.23 g (0.033 mol) of maleic anhydride, and 0.66 g of triethylamine to a three-necked flask and react at 75° C. for 1.5 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0076] (3) 5.43 g (0.015 mol) of epoxydized soybean flavonoids, 0.72 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxyl-terminated carboxyl polydimethylsiloxane and reacted at 80° C. for 2 hours to obtain hydroxyl-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0077] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoid, the crosslinking agent vinyl trisbutyl ketoxime silane, the organic metal catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organic silicon modified soybean flavonoid adhesive.

[0078] When in use, 1.5 g of vinyl trisbutyl ketoxime silane and 0.5 g of dibutyltin dilaurate can be added to 30 g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 30 g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0079] Example 5 Preparation of silicone-modified soybean flavonoid adhesive

[0080] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0081] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 3.23 g (0.033 mol) of maleic anhydride, and 0.66 g of triethylamine to a three-necked flask and react at 80° C. for 3 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0082] (3) 8.15 g (0.0225 mol) of epoxydized soybean flavonoids, 0.72 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxy-terminated carboxyl polydimethylsiloxane and reacted at 80° C. for 2 hours to obtain hydroxy-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0083] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoid, the crosslinking agent vinyl trisbutyl ketoxime silane, the organic metal catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organic silicon modified soybean flavonoid adhesive.

[0084] When in use, 3g of vinyl trisbutyl ketoxime silane and 0.5g of dibutyltin dilaurate can be added to 30g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 30g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0085] Example 6 Preparation of silicone-modified soybean flavonoid adhesive

[0086] (1) 20 g (0.08 mol) of daidzein, 1.2 g of tetrabutylammonium bromide, and 74 g (0.8 mol) of epichlorohydrin were added to a three-necked flask and reacted at 105° C. for 1 hour. 20 g of NaOH solution (50 wt% aqueous solution) and 100 g of dichloromethane were added as solvent and reacted at room temperature for 5 hours. The mixture was extracted with deionized water, filtered, washed, and dried in an oven to obtain epoxydized daidzein.

[0087] (2) Add 30 g (0.03 mol) of hydroxyl-terminated polydimethylsiloxane, 3.23 g (0.033 mol) of maleic anhydride, and 0.66 g of triethylamine to a three-necked flask and react at 85° C. for 4.5 hours to obtain hydroxyl-terminated polydimethylsiloxane;

[0088] (3) 10.86 g (0.03 mol) of epoxydized soybean flavonoids, 0.72 g of triethylamine, and 30 g of ethyl acetate were added to 31 g (0.03 mol) of hydroxy-terminated carboxyl polydimethylsiloxane and reacted at 80° C. for 2 hours to obtain hydroxy-terminated carboxyl polydimethylsiloxane-modified soybean flavonoids;

[0089] (4) The terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoid, the crosslinking agent vinyl trisbutyl ketoxime silane, the organic metal catalyst dibutyltin dilaurate and ethyl acetate are packaged separately to obtain the organic silicon modified soybean flavonoid adhesive.

[0090] When in use, 4.5 g of vinyl trisbutyl ketoxime silane and 0.5 g of dibutyltin dilaurate can be added dropwise to 30 g of terminal hydroxycarboxyl polydimethylsiloxane modified soybean flavonoids, and 30 g of ethyl acetate can be added to make the solid content of the system reach 40% to 50%, thereby obtaining the working solution of the silicone modified soybean flavonoids adhesive.

[0091] Test Example 1 Rheological Test

[0092] The hydroxy-terminated polydimethylsiloxane and the hydroxy-carboxyl-terminated polydimethylsiloxanes prepared in Examples 1-6 were tested using an MCR 502 modular intelligent advanced rheometer. A CP25-2 rotor was used, and a measurement-viscosity curve was configured. The number of data points was set to 25, with a 10-second interval between each measurement point. At least three parallel experiments were performed for each example to ensure test accuracy.

[0093] The results are shown in Figure 3.

[0094] As shown in Figure 3, the viscosity of the obtained hydroxycarboxyl-terminated polydimethylsiloxane increases with increasing temperature and catalyst dosage. The viscosity of the control hydroxycarboxyl-terminated polydimethylsiloxane ranges from 16.214 to 18.106 MPa·s. Among the hydroxycarboxyl-terminated polydimethylsiloxanes obtained in Examples 1 to 6, the hydroxycarboxyl-terminated polydimethylsiloxane obtained in Example 1 has the lowest viscosity, ranging from 279.87 to 289.48 MPa·s, while the hydroxycarboxyl-terminated polydimethylsiloxane obtained in Example 6 has the highest viscosity, ranging from 4212.9 to 4366.3 MPa·s. The hydroxycarboxyl-terminated polydimethylsiloxanes obtained in Examples 1 to 6 all have good fluidity. Therefore, when reacting them with epoxy soy flavonoids to prepare hydroxycarboxyl-terminated polydimethylsiloxane-modified soy flavonoids, no solvent needs to be added during the reaction, which can greatly save costs.

[0095] Test Example 2 Fourier Transform Infrared Spectroscopy Test

[0096] Thermo-Nicolet Nexus 670 FT-IR spectrometer was used to record the FT-IR of the hydroxy-terminated polydimethylsiloxane (control example) and the hydroxy-terminated polydimethylsiloxane prepared in Examples 1 to 6 at 4000 to 500 cm -1 Fourier transform infrared spectroscopy (FT-IR) analysis was performed within the range of 10 nm, with 32 scans. The results are shown in Figure 4.

[0097] The results in Figure 4 show that the control example of hydroxy-terminated polydimethylsiloxane has a peak at 3370 cm -1 There is a clear stretching vibration of hydroxyl groups in the reaction with maleic anhydride, 3370cm -1 The infrared absorption peak disappeared obviously, and the obtained hydroxyl-terminated polydimethylsiloxane had an infrared absorption peak at 1740 cm -1 There is a clear stretching vibration of ester carbonyl at 1620cm, indicating that the reaction of hydroxy-terminated polydimethylsiloxane with maleic anhydride produces ester carbonyl. -1 The anhydride peak disappeared, indicating that the reaction of maleic anhydride was complete.

[0098] Test Example 3 Thermogravimetric test

[0099] The organosilicon-modified soybean flavonoid adhesive prepared in Examples 1 to 6 was prepared into an organosilicon-modified soybean flavonoid adhesive working solution, which was then poured into a polytetrafluoroethylene mold and heated in a vacuum oven at 120°C for 5 hours to form a cured film. The cured film was subjected to thermogravimetric analysis (TGA) using a thermal analyzer (Netzsch STA449C) under a nitrogen atmosphere. The nitrogen flow rate was set to 20 mL / min, the test temperature range was 30-800°C, and the heating rate was 10°C / min. The results are shown in Figures 5 and 6.

[0100] As can be seen from Figures 5 and 6, the TG decomposition temperature curves of the cured films of the silicone-modified soybean flavonoid adhesives prepared in Examples 1-6 are between 30 and 800°C. As the amount of epoxy soybean flavonoids gradually increases, the carbon residue rate of the cured films of Examples 1 to 3 increases from 5.14% to 7.79%; the carbon residue rate of the cured films of Examples 4 to 6 increases from 6.40% to 16.70%. Similarly, the DTG maximum degradation temperature of the cured film is around 591.1°C, which is consistent with the TG degradation trend. The modified soybean flavonoid adhesive provided by the present invention has a better thermal stability structure due to the increase in cross-linking density, the generation of hydrogen bonds or other effects.

[0101] Test Example 4: Bonding Strength Test

[0102] The test is carried out according to the method "4.17 Determination of Gluing Strength" in "GB / T17657-2013 Test Methods for Physical and Chemical Properties of Artificial Boards and Veneer Artificial Boards", including the following steps:

[0103] Take a 30cm*30cm poplar veneer, place the poplar veneer on both sides of the glued veneer with the wood grain perpendicular to each other, and apply the same amount of working solution of the organosilicon modified soybean flavonoid adhesive prepared in Examples 1 to 6 on both sides of the poplar veneer (the amount of glue applied is 220g / m 2 ), under the conditions of 130℃ and 1.0MPa, it was pressed into three-layer plywood, and after pressing, it was placed at room temperature for 1 day to obtain plywood. The plywood was sawed into wooden blocks with a length and width of 100mm*25mm, and the gluing area at the gluing center was 25mm*25mm long and wide. The schematic diagram of plywood sample preparation and force loading direction is shown in Figure 7. The dry bonding strength is directly tested without boiling in water; the wet bonding strength test is based on GB / T17657-2013, and the specimen is placed at 30℃ for one hour after being boiled in boiling water for (72±1h) to obtain the bonding strength. At least three sets of parallel experiments are performed for each embodiment to ensure the accuracy of the test. The results are shown in Figure 8.

[0104] The results in Figure 8 show that the maximum dry bonding strength of the organosilicon-modified soybean flavonoid adhesives prepared in Examples 1 to 6 is 2.05 MPa, and the maximum wet bonding strength is 1.03 MPa. The wet bonding strength of the organosilicon-modified soybean flavonoid adhesives prepared in Examples 1 to 6 all meet the GB / T17657-2013 Grade I standard.

[0105] Test Example 5 Water Contact Angle Test

[0106] The organosilicon-modified daidzein adhesives prepared in Examples 1-6 were prepared into a working solution, which was then poured into a polytetrafluoroethylene mold. Cured films were then heated in a 120°C oven under vacuum for 5 hours. The water contact angles of the cured films were measured using a Powereach JC2000C1 instrument. At least three parallel experiments were performed for each example to ensure accuracy. The results are shown in Figure 9.

[0107] After 10 seconds of testing, it can be seen from the results of Figure 9 that the organosilicon-modified soybean flavonoid adhesives prepared in Examples 1 to 6 have a maximum water contact angle of 108.28° after curing, and the water contact angles of the cured films obtained after curing the organosilicon-modified soybean flavonoid adhesives in Examples 1 to 6 are all greater than 90°, indicating good hydrophobicity.

[0108] Test Example 6 Scanning Electron Microscope Test

[0109] The organosilicon-modified daidzein adhesives prepared in Examples 1-6 were prepared into an organosilicon-modified daidzein adhesive working solution, which was then poured into a polytetrafluoroethylene mold and heated in a vacuum oven at 120°C for 5 hours to form a cured film. Prior to testing, the cured film was cryogenically fractured using liquid nitrogen. The fractured cross-section was gold-sprayed before testing, and the morphology of the fracture interface of the cured adhesive was observed using an EVOma15 (ZEISS, Germany) at a voltage of 10.0 kV. The results are shown in Figure 10.

[0110] As shown in the results of Figure 10, the organosilicon-modified soy flavonoid adhesives prepared in Examples 1 to 6 all contain soy flavonoid particles as fillers. As the amount of soy flavonoid added increases, the surface becomes slightly rougher, but the overall organosilicon-modified soy flavonoid adhesive has a neat fracture cross-section without holes or gaps, showing good cross-linking properties.

[0111] The above are only some embodiments of the present invention. For those skilled in the art, several modifications and improvements can be made without departing from the inventive concept of the present invention, which all fall within the scope of protection of the present invention.

Claims

1. Organosilicon-modified soy flavone adhesive, characterized in that, The silicone-modified soy isoflavone adhesive comprises the following components: hydroxyl carboxyl-terminated polydimethylsiloxane-modified soy isoflavone, a crosslinking agent, an organometallic catalyst, and a first organic solvent. Among them, The hydroxyl carboxyl-terminated polydimethylsiloxane-modified soy isoflavone is mainly synthesized by ring-opening crosslinking reaction of hydroxyl carboxyl-terminated polydimethylsiloxane and epoxy soy isoflavone; The crosslinking agent is selected from at least one of methyltrimethoxysilane, vinyltriisobutyloxime silane, and propyltriacetoxysilane; The organometallic catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, zinc octoate, and bismuth octoate.

2. The silicone-modified soy isoflavone adhesive according to claim 1, characterized in that, During use, the mass of the crosslinking agent is 5% - 15% of the mass of the hydroxyl carboxyl-terminated polydimethylsiloxane-modified soy isoflavone; the mass of the organometallic catalyst is 0.5% - 2% of the mass of the hydroxyl carboxyl-terminated polydimethylsiloxane-modified soy isoflavone.

3. The silicone-modified soy isoflavone adhesive according to claim 1 or 2, characterized in that, The first organic solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dimethyl sulfoxide, and dichloromethane.

4. The organosilicon-modified soy isoflavone adhesive according to claim 1, wherein, The preparation method of the hydroxyl carboxyl-terminated polydimethylsiloxane comprises the following steps: Mix hydroxyl-terminated polydimethylsiloxane, maleic anhydride, and a first phase transfer catalyst, and react at a temperature of 70 - 85°C for 1 - 5 hours to obtain hydroxyl carboxyl-terminated polydimethylsiloxane; The first phase transfer catalyst is selected from at least one of triethylamine, trimethyl octyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, triethyl benzyl ammonium bromide, triethyl hexyl ammonium bromide, and triethyl octyl ammonium bromide; The molar ratio of the hydroxyl-terminated polydimethylsiloxane to maleic anhydride is 1:(1 - 1.2); the dosage of the first phase transfer catalyst is 1% - 3% of the total mass of the hydroxyl-terminated polydimethylsiloxane and maleic anhydride.

5. The silicone-modified soy isoflavone adhesive according to claim 1, wherein The preparation method of the epoxy soy isoflavone comprises the following steps: Mix soy isoflavone, a modifier, and a second phase transfer catalyst, and react at a temperature of 100 - 110°C for 1 - 3 hours to obtain a reaction mixture; Mix the reaction mixture, an aqueous sodium hydroxide solution, and a second organic solvent, and react at room temperature for 4 - 6 hours. The obtained reaction product is separated, purified, and dried to obtain epoxy soy isoflavone; The modifier is selected from one of epichlorohydrin and epibromohydrin; The molar ratio of the soy isoflavone to the modifier is 1:(10 - 15); the dosage of the second phase transfer catalyst is 5% - 8% of the mass of the soy isoflavone; the mass ratio of the soy isoflavone to the aqueous sodium hydroxide solution is 1:(0.8 - 1.5).

6. The silicone-modified soy isoflavone adhesive according to claim 5, wherein The second phase transfer catalyst is selected from at least one of triethylamine, trimethyl octyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, triethyl benzyl ammonium bromide, triethyl hexyl ammonium bromide, and triethyl octyl ammonium bromide; the second organic solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dimethyl sulfoxide, and dichloromethane; the concentration of sodium hydroxide in the aqueous sodium hydroxide solution is 45wt% - 55wt%.

7. The silicone-modified soy isoflavone adhesive according to any one of claims 4 to 6, characterized in that, The preparation method of the hydroxyl carboxyl-terminated polydimethylsiloxane-modified soy isoflavone comprises the following steps: Mix the hydroxyl-terminated carboxyl polydimethylsiloxane, epoxy soyaflavone, the third phase transfer catalyst and the third organic solvent, and react at a temperature of 75-85 °C for 1-3 hours to obtain the hydroxyl-terminated carboxyl polydimethylsiloxane modified soyaflavone; The molar ratio of the hydroxyl-terminated carboxyl polydimethylsiloxane to the epoxy soyaflavone is 1:(0.5-1).

8. The silicone-modified soy isoflavone adhesive according to claim 7, wherein The third phase transfer catalyst is selected from at least one of triethylamine, trimethyloctylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium bromide, triethylhexylammonium bromide, triethyloctylammonium bromide; the dosage of the third phase transfer catalyst is 1%-3% of the mass of the hydroxyl-terminated carboxyl polydimethylsiloxane; the third organic solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dimethyl sulfoxide, dichloromethane.

9. The preparation method of the silicone-modified soy isoflavone adhesive according to any one of claims 1 to 8, characterized in that, It includes the following steps: Mix the hydroxyl-terminated polydimethylsiloxane, maleic anhydride and the first phase transfer catalyst, and react at a temperature of 70-85 °C for 1-5 hours to obtain the hydroxyl-terminated carboxyl polydimethylsiloxane; Mix the hydroxyl-terminated carboxyl polydimethylsiloxane, epoxy soyaflavone, the third phase transfer catalyst and the third organic solvent, and react at a temperature of 75-85 °C for 1-3 hours to obtain the hydroxyl-terminated carboxyl polydimethylsiloxane modified soyaflavone; Individually package the hydroxyl-terminated carboxyl polydimethylsiloxane modified soyaflavone, the crosslinking agent, the organometallic catalyst and the first organic solvent to obtain the product; The crosslinking agent is selected from at least one of methyltrimethoxysilane, vinyl tributanone oxime silane, propyl triacetoxysilane; The organometallic catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, zinc octoate, bismuth octoate; The first organic solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dimethyl sulfoxide, dichloromethane.

10. Use of the organosilicon-modified soyaflavone adhesive according to any one of claims 1-8 in the preparation of wood-based panels.

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