Preparation method of anti-oxygen-inhibition low-hardness UV adhesive

Abstract

The preparation method comprises the following steps: mixing zeolite powder, a titanium nitrate solution, a lanthanum nitrate solution and boric acid, carrying out ball milling in an inert atmosphere, drying, carrying out staged calcination, crushing, and carrying out nitrogen activation treatment to obtain an activated component; placing the activated component in a vacuum reactor, introducing gamma-methacryloxypropyltrimethoxysilane steam, and reacting to obtain a functional component; and uniformly mixing the functional component with the UV adhesive matrix, and performing dual-wavelength ultraviolet curing to obtain the anti-oxidation polymerization inhibition low-hardness UV adhesive. According to the scheme, the surface drying time of the UV adhesive is shortened and the oxygen inhibition surface residual rate is low through the synergistic effect of the components and the optimization of the process.

Description

Technical Field

[0001] The invention relates to the field of power capacitors, and in particular to a method for preparing an anti-oxidation and anti-polymerization low-hardness UV adhesive. Background Art

[0002] When UV glue is triggered by ultraviolet light, the active free radicals generated by the decomposition of photosensitizer will compete with oxygen molecules in the air: on the one hand, the free radicals combine with the monomer to initiate chain polymerization; on the other hand, oxygen, as a diradical structure, preferentially reacts with the active free radicals to generate peroxy radicals, which cannot continue to initiate polymerization due to their high stability, resulting in uncured or sticky surfaces. This oxygen inhibition effect is particularly significant in thin coatings or highly permeable substrates (such as plastics and flexible circuit boards, which require UV glue to have good flexibility) because oxygen continues to diffuse from the environment to the shallow surface layer, inhibiting the cross-linking reaction. Existing solutions include inert gas protection, adding oxygen scavengers (tertiary amines, thiols or phosphine compounds) to regenerate active free radicals, and using cationic polymerization systems (such as iodonium salts and sulfonium salts) to avoid oxygen interference, but these methods have limitations - the inert gas process is costly and complex to operate, amine additives are prone to yellowing and storage stability problems, and thiols are limited in application due to odor and side reactions; although the cationic system is not affected by oxygen inhibition, the available resins and monomers are scarce, and the deep curing efficiency is low. In recent years, new antioxidant and polymerization-inhibiting resins have been introduced with active hydrogen donors through molecular design, achieving low-energy surface drying under LED light sources while taking into account flexibility and low yellowing. At the same time, composite nanofillers and superhydrophobic modification technologies are used to enhance the anti-oxygen permeability and weather resistance of the coating, but there is still a problem of poor flexibility. CN118271529A discloses an antioxidant and polymerization-inhibiting UV-LED curable photosensitive resin and its preparation method and application, which relate to the technical field of dental materials. The antioxidant and polymerization-inhibiting UV-LED curable photosensitive resin provided by the present invention, in parts by weight, the raw materials for preparing the photosensitive resin include: 20 to 60 parts of mercapto-modified oligomers, 20 to 50 parts of trifunctional or higher ethoxy-containing active diluents, 10 to 30 parts of difunctional ethoxy-containing active diluents, 0 to 20 parts of monofunctional ethoxy-containing active diluents, 0 to 5 parts of antioxidant and polymerization-inhibiting aids, and 0.2 to 4 parts of photoinitiators. The photosensitive resin provided by the present invention has the effect of anti-oxidation and polymerization inhibition, and can be cured by UV-LED, and the cured resin block has high hardness and strength. However, it requires the preparation of high-hardness UV glue, which is inconsistent with the problem to be solved by this solution. Summary of the invention

[0003] To solve the above problems, the present invention proposes a preparation method of an antioxidant and anti-inhibition low-hardness UV glue. Through the self-supplied nitrogen doping of titanium nitrate combined with the co-modification of boron and lanthanum, the efficient cooperation of multiple elements within the titanium dioxide lattice is realized. By utilizing the confinement effect of zeolite nanopores to control the grain size, the ultraviolet absorption efficiency and photocatalytic activity are significantly improved. The UV glue has a short surface drying time and a low residual rate of oxygen inhibition on the surface. At the same time, the innovative mesoporous silica toughening agent forms a chemical bond with the matrix through a thiol-ene click reaction, endowing the material with excellent anti-fatigue performance while ensuring ultra-low hardness, and solving the problem of decreased light transmittance caused by traditional toughening fillers.

[0004] To achieve the above object, the technical solution of the present invention is as follows: A preparation method of an antioxidant and anti-inhibition low-hardness UV glue, comprising the following steps: (1) Mix zeolite powder with titanium nitrate solution, lanthanum nitrate solution, and boric acid according to a mass ratio of (5-10):(3-5):(0.5-1.5):(0.2-0.8), add zirconia milling beads and deionized water medium, and mill for 30 min - 60 min under an inert atmosphere, unload, dry, and obtain a cake; (2) Calcinate the cake in stages, use the nitrogen source generated by the decomposition of titanium nitrate to achieve nitrogen doping, and pulverize to obtain an activated component; (3) Graft a surface silane coupling agent onto the activated component; (4) Uniformly mix 10 - 20 parts of the functional component with 80 - 90 parts of the UV glue matrix and then cure it under ultraviolet light to obtain an antioxidant and anti-inhibition low-hardness UV glue.

[0005] In this solution, through the thermal decomposition of titanium nitrate in a reducing atmosphere to self-supply an active nitrogen source and the co-doping of boron and lanthanum, combined with the confinement effect of the nanopores of zeolite molecular sieves, the efficient doping of nitrogen, boron, and lanthanum elements within the titanium dioxide lattice and the precise control of the grain size are realized. While broadening the ultraviolet absorption spectrum, the photocatalytic reaction rate is increased, effectively overcoming the surface curing defects caused by oxygen inhibition; by grafting flexible acrylate groups on the surface and cooperating with the zeolite carrier to construct a three-dimensional network with a low crosslinking density, the UV glue still maintains a low hardness under rapid curing.

[0006] Preferably, in step (1), the mass concentration of the titanium nitrate solution is 20 - 35 wt%, and the pH value is adjusted to 1 - 2 with nitric acid to inhibit the hydrolysis of titanium ions; the mass concentration of the lanthanum nitrate solution is 5 - 10%.

[0007] Preferably, the calcination process in step (2) is divided into: Pre-decomposition stage: Calcinate at 250 - 350 °C for 2 - 3 h to decompose titanium nitrate into a TiO2 precursor and release NO x gas, reaction formula: TiO(NO3)2 → TiO2 + 2NO2↑ + O2↑; Doping stage: Calcinate at 550 - 650 °C for 2 - 3 h in a nitrogen atmosphere containing 3 - 5 vol% hydrogen to promote the reduction of NO x to active nitrogen atoms which are doped into the TiO2 lattice. Meanwhile, boric acid decomposes into B2O3 and lanthanum elements enter the lattice.

[0008] Preferably, the average particle size after pulverization is < 1 μm. The functional components need to be subjected to nitrogen activation treatment: After pulverization, immerse in a 0.05 - 0.1 mol / L hydrochloric acid solution and ultrasonicate for 30 minutes to remove the surface-undoped nitrogen oxides, and then anneal at 250 - 300 °C for 0.5 - 1 h.

[0009] Preferably, the surface grafting in step (3) adopts the gas-phase deposition method: Place the activating components in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and control the pressure at 50 - 100 Pa; Due to the low air pressure in the vacuum reactor, after the γ-methacryloxypropyltrimethoxysilane vapor is introduced, it remains in the gas phase at 120 - 150 °C. After reacting for 2 - 4 h, the silane coupling agent is chemically bonded to the surface of the composite material.

[0010] The core advantage of adopting the gas-phase deposition method for surface grafting lies in achieving a uniform monolayer coating of the silane coupling agent on the surface of the zeolite-titania composite material by precisely controlling the reaction atmosphere and interface contact, avoiding the problems of aggregation or uneven grafting caused by solvent polarity differences in the liquid-phase method; At the same time, the molecular free diffusion characteristics in the gas phase enable it to penetrate deep into the inner wall of the zeolite pores to complete the grafting reaction, maximizing the surface coverage rate of acrylate groups, ensuring that the double-bond active sites fully participate in the cross-linking network construction during UV curing. While reducing the cross-linking density, it significantly reduces the surface uncured area caused by oxygen inhibition of polymerization, and there is no risk of solvent residue. The process is clean and efficient, meeting the strict requirements of flexible electronic packaging for material uniformity and reliability. During the gas-phase deposition process, the silane coupling agent penetrates into the zeolite pores in the form of vapor and undergoes hydrolysis and condensation under the catalysis of the surface hydroxyl groups (-OH) of nano-titania to form Si-O-Ti covalent bonds. The grafted methacrylate groups (C=C) are directly exposed to the UV glue matrix, accelerating the rate of the photoinitiator capturing free radicals, thus breaking through the bottleneck of the inhibition of surface reactions by oxygen molecules.

[0011] Preferably, in the vacuum reactor, the partial pressure of water vapor is 40% - 50%, that is, under the condition of 10 Pa, 4 - 5 Pa is the water vapor pressure, mainly to promote the hydrolysis of the silane coupling agent.

[0012] Preferably, the UV glue matrix in step (4) comprises the following components: by weight, 55-75 parts of polyurethane acrylate, 20-30 parts of isooctyl acrylate, 2-4 parts of photoinitiator, and 5-8 parts of surface-thiolated nano-silica toughening agent.

[0013] Preferably, the nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide in a mass ratio of 1:0.2-0.5, and hydrolyze in an ethanol aqueous solution with pH 9-11 to generate silica sol; b. After the silica sol is aged, centrifuged, and dried, it is calcined at 500-600 °C for 2-3 h to obtain mesoporous silica; c. Reflux and graft the mesoporous silica and mercaptopropyltrimethoxysilane in a mass ratio of 1:0.1-0.3 in toluene for 5-6 h to obtain a surface-thiolated nano toughening agent.

[0014] Mix tetraethyl orthosilicate (TEOS) and cetyltrimethylammonium bromide (CTAB) in a mass ratio of 1:0.2-0.5, add an ethanol-water mixed solvent (volume ratio 4:1), dropwise add ammonia water under stirring to adjust the pH to 9-11, and react at 40-60 °C for 4-6 h to generate silica sol; let it stand and age at 60 °C for 24 h, centrifuge and wash to remove the CTAB template, vacuum dry at 80 °C for 12 h to obtain a mesoporous silica precursor, calcine in a muffle furnace at 550 °C for 3 h with a heating rate of 2 °C / min to remove residual organic matter and stabilize the mesoporous structure, then immerse it in a 3 wt% hydrochloric acid solution and ultrasonically treat for 1 h, centrifuge and dry to generate active silicon hydroxyl groups (Si-OH) on the surface. Further, add it to toluene with KH-590 in a mass ratio of 1:0.1-0.3, and reflux and react under nitrogen protection for 6 h (temperature 110 °C), centrifuge, wash, and dry to obtain a nano toughening agent with surface-grafted mercapto groups (-SH).

[0015] CTAB acts as a template agent to guide the hydrolysis and condensation of TEOS (reaction formula: Si(OC2H5)4 + 4H2O → Si(OH)4 + 4C2H5OH), forming an ordered mesoporous structure (pore size 2-5 nm).

[0016] Preferably, the method of dual-wavelength alternating irradiation for UV curing in step (4) is as follows: The first stage: wavelength 365 nm, light intensity 80 mW / cm², irradiate for 5 s to initiate rapid surface curing; The second stage: wavelength 405 nm, light intensity 120 mW / cm², irradiate for 15 s to promote deep crosslinking.

[0017] Preferably, the zeolite is synthetic zeolite Beta type or MCM-48 type, with a pore size distribution peak of 500 nm - 1.5 μm and a specific surface area of 50 - 200 m² / g.

[0018] This solution also proposes an antioxidant and polymerization retardant low-hardness UV glue prepared by the above method.

[0019] Compared with the prior art, the technical advantages of this solution are as follows: 1. This solution proposes a preparation method for an antioxidant and polymerization retardant low-hardness UV glue. Through nitrogen self-doping by titanium nitrate combined with co-modification of boron and lanthanum, efficient synergy of multiple elements within the titanium dioxide lattice is achieved. Using the zeolite nanochannel confinement effect to precisely control the grain size significantly improves the ultraviolet absorption efficiency and photocatalytic activity. The UV glue has a short surface drying time and a low residual rate of oxygen inhibition polymerization on the surface. At the same time, the innovative mesoporous silica toughening agent forms a chemical bond with the matrix through thiol-ene click reaction, endowing the material with excellent anti-fatigue performance while ensuring ultra-low hardness, and solving the problem of reduced light transmittance caused by traditional toughening fillers.

[0020] 2. The gas-phase deposition method is used to achieve uniform grafting of a monolayer of silane coupling agent, breaking through the technical bottleneck of the mismatch between the solvent polarity of the liquid-phase method and the wettability of the zeolite pores, and there is no risk of solvent residue; combined with the dual-wavelength dynamic regulation curing strategy, the curing efficiency is improved compared with the traditional single-wavelength curing. Specific Embodiments

[0021] The following specific embodiments illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0022] Example 1, A preparation method for an antioxidant and polymerization retardant low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 10:5:1.5:0.8, ball mill for 30 min in an inert atmosphere and then dry to obtain a cake; the mass concentration of the titanium nitrate solution is 30 wt% and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%. (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 300 °C for 1.5 h; Doping stage: Calcination at 600 °C for 2.5 h in a nitrogen atmosphere containing 4 vol% hydrogen, pulverization, and nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonic treatment in 0.08 mol / L hydrochloric acid solution for 35 min, and then annealing at 300 °C for 0.5 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40 Pa; (4) By weight, mix 10 parts of the functional component with 90 parts of the UV glue matrix, and cure under dual-wavelength ultraviolet light to obtain an antioxidant and polymerization inhibitor low-hardness UV glue; the UV glue matrix includes: by weight, 65 parts of polyurethane acrylate, 25 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 6 parts of surface thiolated nano-silica toughening agent; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide at a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to form silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. Reflux and graft the mesoporous silica and mercaptopropyltrimethoxysilane at a mass ratio of 1:0.2 in toluene for 6 h to obtain a surface thiolated nano-toughening agent.

[0023] The parameters of dual-wavelength ultraviolet curing are: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiation for 5 s; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiation for 15 s.

[0024] Example 2, A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid at a mass ratio of 5:3:0.5:0.2, ball mill and dry in an inert atmosphere to obtain a cake; the mass concentration of the titanium nitrate solution is 35 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 10%; (2) Calcinate the cake in stages: Pre-decomposition stage: Calcination at 250 °C for 3 h; Doping stage: Calcination at 550 °C for 3 h in a nitrogen atmosphere containing 3 vol% hydrogen, pulverization, and nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonic treatment in 0.05 mol / L hydrochloric acid solution for 40 min, and then annealing at 250 °C for 1 h (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 130 °C and a pressure of 70 Pa for 3 h to obtain the functional component; in the vacuum reactor, the partial pressure of water vapor is 30 Pa; (4) By weight, mix 20 parts of the functional component with 80 parts of the functional component and the UV glue matrix, and cure under dual-wavelength ultraviolet light to obtain an antioxidant and polymerization inhibitor low-hardness UV glue; the UV glue matrix includes: by weight, 55 parts of polyurethane acrylate, 20 parts of isooctyl acrylate, 2 parts of photoinitiator 819, and 5 parts of surface thiolated nano-silica toughening agent; the nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide in a mass ratio of 1:0.5, and hydrolyze in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 500 °C for 3 h to obtain mesoporous silica; c. Reflux and graft the mesoporous silica and mercaptopropyltrimethoxysilane in toluene in a mass ratio of 1:0.1 for 5 h to obtain the surface thiolated nano-toughening agent; The dual-wavelength ultraviolet curing parameters are as follows: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 s; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiate for 15 s.

[0025] Example 3, a method for preparing an antioxidant and polymerization inhibitor low-hardness UV glue, includes the following steps: (1) Mix MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 8:4:1:0.5, ball mill and dry in an inert atmosphere to obtain a cake; the mass concentration of the titanium nitrate solution is 25 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 320 °C for 2 h; Doping stage: Calcinate at 630 °C in a nitrogen atmosphere containing 5 vol% hydrogen for 2 h, pulverize, and perform nitrogen activation treatment to obtain the activated component; the process of nitrogen activation treatment is: ultrasonic in 0.1 mol / L hydrochloric acid solution for 35 min, and then anneal at 280 °C for 0.7 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 150 °C and a pressure of 100 Pa for 2 h to obtain the functional component; in the vacuum reactor, the partial pressure of water vapor is 40 Pa; (4) Mix 15 parts of functional components with 85 parts of UV glue matrix by weight, and cure them by dual-wavelength ultraviolet to obtain an antioxidant and polymerization-inhibiting low-hardness UV glue; The UV glue matrix includes: 75 parts of polyurethane acrylate, 30 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 7 parts of surface-thiolated nano-silica toughening agent by weight; The nano-silica toughening agent is prepared through the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide at a mass ratio of 1:0.4, and hydrolyze them in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 2.5 h to obtain mesoporous silica; c. Reflux and graft mesoporous silica and mercaptopropyltrimethoxysilane at a mass ratio of 1:0.2 in toluene for 5.5 h to obtain a surface-thiolated nano-toughening agent; The parameters of dual-wavelength ultraviolet curing are as follows: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 seconds; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiate for 15 seconds.

[0026] Comparative example 1, the difference from Example 1 is that only ordinary nano-titanium dioxide is added: A preparation method of an antioxidant and polymerization-inhibiting low-hardness UV glue includes the following steps: Mix 10 parts of nano-titanium dioxide with 90 parts of UV glue matrix by weight, and cure them by dual-wavelength ultraviolet to obtain an antioxidant and polymerization-inhibiting low-hardness UV glue; the UV glue matrix includes: 65 parts of polyurethane acrylate, 25 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 6 parts of surface-thiolated nano-silica toughening agent by weight; The nano-silica toughening agent is prepared through the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide at a mass ratio of 1:0.3, and hydrolyze them in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. Reflux and graft mesoporous silica and mercaptopropyltrimethoxysilane at a mass ratio of 1:0.2 in toluene for 6 h to obtain a surface-thiolated nano-toughening agent; The parameters of dual-wavelength ultraviolet curing are as follows: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 seconds; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiation for 15 seconds.

[0027] Comparative Example 2, different from Example 1 in that lanthanum nitrate and boric acid were not added: A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 type zeolite powder and titanium nitrate solution in a mass ratio of 10:5, ball mill for 30 min in an inert atmosphere and then dry to obtain a material cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; (2) Calcine the material cake in stages: Pre-decomposition stage: calcine at 300 °C for 1.5 h; Doping stage: calcine at 600 °C in a nitrogen atmosphere containing 4 vol% hydrogen for 2.5 h, pulverize, and perform nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonicate in 0.08 mol / L hydrochloric acid solution for 35 min, and then anneal at 300 °C for 0.5 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40 Pa; (4) By weight, mix 10 parts of the functional component with 90 parts of the UV glue matrix, and perform dual-wavelength ultraviolet curing to obtain an antioxidant and polymerization inhibitor low-hardness UV glue; the UV glue matrix includes: by weight, 65 parts of polyurethane acrylate, 25 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 6 parts of surface thiolated nano-silica toughening agent; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide in a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. Mix mesoporous silica and mercaptopropyltrimethoxysilane in a mass ratio of 1:0.2 and reflux and graft in toluene for 6 h to obtain a surface thiolated nano-toughening agent; The dual-wavelength ultraviolet curing parameters are: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiation for 5 seconds; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiation for 15 seconds.

[0028] Comparative Example 3, different from Example 1 in that in step (2), it was not calcined in stages: A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid according to a mass ratio of 10:5:1.5:0.8, ball mill for 30 min under an inert atmosphere, and then dry to obtain a cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcinate the cake: Calcinate at 600 °C in a nitrogen atmosphere containing 4 vol% hydrogen for 2.5 h, pulverize, and perform nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonically treat in a 0.08 mol / L hydrochloric acid solution for 35 min, and then anneal at 300 °C for 0.5 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40 Pa; (4) Mix 10 parts by weight of the functional component with 90 parts by weight of a UV glue matrix, and perform dual-wavelength ultraviolet curing to obtain an antioxidant and polymerization inhibitor low-hardness UV glue; the UV glue matrix includes: 65 parts by weight of polyurethane acrylate, 25 parts by weight of isooctyl acrylate, 3 parts by weight of photoinitiator 819, and 6 parts by weight of a surface-mercapto-functionalized nano-silica toughening agent; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide according to a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. React mesoporous silica and mercaptopropyltrimethoxysilane in toluene by reflux grafting for 6 h according to a mass ratio of 1:0.2 to obtain a surface-mercapto-functionalized nano-toughening agent; The parameters of dual-wavelength ultraviolet curing are: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 s; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiate for 15 s.

[0029] Comparative Example 4, the difference from Example 1 is that the activated component is conventionally modified: A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, comprising the following steps: (1) Mix the MCM-48 zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 10:5:1.5:0.8, ball mill for 30 min under an inert atmosphere, and then dry to obtain a cake. The mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2. The mass concentration of the lanthanum nitrate solution is 8%. (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 300 °C for 1.5 h. Doping stage: Calcinate at 600 °C in a nitrogen atmosphere containing 4 vol% hydrogen for 2.5 h, pulverize, and perform nitrogen activation treatment to obtain an activated component. The process of nitrogen activation treatment is: ultrasonic in 0.08 mol / L hydrochloric acid solution for 35 min, and then anneal at 300 °C for 0.5 h. (3) By weight, mix 10 parts of the activated component with 1 part of γ-methacryloyloxypropyltrimethoxysilane, add to water, stir for 2 h, filter, and dry to obtain a functional component. (4) By weight, mix 10 parts of the functional component with 90 parts of the UV glue matrix, and cure by dual-wavelength ultraviolet to obtain an antioxidant and anti-polymerization low-hardness UV glue. The UV glue matrix includes: by weight, 65 parts of polyurethane acrylate, 25 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 6 parts of surface thiolated nano-silica toughening agent. The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide in a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to form silica sol. The volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C. b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica. c. Reflux and graft the mesoporous silica and mercaptopropyltrimethoxysilane in a mass ratio of 1:0.2 in toluene for 6 h to obtain a surface thiolated nano-toughening agent. The parameters of dual-wavelength ultraviolet curing are: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 s. The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiate for 15 s.

[0030] Comparative Example 5, the difference from Example 1 is that no nitrogen activation treatment is performed: A method for preparing an antioxidant and anti-polymerization low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 10:5:1.5:0.8, ball mill for 30 min in an inert atmosphere, and then dry to obtain a cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 300 °C for 1.5 h; Doping stage: Calcinate at 600 °C in a nitrogen atmosphere containing 4 vol% hydrogen for 2.5 h, and then pulverize to obtain an activated component; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40%; (4) Mix 10 parts by weight of the functional component with 90 parts by weight of a UV glue matrix, and cure under dual-wavelength ultraviolet light to obtain an antioxidant and polymerization-inhibiting low-hardness UV glue; the UV glue matrix includes: 65 parts by weight of polyurethane acrylate, 25 parts by weight of isooctyl acrylate, 3 parts by weight of photoinitiator 819, and 6 parts by weight of a surface-mercapto-functionalized nano-silica toughening agent; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide in a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to form silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. Reflux and graft the mesoporous silica and mercaptopropyltrimethoxysilane in toluene in a mass ratio of 1:0.2 for 6 h to obtain a surface-mercapto-functionalized nano-toughening agent; The dual-wavelength ultraviolet curing parameters are as follows: First stage: Wavelength of 365 nm, light intensity of 80 mW / cm², irradiation for 5 s; Second stage: Wavelength of 405 nm, light intensity of 120 mW / cm², irradiation for 15 s.

[0031] Comparative Example 6, different from Example 1 in that the water partial pressure is low in step 3: A method for preparing an antioxidant and polymerization-inhibiting low-hardness UV glue, comprising the following steps: (1) Mix MCM-48 zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 10:5:1.5:0.8, ball mill for 30 min in an inert atmosphere, and then dry to obtain a cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcining the material cake in stages: Pre-calcination stage: Calcining at 300 °C for 1.5 h; Doping stage: Calcining at 600 °C in a nitrogen atmosphere containing 4 vol% hydrogen for 2.5 h, pulverizing, and performing nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonic treatment in a 0.08 mol / L hydrochloric acid solution for 35 min, and then annealing at 300 °C for 0.5 h; (3) Placing the activated component in a vacuum reactor, introducing γ-methacryloxypropyltrimethoxysilane vapor, and reacting at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 25 Pa; (4) Mixing 10 parts by weight of the functional component with 90 parts by weight of the UV glue matrix, and performing dual-wavelength ultraviolet curing to obtain an antioxidant and polymerization inhibitor low-hardness UV glue; the UV glue matrix includes: 65 parts by weight of polyurethane acrylate, 25 parts by weight of isooctyl acrylate, 3 parts by weight of photoinitiator 819, and 6 parts by weight of surface thiolated nano-silica toughening agent; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide at a mass ratio of 1:0.3, and hydrolyze in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. Aging, drying, and calcining the silica sol at 550 °C for 3 h to obtain mesoporous silica; c. Reflux grafting the mesoporous silica and mercaptopropyltrimethoxysilane at a mass ratio of 1:0.2 in toluene for 6 h to obtain a surface thiolated nano-toughening agent; The parameters of dual-wavelength ultraviolet curing are: The first stage: wavelength of 365 nm, light intensity of 80 mW / cm², irradiating for 5 s; The second stage: wavelength of 405 nm, light intensity of 120 mW / cm², irradiating for 15 s.

[0032] Comparative Example 7, the difference from Example 1 is that no nano-silica toughening agent is added: A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, comprising the following steps: (1) Mixing MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid at a mass ratio of 10:5:1.5:0.8, ball milling for 30 min in an inert atmosphere, and then drying to obtain a material cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcining the material cake in stages: Pre-calcination stage: Calcining at 300 °C for 1.5 h; Doping stage: Calcinate at 600 °C for 2.5 h in a nitrogen atmosphere containing 4 vol% hydrogen, pulverize, and perform nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonicate in a 0.08 mol / L hydrochloric acid solution for 35 min, and then anneal at 300 °C for 0.5 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40%; (4) Mix 10 parts by weight of the functional component with 90 parts by weight of the UV glue matrix, and cure by dual-wavelength ultraviolet light to obtain an antioxidant and polymerization-inhibiting low-hardness UV glue; the UV glue matrix includes: 65 parts by weight of polyurethane acrylate, 25 parts by weight of isooctyl acrylate, and 3 parts by weight of photoinitiator 819; The parameters of dual-wavelength ultraviolet curing are as follows: First stage: Wavelength of 365 nm, light intensity of 80 mW / cm², irradiate for 5 s; Second stage: Wavelength of 405 nm, light intensity of 120 mW / cm², irradiate for 15 s.

[0033] Comparative Example 8, the difference from Example 1 is single-source curing: A method for preparing an antioxidant and polymerization-inhibiting low-hardness UV glue includes the following steps: (1) Mix MCM-48 type zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid in a mass ratio of 10:5:1.5:0.8, ball mill for 30 min in an inert atmosphere, and then dry to obtain a cake; the mass concentration of the titanium nitrate solution is 30 wt%, and the pH is 2; the mass concentration of the lanthanum nitrate solution is 8%; (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 300 °C for 1.5 h; Doping stage: Calcinate at 600 °C for 2.5 h in a nitrogen atmosphere containing 4 vol% hydrogen, pulverize, and perform nitrogen activation treatment to obtain an activated component; the process of nitrogen activation treatment is: ultrasonicate in a 0.08 mol / L hydrochloric acid solution for 35 min, and then anneal at 300 °C for 0.5 h; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 140 °C and a pressure of 80 Pa for 3 h to obtain a functional component; in the vacuum reactor, the partial pressure of water vapor is 40%; (4) Mix 10 parts of functional components with 90 parts of UV glue matrix by weight, and cure them by dual-wavelength ultraviolet to obtain an antioxidant and polymerization-inhibiting low-hardness UV glue; the UV glue matrix includes: 65 parts of polyurethane acrylate, 25 parts of isooctyl acrylate, 3 parts of photoinitiator 819, and 6 parts of surface-thiolated nano-silica toughening agent by weight; The nano-silica toughening agent is prepared by the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide at a mass ratio of 1:0.3, and hydrolyze them in an ethanol aqueous solution with a pH of 10 to generate silica sol; the volume ratio of ethanol to water is 4:1, and the reaction temperature is 50 °C; b. The silica sol is aged, dried, and calcined at 550 °C for 3 h to obtain mesoporous silica; c. Reflux and graft the mesoporous silica and 3-mercaptopropyltrimethoxysilane in toluene at a mass ratio of 1:0.2 for 6 h to obtain a surface-thiolated nano-toughening agent; The parameters of dual-wavelength ultraviolet curing are: Wavelength of 405 nm, light intensity of 120 mW / cm², irradiation for 20 seconds.

[0034] The performance detection method and test results are shown in Table 1.

[0035] Table 1

[0036] From the result analysis of Examples 1-3 and Comparative Examples 1-8, Examples 1-3 of this solution can obtain better mechanical properties and antioxidant and polymerization-inhibiting properties.

[0037] The difference between Comparative Example 1 and Example 1 is that only ordinary nano-titanium dioxide is added. Ordinary TiO2 has no improvement in photocatalytic activity, weak oxygen polymerization inhibition ability, easy agglomeration of TiO2 grains, low specific surface area, poor light absorption efficiency, and poor compatibility with the UV glue matrix, resulting in high modulus, reduced flexibility, shortened dynamic bending life, and reduced packaging reliability. Similarly, there is Comparative Example 2. The difference from Example 1 is that lanthanum nitrate and boric acid are not added. It only has nitrogen doping, narrow light response range, increased oxygen polymerization inhibition residue rate, reduced photocatalytic activity, and the lack of boric acid leads to insufficient construction of the flexible network and increased hardness.

[0038] The difference between Comparative Example 3 and Example 1 is that it is not calcined in stages. This causes the rapid decomposition of titanium nitrate, resulting in coarse TiO2 grains, reduced light absorption efficiency, insufficient doping, and the direct calcination of the solution at high temperature causes the collapse of the zeolite pores and a reduction in the specific surface area.

[0039] The difference between Comparative Example 4 and Example 1 is that the silane coupling agent is modified by stirring in water instead of chemical vapor deposition, resulting in the inability of the liquid-phase method to penetrate the zeolite pores, low surface coverage, and residual water molecules that will also cause curing interface defects and an increase in modulus.

[0040] The difference between Comparative Example 5 and Example 1 is that no nitrogen activation treatment is performed, that is, the remaining nitrogen oxides (such as NO x ) cover the active sites, resulting in a decrease in the grafting rate. Surface impurities hinder the entry of nitrogen atoms into the lattice, reducing the bonding strength of the silane coupling agent, and ultimately increasing the hardness.

[0041] The difference between Comparative Example 6 and Example 1 is that the partial pressure of water is low, resulting in incomplete condensation reaction of the silane coupling agent and a decrease in the grafting rate. Moreover, at low humidity, the driving force for steam diffusion may be insufficient, and the grafting coverage in the pores is low, affecting the compatibility between the functional components and the UV glue substrate, resulting in performance degradation.

[0042] The difference between Comparative Example 7 and Example 1 is that no nano-silica toughening agent is added, resulting in a lack of stress dispersion by nano-particles and poor dynamic bending life.

[0043] The difference between Comparative Example 8 and Example 1 is that single-source curing is used. During the surface curing process, the 405nm initiator has weak absorption, and the surface free radicals are quenched by oxygen more. The long-wave has strong penetrability but low initiation efficiency, and the crosslinking degree of the bottom layer is low, resulting in uneven hardness.

Claims

1. A preparation method of an antioxidant and polymerization inhibitor low-hardness UV glue, characterized in that, It includes the following steps: (1) Mix zeolite powder, titanium nitrate solution, lanthanum nitrate solution, and boric acid according to the mass ratio of (5-10):(3-5):(0.5-1.5):(0.2-0.8), ball mill in an inert atmosphere and then dry to obtain a cake; (2) Calcinate the cake in stages: Pre-decomposition stage: Calcinate at 250-350°C for 2-3 h; Doping stage: Calcinate at 550-650°C in a nitrogen atmosphere containing 3-5 vol% hydrogen for 2-3 h, pulverize, and perform nitrogen activation treatment to obtain an activated component; (3) Place the activated component in a vacuum reactor, introduce γ-methacryloxypropyltrimethoxysilane vapor, and react at 120-150°C and a pressure of 50-100 Pa for 2-4 h to obtain a functional component; (4) By weight, uniformly mix 10-20 parts of the functional component with 80-90 parts of the UV glue matrix, and perform dual-wavelength ultraviolet curing to obtain an antioxidant and polymerization inhibitor low-hardness UV glue.

2. The preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to claim 1, characterized in that, The UV glue matrix includes: by weight, 55-75 parts of polyurethane acrylate, 20-30 parts of isooctyl acrylate, 2-4 parts of photoinitiator, and 5-8 parts of surface thiolated nano-silica toughening agent.

3. The preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to claim 1, characterized in that, In step (1), the mass concentration of the titanium nitrate solution is 20-35 wt%, and the pH is 1-2; the mass concentration of the lanthanum nitrate solution is 5-10%.

4. The preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to claim 1, characterized in that, In step (2), the process of the nitrogen activation treatment is: ultrasonicate in a 0.05-0.1 mol / L hydrochloric acid solution for 30-40 min, and then anneal at 250-300°C for 0.5-1 h.

5. The preparation method of the antioxidant and polymerization inhibitor-containing low-hardness UV adhesive according to claim 1, wherein, In step (3), in the vacuum reactor, the partial pressure of water vapor is 40%-50%.

6. The preparation method of the antioxidant and polymerization inhibitor-containing low-hardness UV adhesive according to claim 1, characterized in that, The nano-silica toughening agent is prepared through the following steps: a. Mix tetraethyl orthosilicate and cetyltrimethylammonium bromide according to the mass ratio of 1:0.2-0.5, and hydrolyze in an ethanol aqueous solution with a pH of 9-11 to generate silica sol; b. The silica sol is aged, dried, and calcined at 500-600°C for 2-3 h to obtain mesoporous silica; c. React mesoporous silica and mercaptopropyltrimethoxysilane according to the mass ratio of 1:0.1-0.3 in toluene by reflux grafting for 5-6 h to obtain a surface thiolated nano-toughening agent.

7. The preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to claim 6, wherein, In step a, the volume ratio of ethanol to water is 4:1, and the reaction temperature is 40-60°C.

8. The preparation method of the antioxidant and polymerization inhibitor-containing low-hardness UV glue according to claim 1, characterized in that, In step (4), the dual-wavelength ultraviolet curing parameters are: The first stage: wavelength 365 nm, light intensity 80 mW / cm², irradiate for 5 s; The second stage: wavelength 405 nm, light intensity 120 mW / cm², irradiate for 15 s.

9. The preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to claim 1, characterized in that, The zeolite is synthetic zeolite Beta type or MCM-48 type, the peak of the pore size distribution is 500 nm-1.5 μm, and the specific surface area is 50-200 m² / g.

10. An antioxidant and polymerization inhibitor low-hardness UV glue prepared by the preparation method of the antioxidant and polymerization inhibitor low-hardness UV glue according to any one of claims 1-9.

Images