A light-curable jade adhesive, its preparation method and application

Abstract

This invention discloses a photocurable jade adhesive, its preparation method, and its application. The jade adhesive is prepared by mixing a difunctional (meth)acrylate monomer, a diluent monomer, a (meth)acrylate-type secondary phosphate, a photoinitiator, and a co-initiator. This adhesive achieves bonding upon photocuring. The jade adhesive not only utilizes its surface properties to wet the jade surface but also leverages the chemical reaction between the phosphate ester and jade components to achieve bonding and repair of fractured jade surfaces. Compared to existing adhesives, it improves shear performance, enhances bonding effectiveness, generally eliminates the risk of misalignment, is insensitive to environmental changes, and exhibits stable bonding. It holds promise for use in adhesive repair methods in jade restoration, providing a new solution for the protection and restoration of jade artifacts.

Description

Technical Field

[0001] This invention belongs to the field of jade adhesive technology, specifically relating to a light-curing jade adhesive, its preparation method, and its application. Background Technology

[0002] Jade artifacts, as precious historical heritage of my country, possess extremely high research value. In recent years, with the large-scale excavation of Neolithic jade artifacts, the demand for the protection and restoration of deteriorated jade artifacts has increased significantly, promoting scientific research in related fields. Among jade restoration techniques, adhesive restoration, as one of the most widely used and effective methods, has gradually gained attention in the industry. Traditional adhesive materials are limited in their application due to drawbacks such as low bonding strength, poor mechanical properties, and low transparency. Modern adhesive materials can be divided into various types, including resin-based, rubber-based, and mixed solution-based materials. Currently, the most commonly used jade adhesives are epoxy resin glue and 502 instant glue, both of which have significant drawbacks. Epoxy resin glue requires external pressure during the bonding process, and the bonding surface is prone to displacement and misalignment. One drawback of 502 instant glue is its sensitivity to environmental changes, easily failing in humid environments; another is its volatility, with the emitted gases having an irritating odor and weak lachrymatory properties; a third drawback is its excessively fast curing speed, making it highly adhesive to clothing and skin, increasing the difficulty of use. With the advancement of science and technology, adhesive materials have developed rapidly, and various new adhesive materials have emerged one after another, bringing new methods for the protection and restoration of cultural relics into a whole new field. Summary of the Invention

[0003] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a light-curable jade adhesive.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned light-cured jade adhesive.

[0005] Another object of the present invention is to provide the application of the above-mentioned light-cured jade adhesive.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A light-curing jade adhesive, comprising the following components by weight:

[0008] 40-80 parts of difunctional or higher (meth)acrylate monomer, 20-60 parts of diluent monomer, 5-20 parts of (meth)acrylate type secondary phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator;

[0009] The relative molecular weight of the difunctional or higher (meth)acrylate monomer is ≥250 g / mol and the viscosity is ≥10 CP; the relative molecular weight of the diluent is <250 g / mol and the viscosity is <10 CP.

[0010] Preferably, the light-cured jade adhesive comprises, by weight, the following components: 51-57 parts of difunctional or higher (meth)acrylate monomer, 34-38 parts of diluent monomer, 5-15 parts of (meth)acrylate type phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

[0011] More preferably, the light-cured jade adhesive comprises, by weight parts, the following components: 51-57 parts of difunctional or higher (meth)acrylate monomer, 34-38 parts of diluent monomer, 5-10 parts of (meth)acrylate type secondary phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

[0012] More preferably, the light-cured jade adhesive comprises, by weight, the following components: 54-57 parts of difunctional or higher (meth)acrylate monomer, 36-38 parts of diluent monomer, 5-10 parts of (meth)acrylate type phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

[0013] Most preferably, the light-cured jade adhesive comprises, by weight, the following components: 54-57 parts of difunctional or higher (meth)acrylate monomer, 36-38 parts of diluent monomer, 5-10 parts of (meth)acrylate type secondary phosphate, 0.7 parts of photoinitiator, and 0.7 parts of co-initiator.

[0014] Preferably, the difunctional or higher (meth)acrylate monomer is at least one of the following: difunctional or higher polyurethane-type (meth)acrylate, difunctional or higher epoxy resin-type (meth)acrylate, difunctional or higher bisphenol A-type (meth)acrylate, and Bis-EFMA.

[0015] More preferably, the difunctional and / or polyfunctional (meth)acrylate monomer is at least one of difunctional polyurethane (meth)acrylate and Bis-EFMA.

[0016] More preferably, the difunctional and / or polyfunctional (meth)acrylate monomer is at least one of di(meth)acrylate and Bis-EFMA.

[0017] Most preferably, the difunctional and / or polyfunctional (meth)acrylate monomer is urethane di(meth)acrylate or a mixture of urethane di(meth)acrylate and Bis-EFMA in a mass ratio of 3:2.

[0018] The structural formula of the Bis-EFMA is as follows:

[0019]

[0020] Preferably, the diluent monomer is at least one of reactive and non-reactive diluent monomers; the reactive diluent is a monomer containing unsaturated terminal alkenyl groups, including monofunctional, difunctional, and polyfunctional monomers containing unsaturated terminal alkenyl groups; more preferably, it is a (meth)acrylate monomer; most preferably, it is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate; the non-reactive diluent monomer is an organic solvent; the organic solvent is at least one of toluene, ethanol, and acetone.

[0021] Preferably, the (meth)acrylate type secondary phosphate is di[2-(methacryloyloxy)ethyl]phosphate.

[0022] Preferably, the photoinitiator is at least one selected from DL-camphorquinone, benzophenone, and 1-phenyl-1,2-propanedione, more preferably DL-camphorquinone.

[0023] Preferably, the co-initiator is at least one of ethyl p-N,N-dimethylaminobenzoate and ethyl p-methacrylate, more preferably ethyl p-N,N-dimethylaminobenzoate.

[0024] The above-mentioned method for preparing a light-cured jade adhesive includes the following steps: mixing (meth)acrylate monomers with difunctionality or higher, diluent monomers, (meth)acrylate type secondary phosphates, photoinitiators and co-initiators in proportion and in the dark to obtain a light-cured jade adhesive.

[0025] The above-mentioned light-cured jade adhesive is used in jade bonding.

[0026] Preferably, in the aforementioned application, the light-cured jade adhesive is polymerized and cured under light irradiation for 20–60 seconds; the light is at least one of blue light and ultraviolet light; the light intensity range is 500–2000 mW / cm². 2 .

[0027] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0028] (1) The jade adhesive provided by the present invention only requires blue light curing during the bonding process, which is convenient and efficient. Unlike the curing method of existing jade adhesives, the jade adhesive of the present invention generally does not have the risk of misalignment of the bonding surface, and is not sensitive to environmental changes, and the bonding effect is stable.

[0029] (2) The jade adhesive formulation provided by the present invention is composed of a difunctional (meth)acrylate monomer, a diluent monomer, a phosphate monomer, a photoinitiator and a co-initiator, which improves the shear performance compared with existing adhesives.

[0030] (3) The jade adhesive provided by the present invention not only utilizes its own surface properties to wet the surface of jade, but also utilizes the characteristic that phosphate ester monomers can chemically react with jade components to achieve bonding and repair of the broken surface of jade, thereby enhancing the bonding effect and having good application prospects. Detailed Implementation

[0031] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0032] Unless otherwise specified in the embodiments of this invention, the conditions shall be performed according to conventional conditions or conditions recommended by the manufacturer. All raw materials and reagents used, unless otherwise specified, are commercially available conventional products.

[0033] The light-cured jade adhesives provided in Examples 1-8 and Comparative Examples 1-3 have raw materials listed in Table 1 by weight, wherein the diluent monomer is hydroxyethyl methacrylate, the photoinitiator is DL-camphorquinone, and the co-initiator is ethyl p-N,N-dimethylaminobenzoate.

[0034] Table 1. Mass composition of Examples 1-6 and Comparative Examples 1-3 and 5-6

[0035]

[0036] The preparation process of jade adhesive is as follows:

[0037] (1) Add 0.05 mol of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (Bis-HEPF) and 0.1 mol of 2-(methacryloyloxy)ethyl isocyanate as reactants to a 250 mL round-bottom flask. Then add a few drops of dibutyltin dilaurate as a catalyst and a small amount of 4-methoxyphenol as a polymerization inhibitor, wherein the amount of polymerization inhibitor is 0.5% of the total mass of the reactants. Finally, add acetone as a solvent and stir at room temperature to dissolve all the substances in the acetone. Place the round-bottom flask in an oil bath and heat it to 43 degrees Celsius with a magnetic stirrer on for 36 hours. After the reaction is complete, take a sample of the liquid in the round-bottom flask and perform Fourier transform infrared spectroscopy to detect whether the sample has an absorption peak of the -NCO group at wavenumber 2270. If an absorption peak is present, extend the reaction time and continue the reaction; if no absorption peak is present, terminate the reaction and proceed with post-processing.

[0038] (2) Place the removed round-mouth flask on a rotary evaporator and heat it in a water bath at 70 degrees Celsius. During heating, remove the round-mouth flask periodically to weigh it until the acetone is completely evaporated. Then remove the sample and the product obtained is Bis-EFMA.

[0039] (3) Accurately weigh the raw material components shown in Table 1 into a brown bottle, wrap the brown bottle with aluminum foil to protect it from light, add a magnetic ball to the bottle, stir at room temperature for 12 hours, and the blue light-induced jade adhesive is obtained.

[0040] The chemical equations for the above reaction steps are shown below:

[0041]

[0042] Comparative Example 4: Commercially available 502 instant adhesive

[0043] To illustrate that the blue light-cured jade adhesive of the present invention has the advantage of improving shear strength, commercially available 502 instant adhesive was used as comparative example 4.

[0044] The characterization methods used for Examples 1-8 and Comparative Example 1 are as follows:

[0045] 1. Double bond conversion rate test of jade adhesive samples: Double bond conversion rate is an experiment to determine the degree of chemical reaction of double bonds in a material over a specified time.

[0046] The test sample was uniformly coated into a thin film on a potassium bromide sheet. The infrared spectrum of the sample before curing was recorded. Then, the test sample was cured by irradiating with a blue light curing lamp at room temperature for 40 seconds, and the infrared spectrum of the sample after curing was recorded. Since the intensity of the stretching vibration peak of the C=C double bond at 1640 wavenumber decreased significantly before and after blue light irradiation, while the characteristic peak of the benzene ring at 1608 wavenumber did not change significantly, the characteristic absorption peak of the benzene ring at 1608 wavenumber was used as the internal standard peak to normalize the infrared spectrum. The double bond conversion rate (DC) was calculated based on the change of the absorption peak of the C=C double bond at 1636 wavenumber before and after curing. Each group of samples was measured 6 times, and the arithmetic mean of the 6 results of each group was taken as the final result of the sample. The calculation formula is shown in (1):

[0047]

[0048] In the formula, A C＝C And A ph The areas of the infrared absorption peaks of the sample at 1640 wavenumber for the C=C double bond and at 1608 wavenumber for the benzene ring are respectively; (A C＝C / A ph ) t and (A) C＝C / A ph )0 represent the normalized absorption peak intensities of the C=C double bond under illumination for t seconds and 0 seconds, respectively. DC is the double bond conversion rate of the sample under blue light illumination for t seconds.

[0049] The test results are shown in Table 2.

[0050] 2. Testing of bending strength and flexural modulus of jade adhesive samples: Bending performance testing is an experiment to determine the mechanical properties of a material under bending load. Currently, the three-point bending method is commonly used when conducting bending tests on resins.

[0051] Using a polyester film as a substrate, the sample was injected into a rectangular silicone mold measuring 25 mm × 2 mm × 2 mm, then covered with another polyester film, flattened, and air bubbles were removed. The sample was evenly divided into five equal parts, and each part was irradiated with a blue light curing lamp for 40 seconds before the cured sample was removed. After curing, the sample was polished using a metallographic sample polishing machine (grinding disc diameter 230 mm, rotation speed 180 rpm). Six samples were prepared for each sample, and the arithmetic mean of the six samples in each group was taken as the final result of the sample.

[0052] The test was conducted using a universal testing machine, with a load rate of 1.00 mm / min and a spline span of 20 mm. The flexural strength (FS) and flexural modulus (FM) of the spline were calculated using formulas (2) and (3), respectively:

[0053]

[0054] In the formula, F is the load, l is the span, b is the width, and h is the thickness.

[0055]

[0056] In the formula, σ represents stress and ε represents strain.

[0057] The test results are shown in Table 3.

[0058] 3. Jade adhesive surface contact angle test: The surface contact angle is an experiment to determine the degree of wettability of a material on a specified surface.

[0059] First, the jade was embedded in resin. The resulting sample stage was divided into two groups. Then, the samples were polished in groups using 500-grit and 2000-grit sandpaper. Each polished sample stage was ultrasonically cleaned in anhydrous ethanol for 30 minutes to remove any abrasive material that might be embedded on the surface of the sample stage. After ultrasonic cleaning, the sample stage was placed in a desiccator to dry for later use.

[0060] Use a disposable syringe to draw an appropriate amount of sample and drop it onto the sample stage surface. After the droplet has stabilized on the sample stage surface for 20 seconds, measure the surface contact angle of the sample. Measure each group of samples 6 times and take the arithmetic mean of the 6 results of each group as the final result.

[0061] The test results are shown in Table 4.

[0062] 4. Shear strength test of jade adhesive samples: The shear performance test is an experiment to determine the maximum load that the adhesive can withstand per unit area parallel to the adhesive surface. It is an important indicator of the adhesive bonding strength.

[0063] First, a sample stage was prepared by embedding the jade in resin. A suitable amount of sample was then applied to the sample stages after polishing with 500-grit and 2000-grit sandpaper, respectively. The jade was then placed in contact with the sample stage. For the four comparative groups, the samples were prepared by allowing them to stand in air for 40 seconds. For the remaining groups, the bonding area was irradiated with a blue light for 40 seconds to complete the sample preparation. Six sample stages were used for each group of tests, and the arithmetic mean of the six measurements for each group was taken as the final result.

[0064] The test was conducted using a universal testing machine, with a load rate set to 1.00 mm / min. The shear strength (SS) of the specimen was calculated using formula (4):

[0065]

[0066] In the formula, F is the load and d is the diameter of the jade.

[0067] The test results are shown in Table 5.

[0068] Table 2 Double bond conversion rate of jade adhesive samples after 40 seconds of blue light curing.

[0069]

[0070]

[0071] Table 3. Flexural strength and flexural modulus of the jade adhesive samples.

[0072]

[0073] Table 4. Contact angle of jade adhesive on jade surface

[0074]

[0075] Table 5 Shear strength of jade adhesive samples

[0076]

[0077] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A light-curing jade adhesive, characterized in that, By mass parts, it includes the following components: 40-80 parts of difunctional or higher (meth)acrylate monomer, 20-60 parts of diluent monomer, 5-20 parts of (meth)acrylate type secondary phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator; The relative molecular weight of the difunctional (meth)acrylate monomer is ≥250 g / mol and the viscosity is ≥10 CP; the relative molecular weight of the diluent monomer is <250 g / mol and the viscosity is <10 CP. The difunctional or higher (meth)acrylate monomers are difunctional polyurethane-type (meth)acrylates and Bis-EFMA; The structural formula of the Bis-EFMA is as follows: ； The diluent monomer is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate; The (meth)acrylate type secondary phosphate is di[2-(methacryloyloxy)ethyl] phosphate.

2. The light-curable jade adhesive according to claim 1, characterized in that, By weight, it includes the following components: 51-57 parts of difunctional or higher (meth)acrylate monomer, 34-38 parts of diluent monomer, 5-15 parts of (meth)acrylate type phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

3. The light-cured jade adhesive according to claim 2, characterized in that, By weight, it includes the following components: 51-57 parts of difunctional or higher (meth)acrylate monomer, 34-38 parts of diluent monomer, 5-10 parts of (meth)acrylate type phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

4. The light-cured jade adhesive according to claim 3, characterized in that, By weight, it includes the following components: 54-57 parts of difunctional or higher (meth)acrylate monomer, 36-38 parts of diluent monomer, 5-10 parts of (meth)acrylate type phosphate, 0.3-1.0 parts of photoinitiator, and 0.3-1.0 parts of co-initiator.

5. The light-cured jade adhesive according to claim 1, characterized in that, The difunctional or higher (meth)acrylate monomers are di(meth)acrylate and Bis-EFMA.

6. The light-cured jade adhesive according to claim 1, characterized in that, The photoinitiator is at least one of DL-camphorquinone, benzophenone and 1-phenyl-1,2-propanedione; The co-initiator is at least one of ethyl p-N,N-dimethylaminobenzoate, ethyl dimethylaminobenzoate, and ethyl dimethylaminomethacrylate.

7. A method for preparing a light-cured jade adhesive according to any one of claims 1 to 6, characterized in that, Includes the following steps: A light-cured jade adhesive is obtained by mixing (meth)acrylate monomers with bifunctionality or higher, diluent monomers, (meth)acrylate type phosphate, photoinitiator and co-initiator in a certain proportion in the dark.

8. The application of the light-cured jade adhesive according to any one of claims 1 to 6 in jade bonding, characterized in that, The adhesive cures under blue light and / or ultraviolet light.

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