Quantum dot catalyzed rapid light-cured cellulose resin adhesive, and preparation method and application thereof

Abstract

The invention discloses a quantum dot catalyzed rapid light-cured cellulose resin adhesive, a preparation method and application, and the preparation method comprises the following steps: carrying out acylating chlorination on a photoinitiator primer by using oxalyl chloride to obtain an acylating chlorination product; dissolving cellulose, a catalyst and the acylating chlorination product in a good solvent, reacting, precipitating in deionized water, collecting the precipitate, and drying to obtain a cellulose macromolecular photoinitiator; mixing and stirring the acrylate monomer A, the acrylate monomer B, the cellulose macromolecular photoinitiator and the quantum dots to obtain the adhesive. According to the method, the rapid light-cured cellulose resin adhesive with excellent performance can be simply and efficiently prepared, the prepared cellulose resin adhesive can be cured for 0.2-1 min under a 365 nm ultraviolet lamp to achieve adhesion of a transparent base material, the method has the advantages of being environmentally friendly, easy to operate and wide in applicable monomer range, and the application range of cellulose is further widened.

Description

Technical Field

[0001] This invention relates to a quantum dot-catalyzed, rapidly photocurable cellulose resin adhesive, its preparation method, and its application, specifically belonging to the field of cellulose modification technology. Background Technology

[0002] Cellulose is one of the most widely sourced and abundant natural polymers on Earth. It has advantages such as high biocompatibility, excellent mechanical properties, low cost and environmental friendliness. It is widely used in composite materials, membrane materials, drug delivery and insulation materials and is an important research project for researchers to address the energy crisis.

[0003] Adhesives, also known as binders or adhesives, are substances that can join two or more homogeneous or heterogeneous materials together, achieving sufficient strength after curing. They are an indispensable material in modern industry and daily life. Currently, adhesives are mainly based on synthetic polymers, with most raw materials derived from petroleum fossil products, easily generating large amounts of waste and pollution. Furthermore, the curing process is mostly heat-curing, which is time-consuming and energy-intensive. Existing technologies lack environmentally friendly, low-energy-consumption adhesives that can be rapidly cured by light. Summary of the Invention

[0004] The purpose of this invention is to provide a novel quantum dot-catalyzed, rapidly photocurable cellulose resin adhesive, its preparation method, and its application. This adhesive also possesses strong bonding strength and rapid photocuring capability.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a quantum dot-catalyzed, rapidly photocurable cellulose resin adhesive, characterized in that its general structural formula is as follows:

[0006]

[0007] Wherein, R is a characteristic functional group of cellulose, which is any one of -H or -CH3, -CH2CH3, -CH2COOH, -COCH3, -CH2CH2OH, -CH2CH2CH2OH, and R1 and R2 are acrylate monomers, which are any two of acrylic acid, methyl methacrylate, hydroxyethyl acrylate, butyl acrylate, lauryl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, and tetrahydrofuran acrylate.

[0008] This invention also provides a method for preparing the above-mentioned quantum dot-catalyzed rapid photocurable cellulose resin adhesive, comprising the following steps:

[0009] Step 1: Acyl chloride is used to chlorinate the photoinitiator primer to obtain the acyl chloride product;

[0010] Step 2: Dissolve cellulose, catalyst, and acyl chloride product in a good solvent and react them. Then precipitate the product in deionized water, collect the precipitate and dry it to obtain the cellulose macromolecular photoinitiator.

[0011] Step 3: Mix and stir acrylate monomer A, acrylate monomer B, cellulose macromolecular photoinitiator, and quantum dots to obtain an adhesive.

[0012] Furthermore, in step 1, the molar ratio of photoinitiator primer to oxalyl chloride is 1:1 to 2.

[0013] Furthermore, the photoinitiator primer is a hydroxyl-containing cleavage photoinitiator, including any one of benzoylformic acid, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl ketone.

[0014] Furthermore, the reaction temperature for acyl chlorination is 40℃, and the reaction time is 2–4 hours.

[0015] Furthermore, in step 2, the reaction temperature is 0–35°C and the time is 12–36 h.

[0016] Furthermore, in step 2, the molar ratio of cellulose, catalyst, and acyl chloride product is 1:0.5 to 1:0.6 to 2.

[0017] Furthermore, the cellulose includes any one of methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, microcrystalline cellulose, and nanocellulose.

[0018] Furthermore, the catalyst includes at least one of 4-dimethylaminopyridine, triethylamine, and pyridine.

[0019] Furthermore, the good solvent includes any one of tetrahydrofuran, dichloromethane, lithium chloride / N,N-dimethylacetamide, lithium chloride / N-methylpyrrolidone, N-methylmorpholine-N-oxide, and 1-butyl-3-methylimidazolium chloride.

[0020] Furthermore, in step 3, the volume ratio of acrylate monomer A to acrylate monomer B is 1:1 to 4, the mass of the cellulose macromolecular photoinitiator is 0.5wt% to 3wt% of the total mass of acrylate monomer A and acrylate monomer B, and the mass of the quantum dots is 1wt‰ to 3wt‰ of the total mass of acrylate monomer A and acrylate monomer B.

[0021] Furthermore, acrylate monomer A and acrylate monomer B are any one or any two of acrylic acid, methyl methacrylate, hydroxyethyl acrylate, butyl acrylate, lauryl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, and tetrahydrofuran acrylate.

[0022] Furthermore, the quantum dots can be any one of perovskite quantum dots, carbon quantum dots, graphene quantum dots, silicon quantum dots, etc.

[0023] Furthermore, the perovskite quantum dots include at least one of CsPbX3 and CsSnX3, wherein X = Cl, Br or I.

[0024] Furthermore, the stirring temperature is 20–50°C, and the stirring time is 0.5–3 hours.

[0025] The aforementioned quantum dot-catalyzed rapid photocuring cellulose resin adhesive can achieve bonding of transparent substrates by curing the adhesive under a 365nm UV lamp for 0.2–1 min. The small amount of quantum dots added did not cause aggregation and had almost no impact on mechanical properties.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] The rapid photocurable cellulose resin adhesive of the present invention has the advantages of being environmentally friendly, simple to operate, having a simple reaction system, and being applicable to a wide range of monomers. The rapid photocurable cellulose resin adhesive prepared after cellulose modification can further improve the high-value utilization of cellulose and enable cellulose to be widely used in various fields.

[0028] The rapid photocuring cellulose resin adhesive of the present invention can be used as a novel bio-based adhesive, possessing excellent mechanical properties and rapid photocuring capability, and its properties can be effectively controlled by adjusting the proportion of cellulose. Attached Figure Description

[0029] Figure 1 The infrared spectra of ethyl cellulose and ethyl cellulose macromolecular initiator in Example 1 are shown.

[0030] Figure 2 The image shows the uniaxial tensile stress-strain curves for Example 1 with and without perovskite quantum dots.

[0031] Figure 3 The graph shows the viscosity of the photosensitive resin adhesive with added perovskite quantum dots in Example 1 as a function of UV irradiation time.

[0032] Figure 4 The graph shows the viscosity of the photosensitive resin adhesive without perovskite quantum dots in Comparative Example 1 as a function of UV irradiation time. Detailed Implementation

[0033] The following is in conjunction with the appendix Figure 1-4 The present invention is further illustrated by specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention. After reading this invention, any modifications of the invention in various equivalent forms by those skilled in the art fall within the scope defined by the appended claims.

[0034] The raw materials and reagents used in the following examples are all commercially available.

[0035] Example 1: Preparation of a fast-curing photocurable cellulose resin adhesive using ethyl cellulose

[0036] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2.5 h in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:2 to prepare the acyl chloride product.

[0037] Step 2: Ethyl cellulose, 4-dimethylaminopyridine, and acyl chloride products were dissolved in tetrahydrofuran at a molar ratio of [ethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:1 and reacted at 25°C for 24 hours to prepare ethyl cellulose macromolecular photoinitiator.

[0038] Step 3: Mix acrylic acid and tetrahydrofuran acrylate at a volume ratio of [acrylic acid]:[tetrahydrofuran acrylate] = 3:7, then add ethyl cellulose macromolecular photoinitiator and perovskite quantum dots. The mass of the ethyl cellulose macromolecular photoinitiator is 2 wt% of the total mass of acrylic acid and tetrahydrofuran acrylate, and the mass of the CsPbBr3 perovskite quantum dots is 2.8 wt% of the total mass of acrylic acid and tetrahydrofuran acrylate. Stir at 25°C for 1 hour to obtain the photosensitive resin adhesive.

[0039] The structural formula of the prepared adhesive is as follows:

[0040]

[0041] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.47 minutes to achieve rapid bonding of transparent substrates.

[0042] Figure 1 The infrared spectra of ethyl cellulose and the ethyl cellulose macromolecular photoinitiator monomer in Example 1 are shown in the figure at 3450 cm⁻¹. -1 The corresponding -OH absorption peak almost disappears at 1750 cm⁻¹; meanwhile, the absorption peak at 1750 cm⁻¹ also disappears. -1 The presence of a strong C=O absorption peak indicates the successful preparation of the ethyl cellulose macromolecular photoinitiator.

[0043] Comparative Example 1: No perovskite quantum dots added

[0044] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2.5 h in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:2 to prepare the acyl chloride product.

[0045] Step 2: Ethyl cellulose, 4-dimethylaminopyridine, and acyl chloride products were dissolved in tetrahydrofuran at a molar ratio of [ethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:1 and reacted at 25°C for 24 hours to prepare ethyl cellulose macromolecular photoinitiator.

[0046] Step 3: Mix acrylic acid and tetrahydrofuran acrylate at a volume ratio of [acrylic acid]:[tetrahydrofuran acrylate] = 3:7, then add ethyl cellulose macromolecular photoinitiator, wherein the mass of the ethyl cellulose macromolecular photoinitiator is 2 wt% of the total mass of acrylic acid and tetrahydrofuran acrylate. Stir at 25°C for 1 hour to obtain the photosensitive resin adhesive.

[0047] The obtained photosensitive resin adhesive was cured under a 365nm ultraviolet lamp for 0.65 minutes to achieve substrate bonding.

[0048] Figure 2 The figures show the uniaxial tensile stress-strain curves of the photocurable films in Example 1 (with perovskite quantum dots) and Comparative Example 1 (without perovskite quantum dots). The mechanical properties of the photocurable film with added perovskite quantum dots are comparable to those of the film without added perovskite quantum dots, indicating that the addition of perovskite quantum dots did not significantly affect its mechanical properties.

[0049] Figure 3 , Figure 4 The viscosity curves of the photosensitive resin adhesive with added perovskite quantum dots in Example 1 and the photosensitive resin adhesive without added perovskite quantum dots in Comparative Example 1 are shown as a function of UV irradiation time. The curing time of the photosensitive resin adhesive with added perovskite quantum dots is significantly shorter than that of the photosensitive resin adhesive without added perovskite quantum dots, indicating that the addition of perovskite quantum dots can accelerate the curing rate.

[0050] Example 2: Preparation of a fast-curing cellulose resin adhesive using hydroxyethyl cellulose

[0051] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2 hours in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:1.5 to prepare the acyl chloride product.

[0052] Step 2: Hydroxyethyl cellulose, 4-dimethylaminopyridine, and acyl chloride products were dissolved in tetrahydrofuran at a molar ratio of [hydroxyethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:0.6 and reacted at 25°C for 24 h to prepare a macromolecular photoinitiator of hydroxyethyl cellulose.

[0053] Step 3: Mix acrylic acid and tetrahydrofuran acrylate at a volume ratio of [acrylic acid]:[tetrahydrofuran acrylate] = 2:8. Then add hydroxyethyl cellulose macromolecular photoinitiator and perovskite quantum dots, wherein the mass of hydroxyethyl cellulose macromolecular photoinitiator is 3wt% of the total mass of acrylic acid and tetrahydrofuran acrylate, and the mass of CsPbCl3 perovskite quantum dots is 1wt‰ of the total mass of acrylic acid and tetrahydrofuran acrylate. Stir at 25°C for 1 hour to obtain the photosensitive resin adhesive.

[0054] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.5 minutes to achieve rapid bonding of transparent substrates.

[0055] Effective control can be achieved by adjusting the proportion of cellulose: adjusting the proportion of cellulose can effectively control the curing speed of photosensitive resin adhesives under 365nm ultraviolet light, while also changing their mechanical properties and bonding strength.

[0056] Comparative Example 2: No perovskite quantum dots added

[0057] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2 hours in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:1.5 to prepare the acyl chloride product.

[0058] Step 2: Hydroxyethyl cellulose, 4-dimethylaminopyridine, and acyl chloride products were dissolved in tetrahydrofuran at a molar ratio of [hydroxyethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:0.6 and reacted at 25°C for 24 h to prepare a macromolecular photoinitiator of hydroxyethyl cellulose.

[0059] Step 3: Mix acrylic acid and tetrahydrofuran acrylate at a volume ratio of [acrylic acid]:[tetrahydrofuran acrylate] = 2:8, then add hydroxyethyl cellulose macromolecular photoinitiator, wherein the mass of hydroxyethyl cellulose macromolecular photoinitiator is 3 wt% of the total mass of acrylic acid and tetrahydrofuran acrylate. Stir at 25°C for 1 hour to obtain photosensitive resin adhesive.

[0060] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.7 minutes to achieve rapid bonding of transparent substrates.

[0061] Example 3: Preparation of a fast-curing cellulose resin adhesive using hydroxyethyl cellulose

[0062] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2 hours in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:1 to prepare the acyl chloride product.

[0063] Step 2: Dissolve hydroxyethyl cellulose, 4-dimethylaminopyridine, and acyl chloride product in dichloromethane at a molar ratio of [hydroxyethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:2 and react at 10°C for 36 h to prepare a macromolecular photoinitiator of hydroxyethyl cellulose.

[0064] Step 3: Mix acrylic acid and butyl acrylate at a volume ratio of [acrylic acid]:[butyl acrylate] = 4:6, then add hydroxyethyl cellulose macromolecular photoinitiator and perovskite quantum dots. The mass of the hydroxyethyl cellulose macromolecular photoinitiator is 0.5 wt% of the total mass of acrylic acid and butyl acrylate, and the mass of the CsPbI3 perovskite quantum dots is 3 wt% of the total mass of acrylic acid and butyl acrylate. Stir at 25°C for 1 hour to obtain the photosensitive resin adhesive.

[0065] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.6 minutes to achieve rapid bonding of transparent substrates.

[0066] Comparative Example 3: No perovskite quantum dots added

[0067] Step 1: Benzoylcarboxylic acid and oxaloyl chloride are reacted at 40°C for 2 hours in a molar ratio of [benzoylcarboxylic acid]:[oxaloyl chloride] = 1:1 to prepare the acyl chloride product.

[0068] Step 2: Dissolve hydroxyethyl cellulose, 4-dimethylaminopyridine, and acyl chloride product in dichloromethane at a molar ratio of [hydroxyethyl cellulose]:[4-dimethylaminopyridine]:[acyl chloride product] = 1:1:2 and react at 10°C for 36 h to prepare a macromolecular photoinitiator of hydroxyethyl cellulose.

[0069] Step 3: Mix acrylic acid and butyl acrylate at a volume ratio of [acrylic acid]:[butyl acrylate] = 4:6, then add hydroxyethyl cellulose macromolecular photoinitiator, wherein the mass of hydroxyethyl cellulose macromolecular photoinitiator is 0.5 wt% of the total mass of acrylic acid and butyl acrylate. Stir at 25°C for 1 hour to obtain photosensitive resin adhesive.

[0070] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.8 minutes to achieve rapid bonding of transparent substrates.

[0071] Example 4: Preparation of a rapid-curing cellulose resin adhesive using nanocellulose

[0072] Step 1: React 1-hydroxycyclohexylphenyl ketone and oxalyl chloride at a molar ratio of [1-hydroxycyclohexylphenyl ketone]:[oxalyl chloride] = 1:1 at 40°C for 3 hours to prepare the acyl chloride product.

[0073] Step 2: Dissolve nanocellulose, triethylamine, and acyl chloride products in lithium chloride / N-methylpyrrolidone at a molar ratio of [nanocellulose]:[triethylamine]:[acyl chloride product] = 1:0.5:1 and react at 35°C for 36 h to prepare nanocellulose macromolecular photoinitiator.

[0074] Step 3: Mix acrylic acid and lauryl methacrylate at a volume ratio of [acrylic acid]:[lauryl methacrylate] = 4:6, then add nano-cellulose macromolecular photoinitiator and perovskite quantum dots. The mass of the nano-cellulose macromolecular photoinitiator is 2.5 wt% of the total mass of acrylic acid and lauryl methacrylate, and the mass of the CsSnI3 perovskite quantum dots is 2.5 wt% of the total mass of acrylic acid and lauryl methacrylate. Stir at 20°C for 0.5 h to obtain the photosensitive resin adhesive.

[0075] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.4 minutes to achieve rapid bonding of transparent substrates.

[0076] Example 5: Preparation of a rapid-curing cellulose resin adhesive using nanocellulose

[0077] Step 1: React 1-hydroxycyclohexylphenyl ketone and oxalyl chloride at a molar ratio of [1-hydroxycyclohexylphenyl ketone]:[oxalyl chloride] = 1:2 at 40°C for 4 hours to prepare the acyl chloride product.

[0078] Step 2: Dissolve nanocellulose, pyridine, and acyl chloride products in a molar ratio of [nanocellulose]:[pyridine]:[acyl chloride product] = 1:0.6:1.5 in lithium chloride / N-methylpyrrolidone and react at 35°C for 36 h to prepare nanocellulose macromolecular photoinitiator.

[0079] Step 3: Mix acrylic acid and methyl methacrylate at a volume ratio of [acrylic acid]:[methyl methacrylate] = 5:5, then add nano-cellulose macromolecular photoinitiator and perovskite quantum dots. The mass of the nano-cellulose macromolecular photoinitiator is 3wt% of the total mass of acrylic acid and methyl methacrylate, and the mass of the CsSnCl3 perovskite quantum dots is 1wt% of the total mass of acrylic acid and methyl methacrylate. Stir at 40℃ for 2 hours to obtain the photosensitive resin adhesive.

[0080] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.2 minutes to achieve rapid bonding of transparent substrates.

[0081] Example 6: Preparation of a rapid-curing cellulose resin adhesive using cellulose acetate

[0082] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone and oxaloyl chloride at a molar ratio of [2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone]:[oxaloyl chloride] = 1:1 at 40°C for 3 hours.

[0083] Step 2: Dissolve cellulose acetate, triethylamine, and acyl chloride product in N-methylmorpholine-N-oxide at a molar ratio of [cellulose acetate]:[triethylamine]:[acyl chloride product] = 1:0.8:2 and react at 35°C for 28 hours to prepare a macromolecular photoinitiator of cellulose acetate.

[0084] Step 3: Mix furfuryl methacrylate and methyl methacrylate at a volume ratio of [furfuryl methacrylate]:[methyl methacrylate] = 2:8, then add cellulose acetate macromolecular photoinitiator and perovskite quantum dots. The mass of the cellulose acetate macromolecular photoinitiator is 2wt% of the total mass of furfuryl methacrylate and methyl methacrylate, and the mass of the CsSnBr3 perovskite quantum dots is 1wt‰ of the total mass of furfuryl methacrylate and methyl methacrylate. Stir at 50℃ for 0.5h to obtain the photosensitive resin adhesive.

[0085] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.7 minutes to achieve rapid bonding of transparent substrates.

[0086] Example 7: Preparation of a rapid-curing cellulose resin adhesive using microcrystalline cellulose

[0087] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone and oxaloyl chloride at 40°C for 2.5 h in a molar ratio of [2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone]:[oxaloyl chloride] = 1:1.5.

[0088] Step 2: Dissolve microcrystalline cellulose, triethylamine, and acyl chloride product in tetrahydrofuran at a molar ratio of [microcrystalline cellulose]:[triethylamine]:[acyl chloride product] = 1:1:1.5 and react at 30°C for 24 hours to prepare a microcrystalline cellulose macromolecular photoinitiator.

[0089] Step 3: Mix furfuryl methacrylate and hydroxyethyl acrylate at a volume ratio of [furfuryl methacrylate]:[hydroxyethyl acrylate] = 4:6. Then add microcrystalline cellulose macromolecular photoinitiator and perovskite quantum dots, wherein the mass of microcrystalline cellulose macromolecular photoinitiator is 3wt% of the total mass of furfuryl methacrylate and hydroxyethyl methacrylate, and the mass of CsSnBr3 perovskite quantum dots is 1wt‰ of the total mass of furfuryl methacrylate and hydroxyethyl acrylate. Stir at 30℃ for 3 hours to obtain the photosensitive resin adhesive.

[0090] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.3 minutes to achieve rapid bonding of transparent substrates.

[0091] Example 8: Preparation of a rapid-curing cellulose resin adhesive using methylcellulose

[0092] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone and oxaloyl chloride at 40°C for 2.5 h in a molar ratio of [2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone]:[oxaloyl chloride] = 1:1.5.

[0093] Step 2: Methylcellulose, pyridine, and acyl chloride products were reacted in lithium chloride / N,N-dimethylacetamide at a molar ratio of [methylcellulose]:[pyridine]:[acyl chloride product] = 1:0.5:2 for 18 h at 35 °C to prepare a macromolecular photoinitiator of methylcellulose.

[0094] Step 3: Mix furfuryl methacrylate and methyl methacrylate at a volume ratio of [furfuryl methacrylate]:[methyl methacrylate] = 3:7, then add methylcellulose macromolecular photoinitiator and carbon quantum dots. The mass of the methylcellulose macromolecular photoinitiator is 3 wt% of the total mass of furfuryl methacrylate and methyl methacrylate, and the mass of the carbon quantum dots is 1 wt% of the total mass of furfuryl methacrylate and methyl methacrylate. Stir at 50°C for 3 hours to obtain the photosensitive resin adhesive.

[0095] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.4 minutes to achieve rapid bonding of transparent substrates.

[0096] Example 9: Preparation of a rapid-curing cellulose resin adhesive using methylcellulose

[0097] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone and oxaloyl chloride in a molar ratio of [2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone]:[oxaloyl chloride] = 1:1 at 40°C for 2 hours.

[0098] Step 2: Dissolve methylcellulose, pyridine, and acyl chloride products in tetrahydrofuran at a molar ratio of [methylcellulose]:[pyridine]:[acyl chloride product] = 1:0.5:0.6 and react at 0°C for 36 h to prepare a macromolecular photoinitiator of methylcellulose.

[0099] Step 3: Mix tetrahydrofurfuryl methacrylate and hydroxyethyl methacrylate at a volume ratio of [tetrahydrofurfuryl methacrylate]:[hydroxyethyl methacrylate] = 4:6. Then add methylcellulose macromolecular photoinitiator and carbon quantum dots, wherein the mass of methylcellulose macromolecular photoinitiator is 1.5 wt% of the total mass of tetrahydrofurfuryl methacrylate and hydroxyethyl methacrylate, and the mass of carbon quantum dots is 2 wt% of the total mass of tetrahydrofurfuryl methacrylate and methyl methacrylate. Stir at 50°C for 2 hours to obtain the photosensitive resin adhesive.

[0100] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.8 minutes to achieve rapid bonding of transparent substrates.

[0101] Example 10: Preparation of a rapid-curing cellulose resin adhesive using carboxymethyl cellulose

[0102] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone and oxaloyl chloride at a molar ratio of [2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone]:[oxaloyl chloride] = 1:2 at 40°C for 3 hours.

[0103] Step 2: Dissolve carboxymethyl cellulose, pyridine, and acyl chloride products in a molar ratio of [carboxymethyl cellulose]:[pyridine]:[acyl chloride product] = 1:0.5:1.5 in lithium chloride / N,N-dimethylacetamide and react at 35°C for 24 h to prepare a carboxymethyl cellulose macromolecular photoinitiator.

[0104] Step 3: Furfuryl methacrylate and methyl methacrylate are mixed at a volume ratio of [furfuryl methacrylate]:[methyl methacrylate] = 3:7. Then, carboxymethyl cellulose macromolecular photoinitiator and silicon quantum dots are added. The mass of the carboxymethyl cellulose macromolecular photoinitiator is 2 wt% of the total mass of the furfuryl methacrylate and methyl methacrylate, and the mass of the silicon quantum dots is 1 wt% of the total mass of the furfuryl methacrylate and methyl methacrylate. The mixture is stirred at 50°C for 3 hours to obtain the photosensitive resin adhesive.

[0105] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.6 minutes to achieve rapid bonding of transparent substrates.

[0106] Example 11: Preparation of a fast-curing cellulose resin adhesive using carboxymethyl cellulose

[0107] Step 1: Prepare the acyl chloride product by reacting 2-hydroxy-2-methyl-1-phenyl-1-propanone and oxalyl chloride in a molar ratio of [2-hydroxy-2-methyl-1-phenyl-1-propanone]:[oxalyl chloride] = 1:2 at 40°C for 3 hours.

[0108] Step 2: Dissolve carboxymethyl cellulose, pyridine, and acyl chloride products in a molar ratio of [carboxymethyl cellulose]:[pyridine]:[acyl chloride product] = 1:0.5:1 in 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) and react at 40°C for 10 h to prepare a carboxymethyl cellulose macromolecular photoinitiator.

[0109] Step 3: Furfuryl methacrylate and methyl methacrylate are mixed at a volume ratio of [furfuryl methacrylate]:[methyl methacrylate] = 3:7. Then, carboxymethyl cellulose macromolecular photoinitiator and graphene quantum dots are added. The mass of the carboxymethyl cellulose macromolecular photoinitiator is 2 wt% of the total mass of the furfuryl methacrylate and methyl methacrylate, and the mass of the graphene quantum dots is 1 wt% of the total mass of the furfuryl methacrylate and methyl methacrylate. The mixture is stirred at 50°C for 3 hours to obtain the photosensitive resin adhesive.

[0110] The obtained photosensitive resin adhesive can be cured under a 365nm ultraviolet lamp for 0.7 minutes to achieve rapid bonding of transparent substrates.

[0111] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A quantum dot-catalyzed, rapidly photocurable cellulose resin adhesive, characterized in that, Its general structural formula is as follows: Wherein, R is a characteristic functional group of cellulose, which is any one of -H or -CH3, -CH2CH3, -CH2COOH, -COCH3, -CH2CH2OH, -CH2CH2CH2OH, and R1 and R2 are acrylate monomers, which are any two of acrylic acid, methyl methacrylate, hydroxyethyl acrylate, butyl acrylate, lauryl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, and tetrahydrofuran acrylate.

2. A method for preparing a quantum dot-catalyzed, rapidly photocurable cellulose resin adhesive, characterized in that, Includes the following steps: Step 1: Acyl chloride is used to chlorinate the photoinitiator primer to obtain the acyl chloride product; Step 2: Dissolve cellulose, catalyst, and acyl chloride product in a good solvent and react them. Then precipitate the product in deionized water, collect the precipitate and dry it to obtain the cellulose macromolecular photoinitiator. Step 3: Mix and stir acrylate monomer A, acrylate monomer B, cellulose macromolecular photoinitiator, and quantum dots to obtain an adhesive.

3. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 2, characterized in that, In step 1, the molar ratio of photoinitiator primer to oxalyl chloride is 1:1 to 2.

4. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 3, characterized in that, The photoinitiator primer is a hydroxyl-containing cleavage photoinitiator, including any one of benzoylformic acid, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl ketone.

5. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 2, characterized in that, In step 2, the molar ratio of cellulose, catalyst, and acyl chloride product is 1:0.5 to 1:0.6 to 2.

6. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 5, characterized in that, The cellulose includes any one of methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, microcrystalline cellulose, and nanocellulose; the catalyst includes at least one of 4-dimethylaminopyridine, triethylamine, and pyridine; and the good solvent includes any one of tetrahydrofuran, dichloromethane, lithium chloride / N,N-dimethylacetamide, lithium chloride / N-methylpyrrolidone, N-methylmorpholine-N-oxide, and 1-butyl-3-methylimidazolium chloride.

7. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 2, characterized in that, In step 3, the volume ratio of acrylate monomer A to acrylate monomer B is 1:1 to 4, the mass of the cellulose macromolecular photoinitiator is 0.5wt% to 3wt% of the total mass of acrylate monomer A and acrylate monomer B, and the mass of the quantum dots is 1wt‰ to 3wt‰ of the total mass of acrylate monomer A and acrylate monomer B.

8. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 7, characterized in that, Acrylate monomer A and acrylate monomer B are any one or any two of acrylic acid, methyl methacrylate, hydroxyethyl acrylate, butyl acrylate, lauryl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, and tetrahydrofuran acrylate.

9. The method for preparing quantum dot-catalyzed rapid photocurable cellulose resin adhesive according to claim 8, characterized in that, The quantum dot can be any one of perovskite quantum dots, carbon quantum dots, graphene quantum dots, or silicon quantum dots.

10. The application of the quantum dot-catalyzed rapid photocuring cellulose resin adhesive according to claim 1, characterized in that, The resulting adhesive was cured under a 365nm UV lamp for 0.2–1 min to achieve bonding of transparent substrates.

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