Functional acrylate material and preparation method thereof

Abstract

The invention provides a functional acrylate material and a preparation method thereof, the functional acrylate material has a structural formula as shown in a formula (I), n is 7-14, and R is a structure as shown in a formula (II) or a formula (III). The solar aging resistance, the water vapor barrier property and the mechanical property can be improved.

Description

Technical Field

[0001] This invention belongs to the field of photosensitive polymer materials technology, specifically relating to a functional acrylate material and its preparation method. Background Technology

[0002] UV curing technology boasts the "5E" characteristics of high efficiency, wide applicability, economy, energy saving, and environmental friendliness, making it widely used in coatings, inks, adhesives, optical films, automobiles, and the photovoltaic industry. However, because UV-curable materials invariably contain reactive (meth)acrylates and / or aromatic rings, conjugated ester groups, etc., their performance in areas such as resistance to outdoor sunlight aging is insufficient, thus limiting the application of UV curing technology.

[0003] Inorganic materials such as quantum dots (CdSe) and perovskites require protection through functional coatings or adhesive embedding to extend their lifespan, block water and oxygen, and reduce their impact. For example, UV-cured perovskite solar cells (PSCs) cure at room temperature, facilitating operation; their low-viscosity formulations ensure good wettability and density on the substrate surface. For rigid glass PSCs, sealing the upper and lower glass edges is necessary to effectively block water and oxygen; simultaneously, the UV encapsulation adhesive's resistance to sunlight aging must be considered.

[0004] Therefore, it is of great significance to provide a photocurable material with good resistance to sunlight aging and excellent water and oxygen barrier properties. Summary of the Invention

[0005] In view of this, the present invention provides a functional acrylate material and its preparation method, which can improve the resistance to sunlight aging, water vapor barrier properties and mechanical properties.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a functional acrylate material having the structural formula shown in formula (I):

[0007] Where n is 7~14, and R is the structure shown in equation (II) or equation (III): .

[0008] Secondly, the present invention also provides a method for preparing the aforementioned functional acrylate material, comprising the following steps: S1. Under the action of the first catalyst, dicyclopentadiene undergoes a ring-opening metathesis polymerization reaction in the first solvent to obtain compound A; S2. Under the action of a second catalyst, compound A and mercaptopropanol undergo a Michael addition reaction in a second solvent to give compound B. S3. Under the action of a third catalyst and hydrogen pressure, compound B undergoes a hydrogenation reaction in a third solvent to obtain compound C. S4. Under the action of the fourth catalyst, compound C and compound D undergo an addition reaction in the fourth solvent to obtain a functional acrylate material; The structural formulas of compounds A, B, C, and D are as follows:

[0009] .

[0010] It should be noted that the synthetic route of the functional acrylate material can be as follows: .

[0011] The functional acrylate material has a saturated alicyclic hydrocarbon structure and acrylate bonds. The functional acrylate material (hydrogenated polydicyclopentadiene-modified acrylate material) is obtained by reacting a polydicyclopentadiene material (compound A) of appropriate molecular weight with mercaptopropanol under mild conditions, where the reaction occurs only with the unhindered double bonds at the terminal positions. This is followed by hydrogenation to obtain a saturated alicyclic hydrocarbon structure, and finally, acrylate bonds are introduced through an addition reaction of hydroxyl and isocyanate groups. In step S1, ethylene can be introduced as a chain transfer agent to control the molecular weight of the polymer.

[0012] Preferably, in step S1: The first catalyst is a ruthenium carbene catalyst; and / or, The first solvent is cyclohexane; and / or, The mass ratio of the dicyclopentadiene to the first solvent is 100:(200~900); and / or, The mass ratio of the first catalyst to the dicyclopentadiene is (0.01~1):100; and / or, The reaction pressure is 0~1 MPa, the reaction temperature is 30~70 ℃, and the reaction time is 1~60 min.

[0013] Preferably, step S1 includes the following steps: S11. Under the action of the first catalyst, dicyclopentadiene undergoes a ring-opening metathesis polymerization reaction in the first solvent to obtain the first reaction solution. S12. Add the first reaction solution to isopropanol to precipitate the polymer, filter, and dry to obtain compound A.

[0014] Preferably, in step S2: The second catalyst is a Lewis base catalyst; and / or, The second solvent is toluene; and / or, The molar ratio of compound A to mercaptopropanol is 1:(2.05~2.1); and / or, The amount of the second catalyst is 1000-3000 ppm of the total mass of compound A, mercaptoethanol, the second solvent, and the second catalyst; and / or, The reaction temperature is 45~60 ℃, and the reaction time is 3~6 h.

[0015] Preferably, step S2 includes the following steps: S21. Under the action of a second catalyst, compound A and mercaptopropanol undergo a Michael addition reaction in a second solvent to obtain a second reaction solution. S22. The second reaction solution is desolventized and dried to obtain compound B.

[0016] Preferably, in step S3: The third catalyst is a supported hydrogenation catalyst; and / or, The third solvent is cyclohexane; and / or, The mass ratio of compound B to the third solvent is 100:(200~900); and / or, The mass ratio of the third catalyst to compound B is (0.1~10):100; and / or, The hydrogen pressure for the reaction is 1~10 MPa, the temperature for the reaction is 100~150 ℃, and the reaction time is 1~10 h.

[0017] Preferably, step S3 includes the following steps: S31. Under the action of a third catalyst and hydrogen pressure, compound B undergoes a hydrogenation reaction in a third solvent to obtain a third reaction solution. S32. The third reaction solution is filtered through a filter membrane and dried to obtain compound C; wherein the pore size of the filter membrane is 0.1~10 μm.

[0018] Preferably, in step S4: The fourth catalyst is at least one selected from dibutyltin dilaurate, bismuth neodecanoate, and zinc neodecanoate; and / or The fourth solvent is toluene; and / or, The molar ratio of compound C to compound D is 1:(1.99~2.01); and / or, The amount of the fourth catalyst is 500-1500 ppm of the total mass of compound C, compound D, the fourth solvent, and the fourth catalyst; and / or, The reaction temperature is 50~80℃, and the reaction time is 3~6 h; and / or, The compound D is obtained by reacting hydroxyethyl acrylate with isocyanate at 40-50 °C until the NCO conversion rate of the isocyanate reaches 48-52%, wherein the isocyanate is isophorone diisocyanate or 4,4-diisocyanate dicyclohexylmethane.

[0019] Preferably, in step S1, the first catalyst is at least one of a first-generation Grubbs catalyst, a second-generation Grubbs catalyst, and a third-generation Grubbs catalyst; and / or, In step S2, the second catalyst is at least one of triphenylphosphine and tetrabutylammonium bromide; and / or, In step S3, the third catalyst is at least one of Ni / Al2O3 supported hydrogenation catalyst, Ni / diatomite supported hydrogenation catalyst, Pd / C supported hydrogenation catalyst, and Ru / Al2O3 supported hydrogenation catalyst.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: The functional acrylate material provided by this invention has an inert saturated alicyclic hydrocarbon structure and acrylate bonds. The saturated alicyclic hydrocarbon structure gives the functional acrylate material high transparency, good resistance to sunlight aging, and excellent hard and tough mechanical properties. Moreover, because the cyclic structure is not easily deformed, the functional acrylate material has good adhesion and bonding properties. At the same time, the structure is a saturated bicycloalkane inert structure, which gives the functional acrylate material good water vapor / oxygen barrier properties. It is expected to broaden the application of photocuring technology in automotive exteriors, quantum dot embedding, photovoltaic industry and other fields. Detailed Implementation

[0021] The present invention will now be described in further detail with reference to specific embodiments, so that those skilled in the art can more clearly understand the present invention.

[0022] Example 1 The preparation of compound A, based on parts by weight of the raw materials, includes the following steps: 100 parts of dicyclopentadiene and 900 parts of cyclohexane were mixed, and 2 parts of ethylene and 0.05 parts of first-generation Grubbs catalyst were added. The mixture was reacted at 0.1 MPa and 60 °C for 30 min. The reaction solution was then precipitated into a polymer in 3000 parts of isopropanol. The polymer was filtered and dried at -0.09 MPa and 60 °C for 5 h to obtain compound A.

[0023] The molecular weight of compound A was determined using high-temperature gel permeation chromatography (HTPC) with 1,2,4-trichlorobenzene as the solvent, a sample concentration of 1 mg / mL, a flow rate of 1 mL / min, and at 135 °C. Polystyrene standards were used as a reference for molecular weight determination. The results showed a weight-average molecular weight (Mw) of 1800, a number-average molecular weight (Mn) of 1480, and a molecular weight distribution (PDI) (Mw / Mn) of 1.22.

[0024] Example 2 The preparation of compound B includes the following steps: Compound A (100 g, 0.068 mol), mercaptopropanol (12.97 g, 0.141 mol), and toluene (70 g) were added to a 500 mL straight four-necked flask. Nitrogen gas was introduced, and triphenylphosphine catalyst (0.36 g, 2000 ppm of total material) was added. The reaction was carried out at 50 °C for 2 h. The solid content was then tested by sampling (drying at 110 °C for 1 h). The solid content remained unchanged for 2 h, at which point the reaction was considered complete (mercaptopropanol has a partial boiling point of 81 °C and can be completely dried at 110 °C). After the reaction was completed, the solvent and a small amount of mercaptopropanol were removed by rotary evaporation, and the mixture was dried to obtain compound B.

[0025] 1 ¹H NMR (400 MHz, CDCl₃) δ 6.08–6.02 (m, 11.20H), 5.61–5.66 (m, 11.20H), 5.30–5.35 (m, 2.40H), 3.30–3.35 (t, 4H), 2.40–2.62 (t, 8H), 2.45–2.50 (m, 11.20H), 2.30–2.35 (m, 22.40H), 1.90–2.00 (m, 22.40H), 1.60–1.80 (m, 19.2H), 1.30–1.35 (m, 11.20H). The clear NMR characterization confirms the successful synthesis of compound B.

[0026] Example 3 The preparation of compound C, based on parts by weight of the raw materials, includes the following steps: 100 parts of compound B were mixed with 900 parts of cyclohexane, and 2 parts of Ni / diatomite supported hydrogenation catalyst were added. The mixture was reacted at 160 °C and 6 MPa hydrogen pressure for 5 h. After the reaction was completed, the catalyst was filtered through a 1 μm pore size filter membrane. The filtrate was dried at -0.09 MPa and 80 °C for 5 h to obtain compound C.

[0027] The double bond addition in compound C was determined using Fourier transform infrared spectroscopy (FTIR). No absorption peak was observed at 975 nm in compound C, indicating that there are no cyclic C=C double bonds in compound C and that hydrogenation was complete.

[0028] Example 4 The preparation of functional acrylate material M1 includes the following steps: Hydroxyethyl acrylate (58.06 g, 0.50 mol) was slowly added dropwise to a four-necked flask containing isophorone diisocyanate IPDI (111.16 g, 0.5 mol). The catalyst was dibutyltin dilaurate (0.08 g), and the polymerization inhibitor was p-hydroxyanisole (0.15 g). The reaction temperature was 45 °C. After 3 h of reaction, the NCO conversion rate of isocyanate was tested by di-n-butylamine titration. When the NCO conversion rate reached 50%, it was used as intermediate compound D1.

[0029] To a reaction flask containing compound C (427.25 g, 0.25 mol) dissolved in toluene (300 g), add catalyst dibutyltin dilaurate (0.72 g), stir for 5 min, and then slowly add intermediate compound D1 to be reacted. The reaction temperature is 70 ℃, and after holding at this temperature for 5 h, take a sample to test the NCO conversion rate of isocyanate. When the NCO conversion rate reaches 100%, the reaction is terminated. Place the reaction solution under an air / nitrogen atmosphere to remove the toluene solvent. After the solvent removal is completed, functional acrylate material M1 is obtained.

[0030] The functional acrylate material M1 is a clear and transparent liquid with a viscosity of 15,000 cps at 85 ℃ and a refractive index of 1.473.

[0031] Example 5 The preparation of functional acrylate material M2 includes the following steps: Hydroxyethyl acrylate (58.06 g, 0.50 mol) was slowly added dropwise to a straight four-necked flask containing 4,4-diisocyanate dicyclohexylmethane HMDI (131.18 g, 0.5 mol). The catalyst was dibutyltin dilaurate (0.10 g), and the polymerization inhibitor was p-hydroxyanisole (0.18 g). The reaction temperature was 45 °C, and after 3 h of reaction, the NCO conversion rate of isocyanate was tested by di-n-butylamine titration. When the NCO conversion rate reached 50%, it was used as intermediate compound D1.

[0032] To a reaction flask containing compound C (427.25 g, 0.25 mol) dissolved in toluene (300 g), add catalyst dibutyltin dilaurate (0.80 g), stir for 5 min, and then slowly add intermediate compound D1 to be reacted. The reaction temperature is 80 ℃, and after holding at this temperature for 5 h, take a sample to test the NCO conversion rate of isocyanate. When the NCO conversion rate reaches 100%, the reaction is terminated. Place the reaction solution under an air / nitrogen atmosphere to remove the toluene solvent. After the solvent removal is completed, functional acrylate material M2 is obtained.

[0033] The functional acrylate material M2 is a clear and transparent liquid with a viscosity of 30,000 cps at 85 ℃ and a refractive index of 1.472.

[0034] Comparative Example 1 Aliphatic epoxy acrylate Genomer* 2235, from Rahn.

[0035] Comparative Example 2 Hydrogenated polybutadiene polyurethane acrylate CN9014 NS, from Sartamomer.

[0036] Performance Tests and Results The functional acrylate material M1 prepared in Example 4, the functional acrylate material M2 prepared in Example 5, Comparative Example 1 and Comparative Example 2 were used as resin components, and the following performance tests were performed.

[0037] 1. Mechanical performance testing (1) Mechanical property testing Test formulation: 7 g resin, 0.4 g photoinitiator Omnirad TPO-L, wherein the photoinitiator Omnirad TPO-L is from IGM Corporation; After being cured into mechanical property test specimens using a mercury lamp, the mechanical properties were tested using a universal tensile testing machine according to the ASTM-D638 standard. Each set of data was tested three times, and the average value was taken. The results are shown in Table 1. Higher tensile strength and tensile modulus indicate higher material hardness; higher elongation at break indicates better material elasticity. Higher tensile strength, tensile modulus, and elongation at break indicate that the material is both hard and tough.

[0038] (2) Hardness performance test Test formulation: 100 g resin, 0.4 g photoinitiator Omnirad TPO-L; After being mixed evenly, the mixture was cured into a film with a thickness of 0.5 cm. The hardness of the coating was tested using the Shore hardness test, and the results are shown in Table 1.

[0039] Table 1 Test results of mechanical and hardness properties of different materials

[0040] As can be seen from Table 1, the tensile strength, tensile modulus, elongation at break and Shore hardness of the resins prepared in Examples 4-5 are significantly better than those of Comparative Example 1 and Comparative Example 2. The functional acrylate material provided by the present invention has significantly improved mechanical properties.

[0041] 2. Sunlight aging resistance QUV test Test formulation: 8 g resin, 2 g monomer IBXA, 0.4 g photoinitiator Omnirad 1173. The monomer IBXA was from Osaka Organic Chemicals, and the photoinitiator Omnirad 1173 was from IGM Corporation. After thorough mixing, the mixture was applied to a PC white board. Xenon lamp aging (1800 W xenon lamp power, 150-1200 W irradiation intensity) was used to test the ΔE and Δb values ​​of the coating at different aging times. The results are shown in Table 2. The smaller the ΔE and Δb values, the better the performance, indicating better resistance to sunlight aging.

[0042] Table 2 Results of QUV test on the resistance to sunlight aging of different materials

[0043] As can be seen from Table 2, under xenon lamp aging, the resins prepared in Examples 4-5 have better resistance to sunlight aging than Comparative Examples 1 and 2. The functional acrylic ester material provided by the present invention has significantly improved resistance to sunlight aging.

[0044] 3. Water vapor barrier capability test Test formulation: 8 g resin, 2 g monomer IBXA, 0.4 g photoinitiator Omnirad 1173; After thorough mixing, membranes with a thickness of 0.03–0.08 cm were prepared using a membrane pressing method. The water vapor barrier capacity of the membranes was then tested, and the results are shown in Table 3.

[0045] Water vapor barrier performance test method: According to Cai et al. (Cai, Xiao, Chen, & Liu, 2020), the WVP (water vapor transmission coefficient) of thin film samples was determined using the cup method. The average diameter of the weighing cup was 3 cm and the height was 5 cm. A thin film sample tray with a diameter slightly larger than the weighing cup was sealed on top of the weighing cup. The relative humidity in the weighing cup was maintained at 0% using 15 g of anhydrous calcium chloride. The weighing cup was then placed in a desiccator containing deionized water at 25°C and 100% relative humidity. The weight of the weighing cup was measured periodically (every 24 hours for 7 days), and the weight change was recorded. The WVP of the thin film sample was calculated as follows:

[0046] In the formula, Δm is the increase in weight of the weighing cup (g); d is the thickness of the thin film sample (m); and A is the area of ​​the thin film (m²). 2 ), t is the time interval (s), and Δp is the pressure difference across the membrane (3167.1 Pa at 25℃).

[0047] Table 3 Test results of water vapor barrier performance of different materials

[0048] As can be seen from Table 3, the water vapor barrier properties of the resin films prepared in Examples 4-5 are better than those in Comparative Examples 1 and 2. The functional acrylate material provided by the present invention has significantly improved water vapor barrier properties.

[0049] In summary, the functional acrylate material provided by this invention can improve resistance to sunlight aging, water vapor barrier properties, and mechanical properties.

[0050] Unless otherwise specified, all raw materials used in this invention are existing substances that can be purchased directly from the market.

[0051] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A functional acrylic material, characterized in that, It has the structural formula shown in equation (I): Where n is 7~14, and R is the structure shown in equation (II) or equation (III): 。 2. The method for preparing the functional acrylate material according to claim 1, characterized in that, Includes the following steps: S1. Under the action of the first catalyst, dicyclopentadiene undergoes a ring-opening metathesis polymerization reaction in the first solvent to obtain compound A; S2. Under the action of a second catalyst, compound A and mercaptopropanol undergo a Michael addition reaction in a second solvent to give compound B. S3. Under the action of a third catalyst and hydrogen pressure, compound B undergoes a hydrogenation reaction in a third solvent to obtain compound C. S4. Under the action of the fourth catalyst, compound C and compound D undergo an addition reaction in the fourth solvent to obtain a functional acrylate material; The structural formulas of compounds A, B, C, and D are as follows: 。 3. The method for preparing the functional acrylate material according to claim 2, characterized in that, In step S1: The first catalyst is a ruthenium carbene catalyst; and / or, The first solvent is cyclohexane; and / or, The mass ratio of the dicyclopentadiene to the first solvent is 100:(200~900); and / or, The mass ratio of the first catalyst to the dicyclopentadiene is (0.01~1):100; and / or, The reaction pressure is 0~1 MPa, the reaction temperature is 30~70 ℃, and the reaction time is 1~60 min.

4. The method for preparing the functional acrylate material according to claim 2, characterized in that, Step S1 includes the following steps: S11. Under the action of the first catalyst, dicyclopentadiene undergoes a ring-opening metathesis polymerization reaction in the first solvent to obtain the first reaction solution. S12. Add the first reaction solution to isopropanol to precipitate the polymer, filter, and dry to obtain compound A.

5. The method for preparing the functional acrylate material according to claim 2, characterized in that, In step S2: The second catalyst is a Lewis base catalyst; and / or, The second solvent is toluene; and / or, The molar ratio of compound A to mercaptopropanol is 1:(2.05~2.1); and / or, The amount of the second catalyst is 1000-3000 ppm of the total mass of compound A, mercaptoethanol, the second solvent, and the second catalyst; and / or, The reaction temperature is 45~60 ℃, and the reaction time is 3~6 h.

6. The method for preparing the functional acrylate material according to claim 2, characterized in that, Step S2 includes the following steps: S21. Under the action of a second catalyst, compound A and mercaptopropanol undergo a Michael addition reaction in a second solvent to obtain a second reaction solution. S22. The second reaction solution is desolventized and dried to obtain compound B.

7. The method for preparing the functional acrylate material according to claim 2, characterized in that, In step S3: The third catalyst is a supported hydrogenation catalyst; and / or, The third solvent is cyclohexane; and / or, The mass ratio of compound B to the third solvent is 100:(200~900); and / or, The mass ratio of the third catalyst to compound B is (0.1~10):100; and / or, The hydrogen pressure for the reaction is 1~10 MPa, the temperature for the reaction is 100~150 ℃, and the reaction time is 1~10 h.

8. The method for preparing the functional acrylate material according to claim 2, characterized in that, Step S3 includes the following steps: S31. Under the action of a third catalyst and hydrogen pressure, compound B undergoes a hydrogenation reaction in a third solvent to obtain a third reaction solution. S32. The third reaction solution is filtered through a filter membrane and dried to obtain compound C; wherein the pore size of the filter membrane is 0.1~10 μm.

9. The method for preparing the functional acrylate material according to claim 2, characterized in that, In step S4: The fourth catalyst is at least one selected from dibutyltin dilaurate, bismuth neodecanoate, and zinc neodecanoate; and / or The fourth solvent is toluene; and / or, The molar ratio of compound C to compound D is 1:(1.99~2.01); and / or, The amount of the fourth catalyst is 500-1500 ppm of the total mass of compound C, compound D, the fourth solvent, and the fourth catalyst; and / or, The reaction temperature is 50~80℃, and the reaction time is 3~6 h; and / or, The compound D is obtained by reacting hydroxyethyl acrylate with isocyanate at 40-50 °C until the NCO conversion rate of the isocyanate reaches 48-52%, wherein the isocyanate is isophorone diisocyanate or 4,4-diisocyanate dicyclohexylmethane.

10. The method for preparing the functional acrylate material according to claim 2, characterized in that, In step S1, the first catalyst is at least one of a first-generation Grubbs catalyst, a second-generation Grubbs catalyst, and a third-generation Grubbs catalyst; and / or, In step S2, the second catalyst is at least one of triphenylphosphine and tetrabutylammonium bromide; and / or, In step S3, the third catalyst is at least one of Ni / Al2O3 supported hydrogenation catalyst, Ni / diatomite supported hydrogenation catalyst, Pd / C supported hydrogenation catalyst, and Ru / Al2O3 supported hydrogenation catalyst.

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