An oxo-modified acrylate compound, a preparation method thereof, and use thereof

Abstract

The present application provides an oxo-modified acrylate compound, a preparation method and applications thereof. The compound contains an oxetane functional group and two (meth)acrylic acid functional groups, and can be used as a monomer for simultaneous radical curing, cationic curing, and radical-cation hybrid system curing. The present application also relates to a method for preparing the oxo-modified acrylate compound and applications of a cured composition thereof.

Description

Technical Field

[0001] This invention relates to the field of photocurable materials, and more specifically, to an oxa-modified acrylate compound, its preparation method, a photocurable composition, and its applications. Background Technology

[0002] Free radical curing systems offer advantages such as fast curing speed, a wide variety of initiators, compatibility with numerous light sources, and relatively mature technology. However, in-depth research reveals that free radical system inks and coatings still suffer from some technical drawbacks, such as difficulty in curing oxygen-inhibited surfaces, volume shrinkage, poor flexibility of the cured film, and initiator migration. Cationic curing systems exhibit low volume shrinkage and excellent adhesion, but also have some limitations, such as slow curing speed, fewer initiator types compatible with different light sources, and higher cost.

[0003] In recent years, to realize the application of photocurable products in different fields, various optimizations have been made to photocurable formulations and compounds used in formulations, leading to the development of free radical-cationic hybrid system compositions that aim to combine the advantages of free radical and cationic curing. However, the types of polymers suitable for free radical-cationic hybrid systems are limited, and the curing speed, hardness, and flexibility of the cured products are not ideal.

[0004] Therefore, hybrid photosensitive polymers represent an important research direction for overcoming the defects of such products. Several patent reports have already been published regarding hybrid photosensitive polymer resins. For example, CN102659720A discloses a dimethacrylate oxetane structure, which is more environmentally friendly and has higher human safety than epoxy compounds such as (meth)acrylate glycidyl ester; CN115746186A discloses an acrylic prepolymer containing oxetane functional groups. This prepolymer has oxetane-butyl groups on its side chains and acrylate groups at its end groups, solving problems such as incomplete system reaction and uneven product properties in existing technologies. However, the oxetane-modified acrylate compounds disclosed in existing patents have poor flexibility and difficulty in achieving a balanced adhesion, which greatly limits their application. Summary of the Invention

[0005] To address the problems existing in the prior art, the main objective of this invention is to provide an oxa-modified acrylate compound, its preparation method, and its applications. This oxa-modified acrylate compound contains one oxacyclobutane functional group and two (meth)acrylate functional groups. When applied to a free radical-cationic hybrid system, it cures rapidly, and the cured film exhibits excellent flexibility and adhesion.

[0006] To achieve the above objectives, the oxa-modified acrylate compound of the present invention has the structure shown in general formula (I):

[0007]

[0008] R1 is methyl or ethyl; R2 is methyl or ethyl; R3 is hydrogen or methyl.

[0009] Accordingly, the present invention also relates to a method for preparing the oxa-modified acrylate compound represented by the above general formula (I):

[0010] (1) Epoxy ring-opening reaction

[0011]

[0012] The raw material shown in general formula (a) was added to the reaction solvent and stirred. A dry acidic substance (b) was slowly introduced at room temperature. The gas phase was monitored until the reaction of the raw material shown in general formula (a) was completed. The intermediate product (c) was obtained after post-processing.

[0013] The acidic substance (b) is an acidic gas, and X is a halogen.

[0014] (2) Condensation reaction

[0015]

[0016] Intermediate product (c) is heated to reflux in the presence of acetone solvent and an acidic catalyst for 8-12 hours. After cooling to room temperature, excess solvent is removed, and the mixture is distilled to obtain intermediate product (d). The acidic catalyst can be any one or a combination of two or more of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, sodium hydroxide, or potassium hydroxide.

[0017] (3) Protective and deprotective reactions

[0018]

[0019] Intermediate product (d) and the raw material shown in general formula (a) are heated and refluxed in the presence of solvent and catalyst to remove the generated water. After post-treatment, intermediate product (e) is obtained. Acidic solvent and alcohol solvent are added, and the mixture is stirred at room temperature for 3-8 hours. After post-treatment, intermediate product (f) is obtained.

[0020] (4) Transesterification

[0021]

[0022] The intermediate product (f) and the raw material shown in general formula (g) undergo further transesterification in the presence of a catalyst to obtain the target product (I).

[0023] According to another aspect of the present invention, a free radical-cationic hybrid system photocurable composition is provided, comprising an initiator, a monomer, and an additive, wherein the monomer is the oxa-modified acrylate compound described above.

[0024] According to another aspect of the present invention, the application of the above-mentioned oxa-modified acrylate compound or the free radical-cationic hybrid system photocurable composition in photocurable products is provided, the photocurable products including protective films for electronic components, interlayer insulating materials, pattern transfer materials, 3D printing materials, coatings, inks or adhesives.

[0025] The technical solution of this invention is obtained from a composition prepared by an oxa-modified acrylate compound. Since the compound contains both oxacyclobutane groups and polyfunctional acrylic groups, the cured film obtained using this compound as a matrix has the fast film-forming / molding speed, high crosslinking density, and solvent resistance of a free radical system, while also possessing the flexibility of a cationic system. It can have good adhesion to the substrate and has superior application value in the fields of protective films for electronic components, interlayer insulating materials, pattern transfer materials, 3D printing, coatings, inks, and adhesives. Detailed Implementation

[0026] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0027] The present invention will be further described in detail below with reference to embodiments, but the scope of the present invention is not limited thereto.

[0028] Preparation Examples

[0029] Example 1

[0030]

[0031] (1) Add 348g of 1(a) and 600g of dichloromethane 1(b) to a 2L four-necked reaction flask. Slowly introduce dry HCl gas (84g) at room temperature. GC monitoring until the reaction of raw material 1(a) is completed. Cool the reaction system in an ice-water bath and filter to obtain 363g of crystalline product 1(c), with a yield of 80%.

[0032] (2) Add 300g of 1(c), 600mL of acetone, and 12g of p-toluenesulfonic acid to a 2L four-necked reaction flask, heat to reflux, react for 10h, cool to room temperature, add sodium bicarbonate to neutralize the reaction system to neutral, filter, remove excess acetone, and distill to obtain 228g of 1(d), with a yield of 60%.

[0033] (3) Add 192g of the above product 1(d), 600ml of toluene, 1g of 18-crown ether-6 catalyst, and 116g of 1(a) to a 2L four-necked reaction flask. Heat to reflux and separate the water produced in the system. Control the reaction in GC until intermediate product 1(d) disappears. Cool and filter the sodium chloride salt produced. Remove the solvent toluene to obtain product 1(e). Add dilute hydrochloric acid and methanol directly without purification. Stir at room temperature for 5 hours. Neutralize the reaction solution with sodium bicarbonate to neutral. Filter and remove the solvent methanol to obtain intermediate 1(f).

[0034] (4) Add the above intermediate 1(f) to a 2L four-necked reaction flask, add 150g of methyl methacrylate, heat to reflux to dehydrate until the water content of the system is less than 500ppm, cool to 60℃, add 1g of tetraethyl titanate catalyst, continue to heat to reflux to carry out transesterification reaction, distill off methanol, stop the reaction after the hydroxyl value of the system no longer changes, add water to destroy the catalyst after the reaction is completed, filter to remove insoluble matter, remove excess methyl methacrylate, and obtain the product as a light yellow transparent liquid, i.e., target product 1(I) 250g.

[0035] Compounds 2-6 with the structures shown in Table 1 were prepared from the corresponding reagents according to the method of Example 1:

[0036] Table 1

[0037]

[0038] Performance testing

[0039] Curing performance test

[0040] Taking the compounds from the above embodiments as examples, the curing performance of the oxa-modified acrylate compounds of the present invention was tested in combination with photoinitiators and monomers.

[0041] Table 2

[0042]

[0043] The resin compositions prepared according to the formulations in Examples 1-9 and Comparative Examples 1-3 above were coated onto a glass plate and subjected to mercury lamp conveyor belt exposure treatment (energy 1000 mJ / cm). 2 Observe its curing process, evaluate it using the touch method, and test the application performance of the composition.

[0044] Curing into film / strip testing

[0045] Flexibility test

[0046] The T-bend performance was tested according to GB / T 30791-2014. The evaluation results are recorded in Table 3.

[0047] Adhesion test

[0048] The adhesion of the cured film was tested according to GB 1720-1979. The evaluation results are recorded in Table 3.

[0049] Table 3

[0050]

[0051] As can be seen from the above description, the above embodiments of the present invention achieve the following technical effects: When the oxetane-modified acrylate compound of the present invention is used as a raw material for photocurable compound curing, the curing performance is comparable to that of conventional oxetane-modified compounds, and the cured product obtained from the composition has ideal flexibility and adhesion.

[0052] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. 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. An oxo-modified acrylate compound having the structure shown in Formula (I): ###0001### Formula (I) wherein R1 is methyl or ethyl; R2 is methyl or ethyl; and R3 is hydrogen or methyl. wherein comprising the following steps:

2. A method for producing the oxo-modified acrylate compound according to claim 1, characterized by producing from raw materials represented by the following general formula (a) and general formula (g), ###0001### (a) ###0002### (g) (1) Ring-opening reaction ring-opening of a starting material shown in general formula (a) in the presence of an acidic substance (b) to obtain an intermediate product (c), ###0002### (2) Condensation reaction heating reaction of the intermediate product (c) in the presence of an acidic catalyst for a period of time to obtain an intermediate product (d), as shown in the following reaction formula: ###0003### (3) Protection and deprotection reaction reaction of the intermediate product (d) and a starting material shown in general formula (a) in the presence of a solvent and a catalyst to obtain an intermediate product (e), and ring-opening in the presence of a solvent to obtain an intermediate product (f); X is halogen. (4) Transesterification reaction reaction of the intermediate product (f) and a starting material shown in general formula (g) in the presence of a catalyst to obtain the target product (I). In the reaction of step (1), the acidic substance (b) is an acidic gas.

3. The method for producing an oxo-modified acrylate compound according to claim 2, characterized by: In the reaction of step (2), the reaction time is 8-12 h, and the acidic catalyst used in the condensation reaction is selected from any one or a combination of two or more of p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid.

4. The method for producing an oxo-modified acrylate compound according to claim 2, characterized by: In the reaction of step (3), the solvent added to the intermediate product (e) is an acidic solvent or an alcoholic solvent, and the reaction is stirred at room temperature for 3-8 h to obtain the intermediate product (f).

5. The method for producing an oxo-modified acrylate compound according to claim 2, characterized by: The free radical-cation hybrid system photocuring composition comprises a photoinitiator, a monomer, and an auxiliary agent, wherein the monomer is the oxo-modified acrylate compound of claim 1.

6. A radical-cationic hybrid system photocuring composition, characterized by 7. Use of the oxo-modified acrylate compound of claim 1 or the free radical-cation hybrid system photocuring composition of claim 6 in a photocuring product, wherein the photocuring product comprises a protective film for electronic components, an interlayer insulating material, a pattern transfer material, a coating, an ink, an adhesive, or a 3D printing material. ​

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