Bio-based non-isocyanate polyurethane as well as preparation method and application thereof

Abstract

The invention discloses bio-based non-isocyanate polyurethane as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting a camphoric acid compound with an epoxy compound to prepare a camphoric acid-based epoxy compound; enabling the camphoric acid-based epoxy compound to react with carbon dioxide to prepare a camphoric acid-based five-membered cyclic carbonate compound; and mixing the camphoric acid-based five-membered cyclic carbonate compound with a curing agent, and carrying out curing treatment, so as to prepare the bio-based non-isocyanate polyurethane. The bio-based non-isocyanate polyurethane provided by the invention has excellent mechanical properties and thermal properties, and the self-healing efficiency of the bio-based non-isocyanate polyurethane can reach 90% or above; meanwhile, reprocessing and recycling can be conducted through physical means, the material can be applied to printing ink, anti-fake recognition, temperature response intelligent materials and the like, the application field of the material is widened, and the material has extremely wide application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of non-isocyanate polyurethanes, and particularly relates to a bio-based non-isocyanate polyurethane and its preparation method and application. Background Art

[0002] Polyurethane (PU) is a kind of polymer material formed by the polycondensation of polyisocyanates and polyols. Due to its excellent mechanical properties, solvent resistance, flexibility and processability, it has been widely used in many fields such as construction, automotive, aerospace, electronic devices, biomedical materials, etc. However, the preparation process of traditional PU usually relies on raw materials containing highly toxic isocyanates, and the synthesis of isocyanates requires the use of highly toxic phosgene. Harmful gases are easily released during its processing, posing potential hazards to the environment and human health. In addition, isocyanate residues may cause material aging and affect the service life. Therefore, developing a green polyurethane synthesis route without isocyanates has become an important research direction in the current field of polymer materials. Non-isocyanate polyurethane (NIPU) is a polyurethane material synthesized through a chemical path without isocyanates. The most representative synthesis method is the addition reaction of five-membered cyclic carbonates and amines. This method avoids the use of isocyanates and endows NIPU with more excellent environmental protection characteristics. However, the existing NIPU materials still have certain limitations in terms of mechanical properties, thermal stability, solvent resistance and processability. Therefore, it is urgent to develop a new bio-based NIPU system to improve its comprehensive performance.

[0003] In recent years, fluorescent anti-counterfeiting materials have received extensive attention due to their visualization characteristics, high stability and the ability to exhibit special optical characteristics under ultraviolet light or specific environments. Especially materials with adjustable fluorescence emission can change colors according to external stimuli (such as temperature, solvent, electric field or pH value), thereby further improving the anti-counterfeiting level. However, there are still some problems with existing fluorescent anti-counterfeiting materials, such as poor stability, weak fluorescence intensity, single color, high preparation cost, etc. Therefore, developing environmentally friendly anti-counterfeiting materials with adjustable fluorescence properties is crucial for information security and intellectual property protection. Summary of the Invention

[0004] The main purpose of the present invention is to provide a bio-based non-isocyanate polyurethane and its preparation method and application to overcome the deficiencies of the prior art.

[0005] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include:

[0006] The embodiment of the present invention provides a preparation method of a bio-based non-isocyanate polyurethane, which includes:

[0007] Reacting a camphoric acid compound with an epoxy compound to obtain a camphoric acid-based epoxy compound;

[0008] React a camphoric acid-based epoxy compound with carbon dioxide to obtain a camphoric acid-based five-membered cyclic carbonate compound;

[0009] In addition, mix the camphoric acid-based five-membered cyclic carbonate compound with a curing agent for curing treatment to obtain a bio-based non-isocyanate polyurethane.

[0010] An embodiment of the present invention also provides a bio-based non-isocyanate polyurethane prepared by the foregoing preparation method.

[0011] An embodiment of the present invention also provides the use of the foregoing bio-based non-isocyanate polyurethane in inks, anti-counterfeiting identification or temperature-responsive intelligent materials.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0013] (1) The present invention uses renewable camphoric acid and carbon dioxide as raw materials, and the prepared bio-based non-isocyanate polyurethane can effectively alleviate the increasingly depleted current petroleum resources and achieve green chemistry;

[0014] (2) The present invention can regulate the crosslinking degree of the bio-based non-isocyanate polyurethane by fixing the proportion of the camphoric acid-based cyclic carbonate and adjusting the proportion of the curing agent diamine and triamine added, and finally realize the regulation of its mechanical properties, thermal properties and fluorescence intensity;

[0015] (3) The bio-based non-isocyanate polyurethane synthesized by the present invention has excellent mechanical properties, thermal stability, solvent resistance, and the fluorescence emission color can change with temperature, which can provide a new way for anti-counterfeiting information security and meet the application requirements of anti-counterfeiting functional materials;

[0016] (4) The bio-based non-isocyanate polyurethane material synthesized by the present invention simultaneously has reprocessability and self-healing properties similar to those of thermoplastics, providing a new idea for solving the problems of minor damage during the use of traditional fluorescent materials and physical recycling after use.

[0017] (5) The synthesis process described in the present invention has the advantages of mild reaction conditions, simple process, and environmental friendliness. Description of the Drawings

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0019] Figure 1 It is a schematic diagram of the preparation technical route of the present invention;

[0020] Figure 2 is the 1H NMR spectrum of camphoric acid-based epoxy compounds in Examples 1-6 of the present invention;

[0021] Figure 3 is the 1H NMR spectrum of camphoric acid-based five-membered cyclic carbonates in Examples 1-6 of the present invention;

[0022] Figure 4 is the Fourier transform infrared spectrum of the bio-based non-isocyanate polyurethane prepared in Examples 1-6 of the present invention;

[0023] Figure 5 is the stress-strain curve of the bio-based non-isocyanate polyurethane prepared in Examples 1-6 of the present invention;

[0024] Figure 6 is the thermogravimetric analysis curve of the bio-based non-isocyanate polyurethane prepared in Examples 1-6 of the present invention;

[0025] Figure 7 is the fluorescence intensity curve of the bio-based non-isocyanate polyurethane prepared in Examples 1-6 of the present invention;

[0026] Figures 8a - 8b is the physical picture of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention under ultraviolet lamp irradiation at room temperature and 90 °C;

[0027] Figure 9 is the solvent resistance diagram of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention;

[0028] Figure 10 is the physical picture of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention before and after hot pressing recovery;

[0029] Figure 11 is the physical picture of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention before and after self-healing. Detailed implementation manners

[0030] In view of the deficiencies of the prior art, through long-term research and a large number of practices, the inventors of this case have been able to propose the technical solution of the present invention. The present invention uses renewable camphoric acid and renewable resource carbon dioxide as raw materials, converts them into camphoric acid-based cyclic carbonates, and uses a mixture of long-chain bio-based diamines and polyether-based triamines as curing agents. By changing the ratio of long-chain bio-based diamines and polyether-based triamines, the internal chain structure of camphoric acid-based non-isocyanate polyurethane is adjusted, and finally its performance is regulated. The prepared camphoric acid-based non-isocyanate polyurethane exhibits excellent thermal stability, mechanical properties, solvent resistance, and fluorescence emission color coordination. The operation of the present invention is simple. Through a simple, green and environmentally friendly synthesis process, the problems of toxicity and environmental pollution in the synthesis of polyurethane from isocyanate are solved. A bio-based non-isocyanate polyurethane material with unconventional fluorescence properties, self-healing and reprocessability is prepared, showing the potential to replace traditional petroleum-based thermosetting materials, and solving the problems of low fluorescence intensity and non-variation of fluorescence color with temperature in traditional polyurethane materials.

[0031] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] Specifically, as an aspect of the technical solution of the present invention, a preparation method of a bio-based non-isocyanate polyurethane involves:

[0033] Reacting a camphoric acid compound with an epoxy compound to obtain a camphoric acid-based epoxy compound;

[0034] Reacting the camphoric acid-based epoxy compound with carbon dioxide to obtain a camphoric acid-based five-membered cyclic carbonate compound;

[0035] And, mixing the camphoric acid-based five-membered cyclic carbonate compound with a curing agent for curing treatment to obtain a bio-based non-isocyanate polyurethane.

[0036] In some preferred embodiments, the preparation method specifically includes: mixing a camphoric acid compound with epichlorohydrin and reacting at 90 - 120 °C for 3 - 6 h, then cooling to 50 - 70 °C and continuing to react for 5 - 8 h, then adding an alkaline solution, and then performing liquid separation, washing, distillation, and drying treatments to obtain a camphoric acid-based epoxy compound.

[0037] Furthermore, the camphoric acid compound includes any one or a combination of more than one of 3-hydroxycamphoric acid, 2-hydroxy-1,3-camphor dicarboxylic acid, camphoric acid, dimethyl camphorate, phenyl camphorate, and is not limited thereto.

[0038] Furthermore, the epoxy compound includes any one or a combination of more than one of ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,4-epoxybutane, epichlorohydrin, and is not limited thereto.

[0039] Furthermore, the mass ratio of the camphoric acid compound to the epoxy compound is 1:8 - 18.

[0040] Furthermore, the alkaline solution includes any one or a combination of more than one of sodium hydroxide solution, potassium hydroxide, and sodium bicarbonate, and is not limited thereto.

[0041] Furthermore, the concentration of the alkaline solution is 30 - 50 wt%.

[0042] Furthermore, the detergent used in the washing treatment includes any one or a combination of more than one of ethanol, NaCl solution, deionized water, and ethyl acetate, and is not limited thereto.

[0043] In some preferred embodiments, the preparation method specifically includes: placing the camphoric acid-based epoxy compound and the catalyst in a closed reaction device, then introducing carbon dioxide and reacting for 8 - 10 h under the conditions that the carbon dioxide pressure in the reaction device is 1 - 3 MPa and the temperature is 130 - 150 °C to obtain the camphoric acid-based five-membered cyclic carbonate compound.

[0044] Furthermore, the catalyst includes any one or a combination of more than one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, dodecylaminotrimethylammonium chloride, and dibutyltin dilaurate, and is not limited thereto.

[0045] Furthermore, the mass ratio of the catalyst to the camphoric acid-based epoxy compound is 5 - 10:100.

[0046] In some preferred embodiments, the preparation method specifically includes: mixing the camphoric acid-based five-membered cyclic carbonate compound, the curing agent, and the solvent and reacting at 60 - 80 °C for 1 - 3 h in an inert gas atmosphere, then drying at 60 - 90 °C for 3 - 6 h to remove the solvent, and then vacuum-curing at 120 - 150 °C for 8 - 12 h to obtain the bio-based non-isocyanate polyurethane.

[0047] Further, the curing agent includes diamine compounds and triamine compounds; wherein, the mass ratio of the diamine compounds to the triamine compounds is 10:0 - 0:10; the diamine compounds include any one or a combination of more than one of p-phenylenediamine, ethylenediamine, polyetheramine D-230, polyetheramine D-400, aliphatic amine Priamine1074, 4,7,10-trioxa-1,13-tridecanediamine; the triamine compounds include any one or a combination of more than one of trimethylamine, triethylamine, N,N-dimethylaniline, triethanolamine, trimethylolpropane tripropyleneglycol ether (amino-terminated), tris(2-aminoethyl)amine, and is not limited thereto.

[0048] Further, the solvent includes any one or a combination of more than one of deionized water, ethyl acetate, methanol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, 2-butanone, acetonitrile, and is not limited thereto.

[0049] Further, the mass ratio of the solvent to the sum of the camphoric acid-based five-membered cyclic carbonate compound and the curing agent is 100 - 500:100.

[0050] In some preferred embodiments, the preparation method of the bio-based non-isocyanate polyurethane includes (the steps are as Figure 1 shown):

[0051] (1) Put the camphoric acid compound into a three-necked flask, add the epoxy compound, the reaction temperature is 90 - 120 °C, after reacting for 3 - 6 h, adjust the reaction temperature to 50 - 70 °C, then dropwise add a 30% - 50% sodium hydroxide solution by mass fraction, and then obtain the camphoric acid-based epoxy compound through liquid separation, vacuum distillation, and drying.

[0052] (2) Put the camphoric acid-based epoxy compound prepared in step (1) into a closed reaction kettle, add a catalyst, the reaction temperature is 130 - 150 °C, the carbon dioxide pressure in the reaction kettle is 1 - 3 MPa, and the reaction time is 8 - 10 h to prepare the camphoric acid-based five-membered cyclic carbonate compound.

[0053] (3) Mix and dissolve the camphoric acid-based five-membered cyclic carbonate compound obtained in step (2) and the curing agent in a solvent, protect with an inert gas, the reaction temperature is 60 - 80 °C, the reaction time is 1 - 3 h, and then pour the reacted liquid onto a 5×5 cm tetrafluoroethylene plate for thermal curing.

[0054] (4) First, put the tetrafluoroethylene plate in step (3) into a blast drying oven at 60 - 90 °C for 3 - 6 h to volatilize the solvent, and then put it into a vacuum drying oven at 120 - 150 °C for 8 - 12 h for thermal curing to prepare the camphoric acid-based non-isocyanate polyurethane.

[0055] Preferably, in the step (1), the camphoric acid compound is at least one of 3-hydroxycamphoric acid, 2-hydroxy-1,3-camphor dicarboxylic acid, camphoric acid, dimethyl camphorate, and phenyl camphorate.

[0056] Preferably, in the step (2), the catalyst is one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, dodecyltrimethylammonium chloride, and dibutyltin dilaurate.

[0057] Preferably, in the step (2), the addition amount of the catalyst is 5-10% of the total mass of the camphoric acid-based epoxy compound.

[0058] Preferably, in the step (3), the curing agent includes a diamine compound and a triamine compound, and a series of camphoric acid-based non-isocyanate polyurethanes are obtained by adjusting the ratio of the two amines.

[0059] Preferably, in the step (3), the diamine compound is one of 1,6-hexanediamine, p-phenylenediamine, ethylenediamine, polyetheramine D-230, polyetheramine D-400, aliphatic amine Priamine1074, and 4,7,10-trioxa-1,13-tridecanediamine.

[0060] Preferably, in the step (3), the triamine compound is one of trimethylamine, triethylamine, N,N-dimethylaniline, triethanolamine, trimethylolpropane tripropyleneglycol ether (amine-terminated), diethylenetriamine, and tris(2-aminoethyl)amine.

[0061] Preferably, in the step (3), the solvent includes any one or a combination of deionized water, ethyl acetate, methanol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, 2-butanone, and acetonitrile.

[0062] Preferably, in the step (3), the inert gas is nitrogen and / or argon.

[0063] Preferably, in the step (3), the addition amount of the solvent is 100-500% of the total mass of the camphoric acid-based five-membered cyclic carbonate compound and the curing agent.

[0064] The present invention uses renewable camphoric acid and carbon dioxide as raw materials to prepare bio-based non-isocyanate polyurethane, which can effectively alleviate the increasingly depleted current petroleum resources. By fixing the proportion of camphoric acid-based cyclic carbonate, the proportion of the curing agent diamine and triamine added can be adjusted to regulate the crosslinking degree of bio-based non-isocyanate polyurethane, and finally the regulation of its mechanical properties, thermal properties and fluorescence intensity can be realized; at the same time, the bio-based non-isocyanate polyurethane synthesized by the present invention has excellent mechanical properties, thermal stability, solvent resistance and the fluorescence emission color can change with temperature, which can provide a new way for anti-counterfeiting information security and meet the application requirements of anti-counterfeiting functional materials.

[0065] The bio-based non-isocyanate polyurethane material synthesized by the present invention has reprocessability and self-healing properties similar to thermoplastics, providing a new idea for solving the problems of minor damage during the use of traditional fluorescent materials and physical recycling after use. The synthesis process described in the present invention has the advantages of mild reaction conditions, simple process, environmental friendliness, etc.

[0066] The fluorescent NIPU material (the aforementioned bio-based non-isocyanate polyurethane) in the present invention is based on a camphoric acid-based non-isocyanate polyurethane system and has special fluorescence emission characteristics. By regulating the internal chain structure and chemical environment of the polymer, the present study has achieved the controllability of fluorescence color, that is, the material can exhibit different fluorescence emission characteristics under different temperature or solvent environments, thus endowing it with potential for multifunctional applications. Compared with traditional fluorescent polyurethanes, the materials in this study not only have higher thermal stability, solvent resistance and mechanical strength, but can also be reprocessed by physical means without affecting their fluorescence properties, providing an important reference for the development of new intelligent optical materials.

[0067] Another aspect of the embodiments of the present invention also provides the bio-based non-isocyanate polyurethane prepared by the aforementioned preparation method.

[0068] In some preferred embodiments, the bio-based non-isocyanate polyurethane exhibits green light under irradiation with an emission wavelength of 365 nm at room temperature.

[0069] In some preferred embodiments, the bio-based non-isocyanate polyurethane exhibits yellow light under irradiation with an emission wavelength of 365 nm at 90 °C - 150 °C.

[0070] In some preferred embodiments, the bio-based non-isocyanate polyurethane is dark brown in visible light.

[0071] In some preferred embodiments, the bio-based non-isocyanate polyurethane can be found to produce an unconventional fluorescence phenomenon and emit green light under a UV analyzer with an emission wavelength of 365 nm at room temperature.

[0072] In some preferred embodiments, the bio-based non-isocyanate polyurethane is heated to 90°C - 150°C, and an unconventional fluorescence phenomenon of emitting yellow light is found under an ultraviolet analyzer with an emission wavelength of 365 nm.

[0073] In some preferred embodiments, after the surface of the bio-based non-isocyanate polyurethane is scratched with a sharp knife, it can be self-healed and restored to its original state by heating on a hot stage at 150°C for 0.5 h.

[0074] Another aspect of the embodiments of the present invention also provides the use of the aforementioned bio-based non-isocyanate polyurethane in inks, anti-counterfeiting identification, or temperature-responsive intelligent materials.

[0075] The bio-based non-isocyanate polyurethane provided by the present invention has excellent mechanical properties, thermal properties, and a self-healing efficiency of up to more than 90%; at the same time, it can be reprocessed and recycled by physical means without changing the original chemical structure and mechanical properties, and it can also emit a green fluorescence phenomenon under ultraviolet light irradiation, and the sample surface emits a yellow fluorescence phenomenon when the temperature changes. At the same time, the preparation method of the present invention has the characteristics of simple process, controllable material properties, bio-based source, reprocessability, unconventional fluorescence phenomenon, etc., and can be applied to inks, anti-counterfeiting identification, temperature-responsive intelligent materials, etc., broadening its application fields and having extremely broad application prospects.

[0076] The technical solutions of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. These embodiments are implemented on the premise of the technical solutions of the invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0077] In the embodiments of the present invention, nuclear magnetic resonance hydrogen spectrum 1 1H-NMR was measured using a 400AVANCEIII type spectrometer (Spectrometer) from Bruker Corporation, 400 MHz, deuterated chloroform (CDCl3). According to the test standard of ASTM D 882, the mechanical properties of the polyurethane specimens were measured on a universal testing machine (UTM, Zwick Instruments, Model: Z1.0) at 1 KN, and the tensile rate was 50 mm / min. The fluorescence emission wavelength was measured in the range of 380 - 710 nm using a 150 W xenon lamp (Xe) fluorescence spectrometer (FL3-111), the fluorescence excitation slit width was set to 2 / 5 nm, and the excitation wavelength was 365 nm. For the solvent resistance test, the samples were respectively placed in water, acidic water (0.5 mol / L), alkaline water (0.5 mol / L), acetone, aqueous acetone solution, and acidic acetone (0.5 mol / L) solution, and whether there was dissolution was observed after heating at 50°C for 2 h. Thermal analysis was tested by a thermogravimetric analyzer (TGA09F1, Germany).

[0078] In the following examples, the experimental materials used can be purchased from regular biochemical reagent companies without special instructions.

[0079] Example 1

[0080] A preparation method of a bio-based non-isocyanate polyurethane with unconventional fluorescence, self-healing and reprocessability, comprising the following steps:

[0081] First step, add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution, stir continuously for 6 h, then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0082] Second step, add 30.0 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. Seal it and flush the reaction vessel with carbon dioxide 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, and raise the temperature to 130 °C. React for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0083] Third step, add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 10.1 g of trimethylolpropane tripropyleneglycol ether (amino-terminated) and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing. Place it in a forced-air oven, dry it at 80 °C for 6 h, then place it in a vacuum oven and dry and cure it at 120 °C for 10 h to obtain PU-1.

[0084] Example 2

[0085] First step, add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution and continuously stir for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0086] Second step, add 30.0 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. Seal the vessel and flush it with carbon dioxide 3 - 5 times to remove the air in the reaction kettle. Then introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0087] Third step, add 10.0 g of camphoric acid-based five-membered cyclic carbonate compound, 8.6 g of trimethylolpropane tripropylene glycol ether (amine-terminated), 2.7 g of aliphatic amine Priamine1074, and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing. Place it in a forced-air oven, dry it at 80 °C for 6 h, then place it in a vacuum oven and dry and cure it at 120 °C for 10 h to obtain PU-2.

[0088] Example 3

[0089] First step, add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution and continuously stir for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0090] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0091] Step 3: Add 10.0 g of camphoric acid-based five-membered cyclic carbonate compound, 6.0 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 5.4 g of aliphatic amine Priamine1074, and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing, place it in a forced-air oven, dry at 80 °C for 6 h, then place it in a vacuum oven and dry and cure at 120 °C for 10 h to obtain PU-3.

[0092] Example 4

[0093] Step 1: Add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution, stir continuously for 6 h, then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a 60 °C vacuum oven and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0094] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0095] Step 3: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 4.3 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 8.1 g of aliphatic amine Priamine1074, and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing, place it in a forced-air oven, dry at 80 °C for 6 h, then place it in a vacuum oven and dry and cure at 120 °C for 10 h to obtain PU-4.

[0096] Example 5

[0097] First step: Add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C and keep it for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution and continuously stir for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0098] Second step: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times to remove the air in the reaction kettle. Then introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0099] Third step: Add 10 g (0.025 mo1) of camphoric acid-based five-membered cyclic carbonate compound, 2.2 g of trimethylolpropane tripropylene glycol ether (amine-terminated), 10.7 g of aliphatic amine Priamine1074, and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing. Place it in a blast drying oven, dry at 80 °C for 6 h, then place it in a vacuum oven and dry and cure at 130 °C for 9 h to obtain PU-5.

[0100] Example 6

[0101] First step: Add 30.0 g of camphoric acid, 1445 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C and keep it for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution to the reaction solution and continuously stir for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0102] The second step is to add 30 g of a camphorate epoxy compound and 0.4 g of tetrabutylammonium bromide to a high-pressure reaction vessel equipped with a mechanical stirring paddle, seal the reaction vessel, and then pass carbon dioxide to flush the reaction vessel 3-5 times. After removing the air in the reaction vessel, pass carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130° C., and react for 8 hours to obtain a camphorate-based five-membered cyclic carbonate compound (2);

[0103] Step 3: Add 10g of camphor acid-based five-membered cyclic carbonate compound, 13.4g of aliphatic amine Priamine1074 and 23g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70°C, start magnetic stirring, introduce nitrogen as protective gas, react for 1h, pour into a 5×5cm tetrafluoroethylene plate for thermal curing, put into a blast oven, dry at 80°C for 6h, put into a vacuum oven, dry and cure at 130°C for 9h, and obtain PU-6.

[0104] Example 7

[0105] The first step is to add 30.0g of camphoric acid, 160g of propylene oxide and 60g of tetrahydrofuran into a three-necked flask. Heat the mixture to 90°C for 4h, then cool it to 55°C, slowly drop 45% potassium hydroxide solution into the reaction solution, continue stirring for 6h, then add a certain amount of deionized water and stir for 0.5h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water for 3-5 times, then take the organic layer and use rotary evaporation to remove part of the ionized water and epichlorohydrin, dry it with anhydrous magnesium sulfate, and then put it into a 60°C vacuum oven to dry for 12h to obtain a camphoric acid-based epoxy compound (1);

[0106] The second step is to add 30 g of a camphorate epoxy compound and 0.4 g of tetrabutylammonium bromide to a high-pressure reaction vessel equipped with a mechanical stirring paddle, seal the reaction vessel, and then pass carbon dioxide to flush the reaction vessel 3-5 times. After removing the air in the reaction vessel, pass carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130° C., and react for 8 hours to obtain a camphorate-based five-membered cyclic carbonate compound (2);

[0107] The third step is to add 10g of camphor acid-based five-membered cyclic carbonate compound, 1.1g of trimethylolpropane tripropylene glycol ether (amino-terminated), 12.1g of aliphatic amine Priamine1074 and 23g of tetrahydrofuran into a three-necked flask. The mixture temperature is raised to 70°C, magnetic stirring is turned on, nitrogen is introduced as a protective gas, and after reacting for 1h, it is poured into a 5×5cm tetrafluoroethylene plate for thermal curing, placed in a blast oven, dried at 80°C for 5h, placed in a vacuum oven, and dried and cured at 130°C for 9h to obtain PU-7.

[0108] Example 8

[0109] Step 1: Add 30.0 g of camphoric acid, 138.7 g of propylene oxide and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then cool it to 55 °C randomly. Slowly add 45% sodium hydroxide solution to the reaction solution and stir continuously for 5 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times. Immediately take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 80 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0110] Step 2: Add 30.0 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirrer. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times to remove the air in the reaction kettle. Then introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, and raise the temperature to 130 °C. React for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0111] Step 3: Add 10 g (0.025 mo1) of camphoric acid-based five-membered cyclic carbonate compound, 3.2 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 9.4 g of aliphatic amine Priamine1074 and 23 g of ethanol into a three-necked flask. Raise the temperature of the mixture to 70 °C, turn on the magnetic stirrer, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing. Place it in a blast drying oven, dry it at 80 °C for 5 h, then place it in a vacuum oven and dry and cure it at 140 °C for 10 h to obtain PU-8.

[0112] Example 9

[0113] Step 1: Add 30.0 g of camphoric acid, 156 g of ethylene oxide and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then cool it to 55 °C randomly. Slowly add 45% sodium bicarbonate solution to the reaction solution and stir continuously for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times. Immediately take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0114] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0115] Step 3: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 5.4 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 6.7 g of aliphatic amine Priamine1074 and 23 g of ethyl acetate into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing, place it in a forced-air oven, dry at 80 °C for 5 h, then place it in a vacuum oven and dry and cure at 130 °C for 9 h to obtain PU-9.

[0116] Example 10

[0117] Step 1: Add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then cool it to 55 °C randomly. Slowly drop 45% sodium hydroxide solution into the reaction solution, stir continuously for 6 h, then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water for 3 - 5 times, then take the organic layer and remove part of the deionized water and epichlorohydrin by rotary evaporation. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0118] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium iodide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0119] Step 3: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 7.5 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 4 g of aliphatic amine Priamine1074 and 23 g of methanol into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce argon as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing, place it in a forced-air oven, dry at 80 °C for 4 h, then place it in a vacuum oven and dry and cure at 120 °C for 8 h to obtain PU-10.

[0120] Example 11

[0121] First step: Add 30.0 g of camphoric acid, 165 g of epichlorohydrin and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C and keep it for 4 h. Then cool it to 55 °C randomly. Slowly add 40% sodium hydroxide solution to the reaction solution and stir continuously for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water for 3 - 5 times. Immediately take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, put it into a vacuum oven at 60 °C and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0122] Second step: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times to remove the air in the reaction kettle. Then introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, and raise the temperature to 130 °C. React for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0123] Third step: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 0.5 g of triethylamine, 1.9 g of 1,6-hexanediamine and 13 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing. Put it into a blast drying oven, dry at 80 °C for 4 h, and then put it into a vacuum oven and dry and cure at 120 °C for 8 h to obtain PU-11.

[0124] Example 12

[0125] First step: Add 30.0 g of camphoric acid, 138.7 g of epichlorohydrin and 60 g of tetrahydrofuran into a three-necked flask. Heat the mixture to 100 °C and keep it for 4 h. Then cool it to 65 °C randomly. Slowly add 35% sodium hydroxide solution to the reaction solution and stir continuously for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water for 3 - 5 times. Immediately take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, put it into a vacuum oven at 60 °C and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0126] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium hydrogensulfate into a high-pressure reaction vessel equipped with a mechanical stirrer paddle. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0127] Step 3: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 2.2 g of trimethylolpropane tripropylene glycol ether (amino-terminated), 8 g of polyetheramine D-400, and 23 g of 2-butanone into a three-necked flask. Raise the temperature of the mixture to 70 °C, turn on the magnetic stirrer, introduce nitrogen as a protective gas, and after reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing. Place it in a blast drying oven, dry at 80 °C for 4 h, then place it in a vacuum drying oven, and dry and cure at 120 °C for 8 h to obtain PU-12.

[0128] Example 13

[0129] Step 1: Add 30.0 g of camphoric acid, 138.7 g of 1,4-epoxybutane, and 60 g of ethyl acetate into a three-necked flask. Heat the mixture to 110 °C for 4 h, then randomly cool to 55 °C. Slowly drop 45% sodium hydroxide solution into the reaction solution while continuously stirring for 8 h, and then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separating funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a 60 °C vacuum drying oven and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0130] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirrer paddle. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0131] Step 3: Add 10 g (0.025 mol) of camphoric acid-based five-membered cyclic carbonate compound, 2.2 g of triethanolamine, 2.3 g of polyetheramine D-230, and 13 g of ethyl acetate into a three-necked flask. Raise the temperature of the mixture to 70 °C, turn on the magnetic stirrer, introduce nitrogen as a protective gas, and after reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing. Place it in a blast drying oven, dry at 80 °C for 4 h, then place it in a vacuum drying oven, and dry and cure at 120 °C for 8 h to obtain PU-13.

[0132] Example 14

[0133] Step 1: Add 30.0 g of dimethyl camphorate, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 55 °C. Slowly add 45% sodium hydroxide solution dropwise to the reaction solution, and continuously stir for 6 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0134] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirrer. After sealing, flush the reaction vessel with carbon dioxide 3 - 5 times to remove the air in the reaction kettle. Then, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, and raise the temperature to 130 °C. React for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0135] Step 3: Add 10 g (0.025 mol) of camphoric acid-based five-membered cyclic carbonate compound, 0.7 g of triethanolamine, 10.7 g of fatty amine Priamine1074, and 23 g of methanol into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm tetrafluoroethylene plate for thermal curing. Place it in a forced-air oven, dry at 80 °C for 4 h, then place it in a vacuum oven and dry and cure at 120 °C for 8 h to obtain PU-14.

[0136] Example 15

[0137] Step 1: Add 30.0 g of 3-hydroxycamphoric acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 90 °C for 4 h, then randomly cool it to 50 °C. Slowly add 45% sodium hydroxide solution dropwise to the reaction solution, and continuously stir for 8 h. Then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0138] Step 2: Add 30 g of camphoric acid-based epoxide compound and 0.4 g of tetrabutylammonium chloride into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 1 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 130 °C, and react for 10 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0139] Step 3: Add 10 g (0.025 mo1) of camphoric acid-based five-membered cyclic carbonate compound, 2.2 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 2.2 g of p-phenylenediamine, and 13 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 60 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing. Place it in a forced-air oven, dry at 60 °C for 6 h, then place it in a vacuum oven, and dry and cure at 120 °C for 12 h to obtain PU-15.

[0140] Example 16

[0141] Step 1: Add 30.0 g of phenyl camphorate, 138.7 g of epichlorohydrin, and 60 g of tetrahydrofuran into a three-necked flask. Heat the mixture to 110 °C for 4 h, then cool it to 55 °C randomly. Slowly drop 45% sodium hydroxide solution into the reaction solution, stir continuously for 6 h, then add a certain amount of deionized water and stir for 0.5 h. Pour the mixture into a separatory funnel, separate the organic layer, wash it with deionized water for 3 - 5 times. Then take the organic layer and remove part of the deionized water and epichlorohydrin by rotary evaporation. After drying with anhydrous magnesium sulfate, place it in a 60 °C vacuum oven and dry for 12 h to obtain camphoric acid-based epoxy compound (1);

[0142] Step 2: Add 30 g of camphoric acid-based epoxide compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirring paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times. After removing the air in the reaction kettle, introduce carbon dioxide gas to 2 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 140 °C, and react for 9 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0143] Step 3: Add 10 g (0.025 mol) of camphoric acid-based five-membered cyclic carbonate compound, 0.5 g of diethylenetriamine, 10.7 g of aliphatic amine Priamine1074, and 23 g of N,N-dimethylformamide into a three-necked flask. Raise the temperature of the mixture to 70 °C, start magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5x5 cm polytetrafluoroethylene plate for thermal curing. Place it in a forced-air oven, dry at 80 °C for 4 h, then place it in a vacuum oven, and dry and cure at 130 °C for 9 h to obtain PU-16.

[0144] Example 17

[0145] Step 1: Add 30.0 g of 2-hydroxy-1,3-camphor dicarboxylic acid, 138.7 g of epichlorohydrin, and 60 g of dimethyl sulfoxide into a three-necked flask. Heat the mixture to 120 °C and keep it for 3 h, then randomly cool it to 70 °C. Slowly dropwise add 35% sodium hydroxide solution into the reaction solution, continuously stir for 5 h, then add a certain amount of deionized water and stir for 0.5 h. Pour the mixed solution into a separatory funnel, separate the organic layer, wash it with deionized water for 3 - 5 times, then take the organic layer and use rotary evaporation to remove part of the deionized water and epichlorohydrin. After drying with anhydrous magnesium sulfate, place it in a vacuum oven at 60 °C for 12 h to obtain camphoric acid-based epoxy compound (1);

[0146] Step 2: Add 30 g of camphoric acid-based epoxy compound and 0.4 g of tetrabutylammonium bromide into a high-pressure reaction vessel equipped with a mechanical stirrer paddle. After sealing, flush the reaction vessel with carbon dioxide for 3 - 5 times to remove the air in the reaction kettle, then introduce carbon dioxide gas to 3 MPa, turn on the stirring speed to 330 rpm, raise the temperature to 150 °C, and react for 8 h to obtain camphoric acid-based five-membered cyclic carbonate compound (2);

[0147] Step 3: Add 10 g of camphoric acid-based five-membered cyclic carbonate compound, 5.4 g of trimethylolpropane tripropyleneglycol ether (amine-terminated), 1.5 g of 1,6-hexanediamine, and 23 g of deionized water into a three-necked flask. Raise the temperature of the mixture to 80 °C, turn on the magnetic stirring, introduce nitrogen as a protective gas. After reacting for 1 h, pour it onto a 5×5 cm polytetrafluoroethylene plate for thermal curing, place it in a blast drying oven, dry it at 90 °C for 3 h, then put it into a vacuum oven and dry and cure it at 150 °C for 8 h to obtain PU-17.

[0148] Performance Characterization:

[0149] 1. Nuclear Magnetic Resonance ( 1 H-NMR)

[0150] At room temperature, using tetramethylsilane as an internal standard, perform 1 H-NMR spectroscopy on AVANCE III (400 MHz), and the sample concentration is 1 - 5 wt%.

[0151] The nuclear magnetic resonance hydrogen spectrum diagrams of camphoric acid-based epoxy compounds in Examples 1 - 6 are as Figure 2 shown, and the nuclear magnetic resonance hydrogen spectrum diagrams of camphoric acid-based five-membered cyclic carbonate compounds in Examples 1 - 6 are as Figure 3 shown.

[0152] 2. Fourier Transform Infrared Spectrogram

[0153] Using a microscopic infrared spectrometer (model: Cary660), the ATR (total reflection) mode was used for testing. The specific test conditions included: the number of scans was set to 32 times, the spectral range of the test was from 4000 to 400 cm- 1 , and air was used as the background to complete the test in absorbance mode.

[0154] The Fourier transform infrared spectra of the bio-based non-isocyanate polyurethanes prepared in Examples 1-6 are as Figure 4 shown. From Figure 4 it can be seen that the bio-based non-isocyanate polyurethanes with unconventional fluorescence properties and reprocessability prepared in Examples 1-6 were all successfully prepared, and all characteristic peaks appeared.

[0155] 3. Mechanical properties

[0156] The mechanical properties of the samples were measured using a universal testing machine (UTM, Zwick Instruments, model: Z1.0), and the tensile rate was maintained at 50 mm / min.

[0157] The stress-strain curves of the bio-based non-isocyanate polyurethanes prepared in Examples 1-6 are as Figure 5 shown. From Figure 5 it can be seen that the mechanical properties of the bio-based non-isocyanate polyurethanes with unconventional fluorescence properties and reprocessability prepared in Examples 1-6 changed with different components and could meet the requirements of different conditions.

[0158] The physical pictures of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention before and after hot pressing recovery are as Figure 10 shown. From Figure 10 it can be seen that taking Example 2 as an example, after the damaged sample was hot pressed and reshaped, the hot pressed sample could be completely formed and had a stable structure, meeting the usage requirements.

[0159] The physical pictures of the bio-based non-isocyanate polyurethane prepared in Example 2 of the present invention before and after self-healing are as Figure 11 shown. From Figure 11 it can be seen that taking Example 2 as an example, after the sample was cut with scissors and placed in an oven at 150 °C for 30 min, it could return to its original state and had a stable structure, meeting the usage requirements.

[0160] 4. Thermal stability

[0161] The thermogravimetric analysis curves of the bio-based non-isocyanate polyurethanes prepared in Examples 1-6 are as Figure 6 shown. From Figure 6 it can be seen that the T of the bio-based non-isocyanate polyurethanes with unconventional fluorescence properties and reprocessability prepared in Examples 1-6 d5The percentage is above 270 °C, indicating that the prepared camphoric acid-based non-isocyanate polyurethane has good thermal stability.

[0162] 5. Fluorescence intensity

[0163] The fluorescence intensity curves of the bio-based non-isocyanate polyurethanes prepared in Examples 1-6 are as Figure 7 shown. The structures of the camphoric acid-based non-isocyanate polyurethanes prepared in Examples 1-6 of the present invention are as Figure 1 shown. Due to the presence of auxochromic groups such as C=O, C-N, N-H, and -OH in the structure, it can exhibit photoluminescence behavior in a highly aggregated state, and this phenomenon is called cluster luminescence. Materials with cluster luminescence properties exhibit green fluorescence under ultraviolet excitation. It is measured using a 150W xenon lamp (Xe) fluorescence spectrometer (FL3-111) with a fluorescence emission wavelength in the range of 380 - 710 nm, the fluorescence excitation slit width is set to 2 / 5 nm, and the excitation wavelength is 365 nm. From Figure 7 it can be seen that the fluorescence intensities of the bio-based non-isocyanate polyurethanes with unconventional fluorescence properties and reprocessability prepared in Examples 1-6 change with different components, which can meet the requirements of different conditions. The physical diagrams of the bio-based non-isocyanate polyurethane prepared in Example 2 under ultraviolet lamp irradiation at room temperature and 90 °C are as Figures 8a - 8b shown. From Figures 8a - 8b it can be seen that under ultraviolet light irradiation at room temperature, the sample emits green fluorescence. When the temperature rises to 90 °C, the wavelength undergoes a red shift, and the sample emits yellow fluorescence.

[0164] 6. Solvent resistance

[0165] Approximately 10 mg of the sample obtained in Example 2 was separately placed into water, acidic water (0.5 mol / L HCl), basic water (0.5 mol / L NaOH), acetone, acidic acetone (0.5 mol / L HCl), and acetonitrile solution, and whether there was dissolution was observed after heating at 50 °C for 2 h, as Figure 9 shown.

[0166] In addition, the inventors of this case also referred to the foregoing examples and conducted tests with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0167] It should be understood that the technical solutions of the present invention are not limited to the limitations of the above specific embodiments. Any technical deformation made according to the technical solutions of the present invention without departing from the spirit of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A preparation method of a bio-based non-isocyanate polyurethane, characterized in that, Comprising: Reacting a camphoric acid compound with an epoxy compound to obtain a camphoric acid-based epoxy compound; Reacting the camphoric acid-based epoxy compound with carbon dioxide to obtain a camphoric acid-based five-membered cyclic carbonate compound; And mixing the camphoric acid-based five-membered cyclic carbonate compound with a curing agent for curing treatment to obtain a bio-based non-isocyanate polyurethane.

2. The preparation method according to claim 1, wherein Specifically comprising: Mixing a camphoric acid compound with epichlorohydrin and reacting at 90 - 120 °C for 3 - 6 h, then cooling to 50 - 70 °C and continuing to react for 5 - 8 h, then adding an alkaline solution, and then performing liquid separation, washing, distillation, and drying treatments to obtain a camphoric acid-based epoxy compound.

3. The preparation method according to claim 2, wherein: The camphoric acid compound includes any one or a combination of more than one of 3-hydroxycamphoric acid, 2-hydroxy-1,3-camphor dicarboxylic acid, camphoric acid, dimethyl camphorate, and phenyl camphorate; And / or, the epoxy compound includes any one or a combination of more than one of ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,4-epoxybutane, and epichlorohydrin; And / or, the mass ratio of the camphoric acid compound to the epoxy compound is 1:8 - 18; And / or, the alkaline solution includes any one or a combination of more than one of sodium hydroxide solution, potassium hydroxide, and sodium bicarbonate; and / or, the concentration of the alkaline solution is 30 - 50 wt%; And / or, the detergent used in the washing treatment includes any one or a combination of more than one of ethanol, NaCl solution, deionized water, and ethyl acetate.

4. The preparation method according to claim 1, wherein Specifically comprising: Placing the camphoric acid-based epoxy compound and a catalyst in a closed reaction device, then introducing carbon dioxide and reacting at a carbon dioxide pressure of 1 - 3 MPa and a temperature of 130 - 150 °C in the reaction device for 8 - 10 h to obtain a camphoric acid-based five-membered cyclic carbonate compound.

5. The preparation method according to claim 4, wherein: The catalyst includes any one or a combination of more than one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, dodecylaminotrimethylammonium chloride, and dibutyltin dilaurate; And / or, the mass ratio of the catalyst to the camphoric acid-based epoxy compound is 5 - 10:

100.

6. The preparation method according to claim 1, wherein, Specifically comprising: Mixing the camphoric acid-based five-membered cyclic carbonate compound, a curing agent, and a solvent and in an inert gas atmosphere, first reacting at 60 - 80 °C for 1 - 3 h, then drying at 60 - 90 °C for 3 - 6 h to remove the solvent, and then vacuum curing at 120 - 150 °C for 8 - 12 h to obtain a bio-based non-isocyanate polyurethane.

7. The preparation method according to claim 6, characterized in that: The curing agent includes diamine compounds and triamine compounds; wherein, the mass ratio of the diamine compounds to the triamine compounds is 10:0 - 0:10; the diamine compounds include any one or a combination of more than one of p-phenylenediamine, ethylenediamine, polyetheramine D-230, polyetheramine D-400, aliphatic amine Priamine1074, 4,7,10-trioxa-1,13-tridecanediamine; the triamine compounds include any one or a combination of more than one of trimethylamine, triethylamine, N,N-dimethylaniline, triethanolamine, trimethylolpropane tripropyleneglycol ether (amino-terminated), tris(2-aminoethyl)amine; and / or, the solvent includes any one or a combination of more than one of deionized water, ethyl acetate, methanol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, 2-butanone, acetonitrile; and / or, the mass ratio of the solvent to the sum of the camphoric acid-based five-membered cyclic carbonate compound and the curing agent is 100 - 500:

100.

8. A bio-based non-isocyanate polyurethane prepared by the preparation method according to any one of claims 1 - 7.

9. The bio-based non-isocyanate polyurethane according to claim 8, characterized in that: The bio-based non-isocyanate polyurethane emits green light under irradiation with an emission wavelength of 365 nm at room temperature; and / or, the bio-based non-isocyanate polyurethane emits yellow light under irradiation with an emission wavelength of 365 nm at 90°C - 150°C.

10. Use of the bio-based non-isocyanate polyurethane according to claim 8 or 9 in inks, anti-counterfeiting identification or temperature-responsive intelligent materials.

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