Oxa-modified acrylate compound as well as preparation method and application thereof

Abstract

The invention provides an oxa-modified acrylate compound as well as a preparation method and application thereof. The compound contains an oxetane functional group and two (methyl) acrylic functional groups, and can be used as monomers for free radical curing, cation curing and free radical-cation hybrid system curing at the same time. The invention also relates to a method for preparing the oxa-modified acrylate compounds according to the invention and to the use of the cured compositions thereof. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of photocurable materials, and in particular to an oxygen-modified acrylate compound, a preparation method, a photocurable composition and applications thereof. Background Art

[0002] The free radical curing system has the advantages of fast curing speed, a wide range of initiators, a wide range of compatible light sources, and relatively mature technology. However, in-depth research has found that free radical system inks and coatings still have some technical defects, such as: difficulty in curing due to oxygen inhibition surface, volume shrinkage, poor flexibility of the cured film, initiator migration, etc. The cationic curing system has small volume shrinkage and excellent adhesion, but it also has some defects, such as: slow curing speed, fewer types of initiators that are compatible with different light sources, and high prices.

[0003] In recent years, in order to realize the application of photocurable products in different fields, different optimizations have been made to the photocurable formulas and the compounds used in the formulas, and free radical-cationic hybrid system compositions have been developed, which are committed to combining the advantages of free radical and cationic curing. However, there are few types of polymers suitable for free radical-cationic hybrid systems, and the curing speed and hardness and flexibility of the cured products are not good.

[0004] Therefore, hybrid photosensitive polymers are an important research direction to overcome the defects of such products. At present, there are some patent reports on hybrid photosensitive polymer resins. For example, CN102659720A discloses a dimethacrylate oxetane structure, which is more environmentally friendly than epoxy compounds such as (meth) acrylate glycidyl ester and has higher human safety; CN115746186A discloses an acrylic prepolymer containing an oxetane functional group, the side chain of the prepolymer has an oxetane group, and the end group has an acrylate group, which solves the problems of incomplete system reaction and uneven product properties in the prior art. However, the oxygen-modified acrylate compounds disclosed in the existing patents have poor flexibility and are difficult to balance before adhesion, which greatly limits their application. Summary of the invention

[0005] In view of the problems existing in the prior art, the main purpose of the present invention is to provide an oxo-modified acrylate compound, a preparation method and its application. The oxo-modified acrylate compound contains one oxetane functional group and two (meth) acrylic functional groups, and when applied to a free radical-cation hybrid system, it cures quickly, and the cured film has excellent flexibility and adhesion.

[0006] In order to achieve the above-mentioned object, the oxygen-modified acrylate compound of the present invention has a structure shown in the following general formula (I):

[0007]

[0008] The 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 oxo-modified acrylate compound represented by the general formula (I):

[0010] (1) Epoxy ring-opening reaction

[0011]

[0012] The raw material represented by the general formula (a) is added to the reaction solvent and stirred, and the dry acidic substance (b) is slowly introduced at room temperature. The gas phase is followed to react until the reaction of the raw material represented by the general formula (a) is completed, and the intermediate product (c) is obtained by post-treatment.

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

[0014] (2) Condensation reaction

[0015]

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

[0017] (3) Protection and deprotection reaction

[0018]

[0019] The intermediate product (d) and the raw material represented by the general formula (a) are heated to reflux in the presence of a solvent and a catalyst to remove the generated water, and then post-treated to obtain the intermediate product (e). An acidic solvent and an alcohol solvent are further added, and the mixture is stirred at room temperature for 3-8 hours, and then post-treated to obtain the intermediate product (f).

[0020] (4) Transesterification reaction

[0021]

[0022] The intermediate product (f) and the raw material represented by the general formula (g) are further subjected to an ester exchange reaction in the presence of a catalyst to obtain the target product (I).

[0023] According to another aspect of the present invention, a free radical-cation hybrid system photocurable composition is provided, comprising an initiator, a monomer and an auxiliary agent, wherein the monomer is the above-mentioned oxygen-modified acrylate compound.

[0024] According to another aspect of the present invention, there is provided an application of the above-mentioned oxygen-modified acrylate compound or the free radical-cation hybrid system photocurable composition in a photocurable product, wherein the photocurable product includes a protective film of an electronic component, an interlayer insulating material, a pattern transfer material, a 3D printing material, a coating, an ink or an adhesive.

[0025] By applying the technical solution of the present invention, a composition prepared from an oxygen-modified acrylate compound is obtained. Since the compound contains both an oxetane group and a multifunctional acrylic group, the cured film obtained with the compound as a matrix has both the faster film-forming / molding speed, high crosslinking density, and solvent resistance of a free radical system, and the flexibility of a cationic system, and can have good adhesion to a substrate. It has excellent application value in the fields of protective films of electronic components, interlayer insulating materials, pattern transfer materials, 3D printing, coatings, inks, adhesives, etc. DETAILED DESCRIPTION

[0026] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

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

[0028] Preparation Example

[0029] Example 1

[0030]

[0031] (1) In a 2L four-necked reaction flask, 348g of 1(a) and 600g of dichloromethane 1(b) were added, and dry HCl gas (84g) was slowly introduced at room temperature. GC tracking detection was performed until the reaction of the raw material 1(a) was completed. The reaction system was cooled in an ice-water bath and filtered to obtain 363g of crystalline product 1(c) with a yield of 80%.

[0032] (2) In a 2L four-necked reaction flask, 300 g of the above 1(c), 600 mL of acetone, and 12 g of p-toluenesulfonic acid were added, and the mixture was heated to reflux and reacted for 10 h. The mixture was cooled to room temperature, and sodium bicarbonate was added to neutralize the reaction system until it was neutral. The mixture was filtered to remove excess acetone, and 228 g of 1(d) was obtained by distillation. The yield was 60%.

[0033] (3) In a 2L four-necked reaction flask, 192 g of the above product 1(d), 600 ml of toluene, 1 g of 18-crown ether-6 catalyst, and 116 g of 1(a) were added. The mixture was heated to reflux and the water produced in the system was separated. The GC was controlled until the intermediate product 1(d) disappeared. The mixture was cooled and the produced sodium chloride salt was filtered. The toluene solvent was removed to obtain the product 1(e). Dilute hydrochloric acid and methanol were directly added without purification. The mixture was stirred at room temperature for 5 hours. The reaction solution was neutralized with sodium bicarbonate until neutral, filtered, and the methanol solvent was removed to obtain the intermediate 1(f).

[0034] (4) The intermediate 1(f) was added to a 2L four-necked reaction flask, followed by 150 g of methyl methacrylate. The temperature was raised to reflux for dehydration until the water content of the system was less than 500 ppm. The temperature was lowered to 60°C, and 1 g of tetraethyl titanate was added as a catalyst. The temperature was further raised to reflux for transesterification reaction. Methanol was distilled off. The reaction was stopped after the hydroxyl value of the system no longer changed. After the reaction was completed, water was added to destroy the catalyst. The insoluble matter was removed by filtration. The excess methyl methacrylate was removed to obtain a light yellow transparent liquid, i.e., 250 g of the target product 1(I).

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

[0036] Table 1

[0037]

[0038] Performance Testing

[0039] Curing performance test

[0040] Taking the compound of the above embodiment as an example, the curing performance of the oxygen-modified acrylate compound of the present invention was tested by adding a photoinitiator and a monomer.

[0041] Table 2

[0042]

[0043] The resin compositions prepared according to the formulations in Examples 1-9 and Comparative Examples 1-3 were coated on glass plates and subjected to mercury lamp caterpillar exposure treatment (energy 1000 mJ / cm 2 ), observe its curing condition, evaluate it by finger touch method, and test the application performance of its composition.

[0044] Curing film / strip test

[0045] Flexibility test

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

[0047] Adhesion test

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

[0049] Table 3

[0050]

[0051] From the above description, it can be seen that the above-mentioned 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 curing a photocurable compound, the curing property is equivalent to that of the compound modified with the previous oxetane compound, and the cured product obtained from the composition has ideal flexibility and adhesion.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An oxygen-modified acrylate compound having a structure shown in formula (I): in, The R1 is methyl or ethyl; R2 is methyl or ethyl; R3 is hydrogen or methyl.

2. A method for preparing the oxygen-modified acrylate compound as claimed in claim 1, wherein the compound is prepared from the raw materials represented by the following general formula (a) and general formula (g), characterized in that: The following steps are involved: (1) Epoxy ring-opening reaction The raw material represented by the general formula (a) is subjected to ring opening in the presence of an acidic substance (b) to obtain an intermediate product (c). (2) Condensation reaction The intermediate product (c) is heated and reacted under the action of an acidic catalyst for a period of time to obtain the intermediate product (d). The reaction formula is as follows: (3) Protection and deprotection reaction The intermediate product (d) and the raw material represented by the general formula (a) react in the presence of a solvent and a catalyst to obtain an intermediate product (e), which is then ring-opened by adding a solvent to obtain an intermediate product (f). (4) Transesterification reaction The intermediate product (f) reacts with the raw material represented by the general formula (g) in the presence of a catalyst to obtain the target product (I).

3. The method for preparing an oxygen-modified acrylate compound according to claim 2, characterized in that: In the reaction of step (1), the acidic substance (b) is an acidic gas, and X is a halogen.

4. The method for preparing an oxygen-modified acrylate compound according to claim 2, characterized in that: In the reaction of step (2), the reaction time is 8-12 hours, and the acidic catalyst used in the condensation reaction is selected from any one of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, sodium hydroxide or potassium hydroxide, or a combination of two or more thereof.

5. The method for preparing an oxygen-modified acrylate compound according to claim 2, characterized in that: In the reaction of step (3), an acidic solvent or an alcohol solvent is added to the intermediate product (e), and the reaction is stirred at room temperature for 3-8 hours to obtain the intermediate product (f).

6. A free radical-cation hybrid system photocurable composition, characterized in that The free radical-cation hybrid system photocurable composition comprises the oxo-modified acrylate compound according to claim 1.

7. The free radical-cation hybrid system photocurable composition according to claim 6, comprising a photoinitiator, a monomer and an auxiliary agent, wherein the monomer is the oxygen-modified acrylate compound according to claim 1.

8. Use of the oxygen-modified acrylate compound according to claim 1 or the free radical-cation hybrid system photocurable composition according to any one of claims 6 or 7 in a photocurable product, wherein the photocurable product includes a protective film of an electronic component, an interlayer insulating material, a pattern transfer material, a coating, an ink, an adhesive or a 3D printing material.

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