A polyacrylate coating, its preparation method and application

Abstract

This invention provides a polyacrylate coating, its preparation method, and its application. The polyacrylate coating comprises acrylate oligomers, acrylate polymer-grafted metal-organic framework materials, reactive diluents, and photoinitiators. By selecting acrylate polymer-grafted metal-organic framework materials as additives, they can not only be uniformly dispersed in the coating system, ensuring long-term stability and effectiveness, but also have high affinity. They can utilize their high affinity to form a highly cross-linked polyacrylate / MOF composite coating with acrylate oligomers, further enhancing the toughness of the coating, making it suitable as an inner layer coating for optical fibers.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to a polyacrylate coating, its preparation method, and its application. Background Technology

[0002] With the rapid development of optical communication technology, optical fiber, as a fundamental material, has been widely used in many fields. However, optical fibers, drawn from glass or plastic, are thin and brittle, easily damaged, and require multi-layer coatings for protection, providing strength protection, waterproofing, and stress buffering. Traditional optical fiber coatings consist of inner and outer layers. In practice, to ensure the service life and performance of the optical fiber, the inner coating required for high-speed drawing needs to have high toughness to maximize the protection of the bare fiber, improve its resistance to external forces, and reduce the attenuation caused by micro-bending to a certain extent.

[0003] Metal-organic frameworks (MOFs) have attracted widespread attention in recent years due to their superior properties compared to other porous materials, including very large surface area, permanent porosity, customizable pore size and distribution, chemical versatility, structural flexibility, ease of functionalization, and high mechanical and thermal stability. MOF-based nanocomposites, formed by incorporating MOF nanoparticles into polymer coating systems, not only combine the characteristics of both MOFs and polymers but also overcome the brittleness and insufficient strength of coatings formed after curing, making them an effective approach for preparing high-toughness composite inner layer coatings. However, the poor dispersibility of nanoparticles in resin coatings is a challenge in the preparation of composite coatings, and MOF nanoparticles also face this problem.

[0004] Therefore, in order to address the above-mentioned technical problems, there is an urgent need to develop a polyacrylate coating with good compatibility and high toughness. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a polyacrylate coating, its preparation method, and its application. By selecting acrylate polymers grafted with metal-organic framework materials as additives, these materials can not only be uniformly dispersed in the polyacrylate coating system, ensuring long-term stability and effectiveness, but also utilize their high affinity interactions to form a highly crosslinked polyacrylate / MOF composite coating with acrylate oligomers, further enhancing the toughness of the coating, making it suitable as an inner layer coating for optical fibers.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a polyacrylate coating, the polyacrylate coating comprising an acrylate oligomer, an acrylate polymer grafted with a metal-organic framework material, a reactive diluent, and a photoinitiator.

[0008] The polyacrylate coating provided by the present invention comprises acrylate oligomers, acrylate polymer grafted metal-organic framework materials, reactive diluents and photoinitiators. By adding the acrylate polymer grafted metal-organic framework materials, the polyacrylate coating is highly uniformly dispersed, and the coating has high toughness and mechanical strength after formation, making it suitable as an inner layer coating for optical fibers.

[0009] Specifically, on the one hand, compared with traditional nanoparticles, the metal-organic framework (MOF) in the acrylate polymer-grafted metal-organic framework material added in this invention has a larger specific surface area. It can effectively enhance the interfacial region between the polyacrylate chains and the polyacrylate resin at the atomic level. Simultaneously, utilizing the high affinity interaction between the MOF and organic compounds, the polyacrylate coating provided by this invention can form a highly cross-linked polyacrylate / MOF composite coating, thereby exhibiting high strength and high toughness. Furthermore, the MOF, as an additive, can participate in the photocuring reaction of the optical fiber coating through the Lewis acid sites and functional groups of the organic linker. Further increasing the crosslinking degree of polyacrylate improves the mechanical strength of the coating. On the other hand, since the acrylate polymer grafted metal-organic framework material has abundant acrylate polymers on its surface, it has similar miscibility with the acrylate oligomers in the coating, which can effectively overcome the problems of poor compatibility and uneven dispersion of existing composite coatings. It has excellent dispersion uniformity and more stable and balanced performance than other coating products. In addition, since the surface of the acrylate polymer grafted metal-organic framework material has polyacrylate polymer chains, it can act as a damper to help the coating resist external stress and further enhance the toughness of the polyacrylate coating.

[0010] Preferably, the polyacrylate coating comprises the following components in parts by weight:

[0011]

[0012] In this invention, the content of acrylate oligomer in the polyacrylate coating is 15 to 75 parts by weight, for example, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight or 70 parts by weight.

[0013] In this invention, the content of acrylate polymer-grafted metal-organic framework material in the polyacrylate coating is 1 to 5 parts by weight, for example, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, etc.

[0014] In this invention, the content of the reactive diluent in the polyacrylate coating is 5 to 25 parts by weight, for example, 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight or 23 parts by weight, etc.

[0015] In this invention, the content of photoinitiator in the polyacrylate coating is 0.1 to 5 parts by weight, for example, it can be 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, etc.

[0016] In this invention, there are no special requirements for the functionality or specific type of the acrylate oligomer and the specific type of the acrylate polymer grafted with the metal-organic framework material. However, in order to obtain a polyacrylate coating with superior performance, the following preferences are made:

[0017] Preferably, the acrylate oligomer includes any one or a combination of at least two of difunctional acrylate oligomers, trifunctional acrylate oligomers, or tetrafunctional acrylate oligomers, and more preferably a difunctional acrylate oligomer. The functionality should not be too high, as higher functionality leads to higher crosslinking and thus poorer flexibility.

[0018] Preferably, the acrylate oligomer includes any one or a combination of at least two of the following: polyurethane acrylate oligomer, epoxy acrylate oligomer, methacrylate oligomer, silicone-modified acrylate oligomer, fluorine-modified polyacrylate oligomer, polyether acrylate oligomer, polyester acrylate oligomer, phosphate acrylate oligomer, or carboxyl acrylate oligomer.

[0019] Preferably, the acrylate polymers in the acrylate polymer-grafted metal-organic framework material include any one or a combination of at least two of the following: tert-butyl polyacrylate, N,N-dimethylaminoethyl methacrylate, polymethyl methacrylate, polyhydroxyethyl methacrylate, or polyhydroxypropyl methacrylate.

[0020] Preferably, the metal-organic framework material in the acrylate polymer-grafted metal-organic framework material includes UiO-66(Zr).

[0021] In this invention, the preparation method of the acrylate polymer-grafted metal-organic framework material is not specifically limited. However, in order to obtain a polyacrylate coating with better toughness, taking acrylate polymer-grafted UiO-66(Zr) as an example, the preparation method is limited to the following steps:

[0022] (1) First, ZrCl4 and 2-aminoterephthalic acid were dissolved in N,N-dimethylformamide (DMF), ultrasonicated at room temperature, acetic acid was added, and stirred at room temperature to obtain a mixture; the mixture was sealed in an autoclave reactor and placed in an oven. After natural cooling, the solid product obtained by centrifuging the suspension was calcined to obtain UiO-66-NH2.

[0023] (2) Disperse the UiO-66-NH2 obtained in step (1) in dichloromethane (DCM), add 2-bromoisobutyryl bromide and triethylamine, and obtain UiO-66-Br through bromination reaction;

[0024] (3) The UiO-66-g-Br, acrylate monomer, catalyst, co-catalyst and solvent obtained in step (2) are subjected to ultrasonic mixing reaction to obtain the acrylate polymer grafted with UiO-66(Zr).

[0025] Preferably, the time for room temperature ultrasound in step (1) is 0.5 to 2 hours, for example, 0.7 hours, 0.9 hours, 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours or 1.9 hours.

[0026] Preferably, the stirring time at room temperature in step (1) is 1 to 5 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours.

[0027] Preferably, the centrifugation speed in step (1) is 7000-10000 rpm, such as 7500 rpm, 8000 rpm, 8500 rpm, 9000 rpm, or 9500 rpm.

[0028] Preferably, the catalyst in step (3) is a monovalent copper compound, including but not limited to copper salts such as CuBr and CuCl, and monovalent copper complexes such as CuBr(PPh3)3 and [Cu(CH3CN)4]PF6.

[0029] Preferably, the cocatalyst in step (3) comprises pentamethyldiethylenetriamine (PMDETA).

[0030] In this invention, the reaction temperature in step (3) is related to the type of acrylate monomer and can be adjusted according to the actual situation. Different reaction times can obtain polymer layers of different thicknesses. Preferably, the reaction temperature in step (3) is 25 to 120°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or 110°C, etc., and the reaction time in step (3) is 6 to 50 hours, such as 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours or 45 hours, etc.

[0031] Preferably, the reactive diluent comprises acrylate monomers.

[0032] In this invention, no special limitation is placed on the functionality of the acrylate monomers, including but not limited to monofunctional, difunctional or trifunctional acrylate monomers.

[0033] Preferably, the acrylate monomers include any one or a combination of at least two of polyurethane acrylate monomers, epoxy acrylate monomers, methacrylate monomers, silicone acrylate monomers, or polyester acrylate monomers.

[0034] Preferably, the photoinitiator includes a free radical photoinitiator, and more preferably a free radical photoinitiator capable of absorbing light with a wavelength of 350–410 nm.

[0035] Preferably, the free radical photoinitiator includes any one or a combination of at least two of the following: benzoin compounds, benzoyl photochemical compounds, dialkoxyacetophenone, α-hydroxyalkyl phenyl ketone, α-aminealkyl phenyl ketone, acylphosphine oxide, benzophenone, or heterocyclic aromatic ketone compounds.

[0036] In a second aspect, the present invention provides a method for preparing a polyacrylate coating as described in the first aspect, the method comprising: mixing an acrylate oligomer, an acrylate polymer grafted with a metal-organic framework material, an active diluent and a photoinitiator to obtain the polyacrylate coating.

[0037] Thirdly, the present invention provides an application of the polyacrylate coating as described in the first aspect as an inner layer coating for optical fibers.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The polyacrylate coating provided by this invention comprises acrylate oligomers, acrylate polymer-grafted metal-organic framework materials, reactive diluents, and photoinitiators. By selecting acrylate polymer-grafted metal-organic framework materials as additives, they can not only be uniformly dispersed in the polyacrylate coating system, ensuring long-term stability and effectiveness, but also form a highly cross-linked polyacrylate / MOF composite coating with acrylate oligomers through their high affinity interaction, further enhancing the toughness of the coating, making it suitable as an inner layer coating for optical fibers. Detailed Implementation

[0040] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0041] Preparation Example 1

[0042] A poly(tert-butyl acrylate) grafted metal-organic framework material, UiO-66-PtBA, is prepared by the following steps:

[0043] (1) First, 0.66 mM ZrCl4 and 0.6 mM 2-aminoterephthalic acid were dissolved in 20 mL DMF and sonicated at room temperature for 30 min. Then, 0.24 mM acetic acid was added and stirred at room temperature for 1 h. The resulting mixture was sealed in an autoclave reactor and placed in an oven at 120 °C for 24 h. After natural cooling, the suspension was centrifuged at 8500 rpm for 15 min, washed once with DMF, and washed three times with methanol. Finally, the solid product was calcined at 60 °C for 24 h to obtain UiO-66-NH2.

[0044] (2) Disperse 100 mg of UiO-66-NH2 obtained in step (1) in a flask containing 20 mL of DCM and sonicate for 30 min; then add 5 mL of triethylamine to the flask, and then add 1 mL of 2-bromoisobutyl bromide at 0 °C. Stir the mixture at 0 °C for 2 h, store at room temperature for 24 h, centrifuge the resulting suspension at 8500 rpm for 15 min, then wash once with DCM and three times with methanol; finally, dry the solid product at 60 °C for 24 h to obtain UiO-66-Br.

[0045] (3) 20 mg of UiO-66-Br obtained in step (2), 35 mg of CuBr and 85 mg of Me6TREN, 10 mL of tert-butyl acrylate (tBA) and 10 mL of DMF were added to a round-mouth flask and then degassed by three nitrogen cycles. The sample was heated in an oil bath at 60 °C for 24 h. After the reaction was completed, it was centrifuged at 8500 rpm for 15 min and then washed three times with methanol. The solid product was dried at 60 °C for 48 h to obtain the polytert-butyl acrylate grafted metal-organic framework material UiO-66-PtBA.

[0046] Preparation Example 2

[0047] A polymethyl methacrylate-grafted metal-organic framework material, UiO-66-PMMA, differs from Preparation Example 1 in that methyl methacrylate (MMA) is used instead of tert-butyl acrylate, while other substances, parameters, and preparation methods are the same as in Preparation Example 1.

[0048] Preparation Example 3

[0049] A polymethyl methacrylate-grafted metal-organic framework material, UiO-66-PHEMA, differs from Preparation Example 1 in that hydroxyethyl methacrylate (HEMA) is used instead of tert-butyl acrylate. All other materials, parameters, and preparation methods are the same as in Preparation Example 1.

[0050] Comparative Preparation Example 1

[0051] A metal-organic framework material, UiO-66-NH2, is prepared by the following method: 0.66 mM ZrCl4 and 0.6 mM 2-aminoterephthalic acid are dissolved in 20 mL DMF and sonicated at room temperature for 30 min. Then, 0.24 mM acetic acid is added and stirred at room temperature for 1 h. The resulting mixture is sealed in an autoclave reactor and placed in an oven at 120 °C for 24 h. After natural cooling, the suspension is centrifuged at 8500 rpm for 15 min, washed once with DMF, and washed three times with methanol. Finally, the solid product is calcined at 60 °C for 24 h to obtain the metal-organic framework material UiO-66-NH2.

[0052] Example 1

[0053] A polyacrylate coating, comprising the following components by weight:

[0054]

[0055] Specifically, the acrylate oligomer is an aliphatic polyurethane acrylate oligomer, purchased from Guangdong Haohui New Materials Co., Ltd., with the brand name HP6219.

[0056] The acrylate polymer-grafted metal-organic framework material is the polytert-butyl acrylate-grafted metal-organic framework material UiO-66-PtBA provided in Preparation Example 1.

[0057] The reactive diluent is specifically isobornyl methacrylate monomer;

[0058] The photoinitiator is (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide;

[0059] The method for preparing the polyacrylate coating provided in this embodiment includes: uniformly mixing acrylate oligomers, acrylate polymer grafted with metal-organic framework materials, reactive diluents and photoinitiators to obtain the polyacrylate coating.

[0060] Example 2

[0061] A polyacrylate coating, comprising the following components by weight:

[0062]

[0063] Specifically, the acrylate oligomer is an aliphatic polyurethane acrylate oligomer, purchased from Guangdong Haohui New Materials Co., Ltd., with the brand name HP6219.

[0064] The acrylate polymer-grafted metal-organic framework material is the polymethyl methacrylate-grafted metal-organic framework material UiO-66-PMMA provided in Preparation Example 2;

[0065] The reactive diluent is specifically isobornyl methacrylate monomer;

[0066] The photoinitiator is α-hydroxyalkyl phenyl ketone;

[0067] The method for preparing the polyacrylate coating provided in this embodiment includes: uniformly mixing acrylate oligomers, acrylate polymer grafted with metal-organic framework materials, reactive diluents and photoinitiators to obtain the polyacrylate coating.

[0068] Example 3

[0069] A polyacrylate coating, comprising the following components by weight:

[0070]

[0071] Specifically, the acrylate oligomer is an aliphatic polyurethane acrylate oligomer, purchased from Guangdong Haohui New Materials Co., Ltd., with the brand name HP6219.

[0072] The acrylate polymer-grafted metal-organic framework material is the hydroxyethyl methacrylate-grafted metal-organic framework material UiO-66-PHEMA provided in Preparation Example 3;

[0073] The reactive diluent is specifically isobornyl methacrylate monomer;

[0074] The photoinitiator is benzophenone;

[0075] The method for preparing the polyacrylate coating provided in this embodiment includes: uniformly mixing acrylate oligomers, acrylate polymer grafted with metal-organic framework materials, reactive diluents and photoinitiators to obtain the polyacrylate coating.

[0076] Examples 4-6

[0077] A polyacrylate coating differs from Example 1 only in that the amount of acrylate polymer grafted with metal-organic framework material added is 1 part by weight (Example 4), 5 parts by weight (Example 5), and 0.5 parts by weight (Example 6), respectively. The other components, amounts, and preparation methods are the same as in Example 1.

[0078] Comparative Example 1

[0079] A polyacrylate coating differs from Example 1 only in that the metal-organic framework material UiO-66-NH2 provided in Comparative Preparation Example 1 is used instead of the polytert-butyl acrylate-grafted metal-organic framework material UiO-66-PtBA provided in Preparation Example 1. All other components, dosages, and preparation methods are the same as in Example 1.

[0080] Comparative Example 2

[0081] A polyacrylate coating differs from Example 1 only in that no acrylate polymer grafted metal-organic framework material is added; all other components, dosages, and preparation methods are the same as in Example 1.

[0082] Toughness characterization:

[0083] (1) Sample preparation: First, place the coater on a clean glass plate, then add an appropriate amount of bubble-free polyacrylate coating, turn on the coater to scrape the film and prepare the sample, and then place the substrate with the coated sample on an irradiation energy of 1000mJ / cm². 2 The film was cured under a UV curing lamp, and the cured sample film was prepared as a dumbbell-shaped or rectangular sample film with a length, width (middle section of dumbbell shape) and thickness of 10±2cm, 12.5±0.1mm and 0.15±0.01mm, respectively.

[0084] (2) Elongation at break test: The tensile force of the sample film was tested using a universal testing machine (refer to GB / T1040.2-2006). The test results are shown in Table 1.

[0085] Table 1

[0086] Elongation at break / % Example 1 144 Example 2 128 Example 3 114 Example 4 132 Example 5 124 Example 6 125 Comparative Example 1 128 Comparative Example 2 120

[0087] According to the data in Table 1:

[0088] The polyacrylate coating provided by the present invention has high coating toughness and a coating elongation at break of up to 144%. Compared with Example 1, the polyacrylate coating provided in Comparative Example 1 did not have the metal-organic framework material added polymer grafted, and the coating elongation at break was only 128%. The polyacrylate coating provided in Comparative Example 2 did not have the metal-organic framework material added, and the coating elongation at break was only 120%.

[0089] The applicant declares that this invention illustrates a polyacrylate coating, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used in the product, addition of auxiliary components, and selection of specific methods, all fall within the protection and disclosure scope of this invention.

Claims

1. A polyacrylate coating, characterized in that, The polyacrylate coating comprises the following components in parts by weight: 15-75 parts by weight of acrylate oligomer; 1-5 parts by weight of acrylate polymer grafted metal-organic framework material; 5-25 parts by weight of reactive diluent; Photoinitiator 0.1~5 parts by weight; The metal-organic framework material in the acrylate polymer-grafted metal-organic framework material is UiO-66(Zr).

2. The polyacrylate coating according to claim 1, characterized in that, The acrylate oligomers include any one or a combination of at least two of the following: difunctional acrylate oligomers, trifunctional acrylate oligomers, or tetrafunctional acrylate oligomers.

3. The polyacrylate coating according to claim 2, characterized in that, The acrylate oligomer is a difunctional acrylate oligomer.

4. The polyacrylate coating according to claim 1, characterized in that, The acrylate oligomers include any one or a combination of at least two of the following: polyurethane acrylate oligomers, epoxy acrylate oligomers, methacrylate oligomers, silicone-modified acrylate oligomers, fluorine-modified polyacrylate oligomers, polyether acrylate oligomers, polyester acrylate oligomers, phosphate acrylate oligomers, or carboxyl acrylate oligomers.

5. The polyacrylate coating according to claim 1, characterized in that, The acrylate polymers in the acrylate-grafted metal-organic framework material include any one or a combination of at least two of the following: tert-butyl polyacrylate, N,N-dimethylaminoethyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate.

6. The polyacrylate coating according to claim 1, characterized in that, The reactive diluent includes acrylate monomers.

7. The polyacrylate coating according to claim 6, characterized in that, The acrylate monomers include any one or a combination of at least two of the following: polyurethane acrylate monomers, epoxy acrylate monomers, methacrylate monomers, silicone acrylate monomers, or polyester acrylate monomers.

8. The polyacrylate coating according to claim 1, characterized in that, The photoinitiator includes a free radical photoinitiator.

9. The polyacrylate coating according to claim 8, characterized in that, The free radical photoinitiator includes any one or a combination of at least two of the following: benzoin compounds, benzoyl photoinitiators, diekoxyacetophenone, α-hydroxyalkylacetophenone, α-aminealkylacetophenone, acylphosphine oxide, benzophenone, or heterocyclic aromatic ketone compounds.

10. A method for preparing a polyacrylate coating as described in any one of claims 1 to 9, characterized in that, The preparation method includes: mixing acrylate oligomers, acrylate polymers grafted with metal-organic framework materials, reactive diluents and photoinitiators to obtain the polyacrylate coating.

11. The application of a polyacrylate coating as described in any one of claims 1 to 9 as an inner layer coating for optical fibers.

Images