Oxetane monomer compound, preparation method therefor and use thereof

Abstract

The present application provides an oxetane monomer compound, a preparation method therefor and the use thereof. The oxetane monomer compound has a structure represented by general formula I. The compound of the present application is a monofunctional oxetane monomer having a combination of dicyclopentadiene and oxetane, and can participate in cationic photocuring. The preparation method for the substance is simple and feasible, involves mild conditions, readily available starting materials and low costs, and therefore has wide application prospects.

Description

An oxacyclobutane monomer compound, its preparation method and application Technical Field

[0001] This application belongs to the field of cationic photocuring and relates to an oxacyclobutane monomer compound, its preparation method, and its application. Background Technology

[0002] Oxycyclic butane monomers are important raw materials for cationic photocurable products. Commonly used oxycyclic butane monomers, such as 3,3'-[oxybis(methylene)dimethyl]bis[3-ethyl]oxycyclic butane, have been reported in patent JP3931448B2. Oxycyclic butane monomers such as 3-ethyl-3-[(benzyloxy)methyl]oxycyclic butane, 3-ethyl-3-oxabutane methanol, and 3-ethyl-3-[(ethylene oxide-2-ylmethoxy)methyl]oxycyclic butane have advantages such as low viscosity, low curing shrinkage, and fast curing speed. Their application in coatings for UV curing cans was reported as early as JP1998158581A, filed on December 5, 1996.

[0003] Recently, cationic curing systems have become a development trend, considered beneficial to the performance of cured products, and have made progress in coatings, adhesives, ink compositions, and photosensitive insulating compositions. However, these compositions often use compounds such as epoxy resins and glycidyl ethers, with limited selection of oxetane compounds. Summary of the Invention

[0004] This application provides an oxetane monomer compound, its preparation method, and its application. The compound of this application is a monofunctional oxetane monomer with a combination of dicyclopentadiene and oxetane, which has a high glass transition temperature and hardness, and has better adhesion in interlayer insulating film applications. The preparation method of this material is simple and easy to implement, with mild conditions, readily available raw materials, and low cost.

[0005] In a first aspect, this application provides an oxetane monomer compound having the structure shown in general formula I:

[0006] Where A is hydrogen, hydroxyl, halogen, C1-C5 haloalkyl, C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 hydroxyalkyl; n is an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5).

[0007] Furthermore, the oxobutane compound is selected from any one of the following substances A-1 to A-7:

[0008]

[0009] Secondly, this application provides a method for preparing oxacyclobutane compounds, the method comprising the following steps:

[0010] Step S1, Synthesis of the intermediate dicyclopentadienol: Dicyclopentadiene is reacted with compound d to generate compound b, as shown in the following reaction formula:

[0011] ;

[0012] Step S2, synthesis of intermediate heterocyclic butane-3-p-toluenesulfonate methyl ester: Compound a reacts with p-toluenesulfonyl chloride to generate compound c, as shown in the following reaction formula:

[0013] ;

[0014] Step S3, Synthesis of oxetane monomers: Compound b reacts with compound c to generate oxetane monomers of general formula I, as shown in the following reaction equation:

[0015] ;

[0016] Where A is hydrogen, hydroxyl, halogen, C1-C5 haloalkyl, C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 hydroxyalkyl; n is an integer from 0 to 5.

[0017] It should be noted that both dicyclopentadiene and 3-hydroxymethyl-3-ethyloxetane used in this application are commercially available or prepared by known synthetic methods.

[0018] Preferably, in step S1, the reaction is carried out under the catalysis of an acidic catalyst.

[0019] Preferably, the acidic catalyst is selected from any one or a combination of at least two of methanesulfonic acid, sulfuric acid, or p-toluenesulfonic acid.

[0020] Preferably, in step S1, the molar ratio of dicyclopentadiene to the acid catalyst is 1:0.1 to 1:10, for example: 1:0.1, 1:0.3, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8 or 1:10.

[0021] Preferably, in step S1, the molar ratio of dicyclopentadiene to compound d is 1:1 to 1:20, for example, 1:1, 1:3, 1:5, 1:7, 1:10, 1:12, 1:15, 1:17 or 1:20.

[0022] Preferably, in step S1, the reaction temperature is 70–120°C, such as 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C; and the reaction time is 1–10 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 8 h, or 10 h.

[0023] Preferably, in step S1, the reaction is carried out in a solvent selected from any one or a combination of at least two of water, toluene, xylene, or chlorobenzene.

[0024] Preferably, in step S2, the molar ratio of p-toluenesulfonyl chloride to compound a is 1:0.8 to 1:5, for example: 1:0.8, 1:0.9, 1:1.0, 1:1.5, 1:2, 1:3, 1:3.5, 1:4 or 1:5.

[0025] Preferably, in step S2, the reaction is carried out in an alkaline environment.

[0026] Preferably, the alkaline environment is provided by an acid-binding agent, which is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine, sodium carbonate, or sodium bicarbonate.

[0027] Preferably, in step S2, the molar ratio of toluenesulfonyl chloride to the acid-binding agent is 1:1 to 1:5, for example: 1:1, 1:2, 1:3, 1:4 or 1:5.

[0028] Preferably, in step S2, the reaction is carried out in the presence of a catalyst.

[0029] Preferably, the catalyst is tetrabutylammonium bromide (TBAB) or 18-crown-6 ether, etc.

[0030] Preferably, in step S2, the reaction temperature is 20–80°C, such as 20°C, 25°C, 30°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, or 80°C; and the reaction time is 1–24 h, such as 1 h, 2 h, 5 h, 7 h, 9 h, 10 h, 12 h, 15 h, 17 h, 20 h, 22 h, or 24 h.

[0031] Preferably, in step S2, the reaction is carried out in an organic solvent selected from any one or a combination of at least two of acetone, DMF, dichloromethane, toluene, xylene, or chlorobenzene.

[0032] Preferably, in step S3, the molar ratio of compound b to compound c is 1:0.8 to 1:5, for example, 1:0.8, 1:0.9, 1:1.0, 1:1.5, 1:2, 1:3, 1:3.5, 1:4 or 1:5.

[0033] Preferably, in step S3, the reaction is carried out in the presence of an alkaline substance.

[0034] Preferably, the alkaline substance is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine, sodium carbonate, sodium hydride, or sodium methoxide.

[0035] Preferably, in step S3, the molar ratio of compound c to the alkaline substance is 1:1 to 1:5, for example: 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 or 1:5.

[0036] Preferably, in step S3, the reaction temperature is 10–140°C, for example, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, or 140°C; and the reaction time is 1–24 h, for example, 1 h, 2 h, 5 h, 7 h, 9 h, 10 h, 12 h, 15 h, 17 h, 20 h, 22 h, or 24 h.

[0037] Preferably, in step S3, the reaction is carried out in an organic solvent selected from any one or a combination of at least two of DMF, dichloromethane, toluene, xylene, or chlorobenzene.

[0038] Thirdly, this application provides a photocurable composition comprising the oxetane monomer compound as described above, wherein the oxetane monomer compound serves as a crosslinking agent.

[0039] In this application, the photocurable composition further includes a photosensitive resin, a photosensitizer, and a solvent.

[0040] Preferably, the photosensitizer is selected from cationic photoinitiators.

[0041] Fourthly, this application provides the use of the oxobutane monomer compound or photocurable composition as described above in coatings, 3D printing, hard coatings, ink compositions or interlayer insulating films, especially in interlayer insulating films.

[0042] Compared with the prior art, this application has the following advantages:

[0043] The compound of this application is a monofunctional oxetane monomer with a combination of dicyclopentadiene and oxetane, and has a high glass transition temperature and hardness, and excellent adhesion in interlayer insulating film applications; the preparation method of this material is simple and easy, the conditions are mild, the raw materials are readily available and the cost is low, and it has broad application prospects. Detailed Implementation

[0044] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.

[0045] Example 1

[0046] (1) Preparation of intermediate b-1:

[0047]

[0048] In a 5000mL four-necked flask, 350g of dicyclopentadiene and 800g of a 30% methanesulfonic acid aqueous solution were added sequentially. The temperature was raised to 85℃ and the reaction was carried out for 4 hours. The reaction was controlled by GC until the raw material content was <1%. The mixture was then cooled to room temperature and separated into layers. The aqueous phase was extracted with dichloromethane, and the pH was adjusted to 8-9 with liquid alkali. The mixture was washed three times with water until neutral. The organic phase was desolventized under reduced pressure and then distilled under reduced pressure to obtain a colorless to pale yellow transparent liquid with a purity of over 99%.

[0049] (2) Preparation of intermediate c-1:

[0050]

[0051] In a 5000mL four-necked flask, 200g NaOH, 681g 3-ethyl-3-methanoloxetane, 4g TBAB, and 400g toluene were added sequentially. The mixture was stirred and heated to 38-40℃. A solution of 732.6g p-toluenesulfonyl chloride / 2400g toluene was added dropwise. After the addition was complete, the mixture was kept at 40℃ for 2 hours. The heating was then turned off and the reaction was carried out at room temperature for 15 hours. The mixture was filtered, and the filtrate was washed twice with water to remove the solvent, yielding approximately 900g of crude methyl 3-ethyloxetane-3-p-toluenesulfonate intermediate.

[0052] (3) Preparation of compound A-1:

[0053]

[0054] In a 5000mL four-necked flask under nitrogen protection, 1000g of DMF was added. NaH was added in portions under a 20°C water bath, and the mixture was stirred for 5 minutes. 500g of DMF solution of compound b-1 was added dropwise under an ice-water bath at 15°C, maintaining the internal temperature at 20°C. After the addition was complete, the mixture was kept in a 15°C water bath for 2 hours. Then, 900g of DMF solution of compound c-1 was added dropwise, and the mixture was kept in a 20°C water bath for 5 hours. After the reaction of compound c-1 was completed under GC control, the reaction was stopped. 1.2L of water was slowly added dropwise under an ice-water bath to quench the stirring until the salt block was completely dissolved. The mixture was extracted with 1.5L of ethyl acetate, and the organic phases were combined. 1L of ethyl acetate was added, and the mixture was washed three times with water until the pH reached 8. The solution was removed under reduced pressure to obtain approximately 863g of crude product. The crude product, compound A-1, was obtained by vacuum distillation and was found to be over 98% colorless and transparent.

[0055] The structure of compound A-1 was characterized, and the results are shown below:

[0056] ¹H NMR (500 MHz, deuterated chloroform) δ 5.74 – 5.64 (m, 2H), 4.10 (q, J = 7.0 Hz, 1H), 4.01 (d, J = 12.5 Hz, 2H), 3.72 (d, J = 12.5 Hz, 2H), 3.48 (d, J = 12.3 Hz, 1H), 3.39 (d, J = 12.5 Hz, 1H), 2.68 – 2.53 (m, 1H), 2.37 (p, J = 7.0 Hz, 1H), 2.23 – 2.07 (m, 2H), 1.87 – 1.49 (m, 8H), 0.84 (t, J = 8.0 Hz, 3H).

[0057] Example 2

[0058] Following the method of Example 1, the aqueous solution of methanesulfonic acid was replaced with a ethylene glycol solution of methanesulfonic acid, while the other raw materials remained unchanged. The reaction conditions were the same as in Example 1, yielding the corresponding oxetane monomer compound A-2:

[0059]

[0060] The structure of compound A-2 was characterized, and the results are shown below:

[0061] ¹H NMR (500 MHz, deuterated chloroform) δ 5.75 – 5.63 (m, 2H), 4.12 – 3.99 (m, 3H), 3.71 (d, J = 12.4 Hz, 2H), 3.68 – 3.47 (m, 6H), 2.68 – 2.57 (m, 3H), 2.23 – 2.07 (m, 2H), 1.85 – 1.51 (m, 7H), 0.85 (t, J = 8.0 Hz, 3H).

[0062] Example 3

[0063] Following the method of Example 1, the aqueous solution of methanesulfonic acid was replaced with a diethylene glycol solution of methanesulfonic acid, while the other raw materials remained unchanged. The reaction conditions were the same as in Example 1, yielding the corresponding oxetane monomer compound A-3:

[0064]

[0065] The structure of compound A-3 was characterized, and the results are shown below:

[0066] 1 ¹H NMR (500 MHz, deuterated chloroform) δ 5.76 – 5.64 (m, 2H), 4.11 – 4.02 (m, 3H), 3.77 – 3.50 (m, 11H), 3.44 (d, J = 12.3 Hz, 1H), 2.72 – 2.58 (m, 2H), 2.47 (pd, J = 7.1, 1.8 Hz, 1H), 2.38 (h, J = 7.0 Hz, 1H), 2.25 – 2.16 (m, 1H), 2.16 – 2.08 (m, 1H), 1.86 – 1.51 (m, 6H), 0.85 (t, J = 8.0 Hz, 3H).

[0067] Example 4

[0068] Following the method of Example 1, the aqueous solution of methanesulfonic acid was replaced with a triethylene glycol solution of methanesulfonic acid, while the other raw materials remained unchanged. The reaction conditions were the same as in Example 1, yielding the corresponding oxetane monomer compound A-4:

[0069]

[0070] The structure of compound A-4 was characterized, and the results are shown below:

[0071] 1¹H NMR (500 MHz, deuterated chloroform) δ 5.77 – 5.64 (m, 2H), 4.11 – 4.01 (m, 2H), 3.78 – 3.46 (m, 17H), 2.70 – 2.60 (m, 2H), 2.52 – 2.33 (m, 2H), 2.23 – 2.07 (m, 2H), 1.86 – 1.67 (m, 4H), 1.63 – 1.52 (m, 2H), 0.86 (t, J = 8.0 Hz, 3H).

[0072] Example 5

[0073] Following the method of Example 1, the reactant 3-ethyl-3-methanoloxetane was replaced with 3-pentyl-3-hydroxymethyloxetane, while the other starting materials remained unchanged. The reaction conditions were the same as in Example 1, yielding the corresponding oxetane monomer compound A-5:

[0074]

[0075] The structure of compound A-5 was characterized, and the results are shown below:

[0076] ¹H NMR (500 MHz, deuterated chloroform) δ 5.75 – 5.63 (m, 2H), 4.10 (q, J = 7.0 Hz, 1H), 3.94 (d, J = 12.4 Hz, 2H), 3.66 (d, J = 12.4 Hz, 2H), 3.48 (d, J = 12.3 Hz, 1H), 3.37 (d, J = 12.4 Hz, 1H), 2.68 – 2.60 (m, 1H), 2.55 (p, J = 7.0 Hz, 1H), 2.37 (p, J = 7.0 Hz, 1H), 2.19 (dtd, J = 12.5, 7.1, 1.0 Hz, 1H). 2.16 – 2.07 (m, 1H), 1.82 (dt, J = 12.2, 7.1 Hz, 1H), 1.77 – 1.51 (m, 6H), 1.41 – 1.21 (m, 6H), 0.89 (t, J = 7.7 Hz, 3H).

[0077] Performance testing

[0078] The following section, in conjunction with the structural and compositional evaluations of the embodiments, further elucidates the performance of oxacyclobutane monomer compounds:

[0079] 1. Hard-coating

[0080] Sensitivity test

[0081] Taking the oxetane compounds of the above embodiments as examples, the curing performance of the oxetane compounds described in this application was tested by combining compounds with ethylene oxide groups and cationic photoinitiators.

[0082] Following the formulation shown in Table 1, the raw materials were mixed evenly in a light-protected environment to obtain a photocurable composition. Unless otherwise specified, all parts shown are by weight, and the test results are summarized in Table 1.

[0083]

[0084] in:

[0085] Photosensitizer PAG-202: ;

[0086] TCM104: 3-Benzyloxymethyl-3-ethyloxetane;

[0087] TTA-21: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate;

[0088] The above composition was stirred under a yellow light lamp, and the mixture was then rolled onto a PET template to form a film. The film was dried at 90°C for 5 minutes to remove the solvent, resulting in a coating film with a thickness of approximately 10 μm. The substrate with the coating film was cooled to room temperature and then exposed to a high-pressure mercury lamp (exposure machine model RW-UV70201, exposure dose 150 mJ / cm²). 2 The coating was tested by irradiation to observe whether it could cure into a film. The evaluation criteria are as follows:

[0089] Completely cured: ;

[0090] Incomplete curing: ;

[0091] Uncured film: ×;

[0092] The evaluation results are recorded in Table 2.

[0093] Glass transition temperature test

[0094] Glass transition temperature (Tg): After the compositions in Table 1 above were completely cured, the glass transition temperatures of the compositions in the application examples and comparative examples were determined by differential scanning calorimetry (DSC). The test results are recorded in Table 2.

[0095] Hardness test

[0096] The composition in Table 1 above was applied to a PET template and rolled to form a film with a thickness of approximately 10 μm. The film was then exposed using a high-pressure mercury lamp (exposure machine model RW-UV70201, exposure dose 500 mJ / cm²). 2 After exposure to complete curing, the hardness of the cured film was tested according to GB / T 6739-1996. The test results are recorded in Table 2.

[0097]

[0098] As can be seen from the above description, the formulations containing the oxetane compounds A-1, A-2, A-3, A-4, and A-5 of this application in Table 2 can all be cured, and have higher glass transition temperatures and hardness compared to other oxetane monomers containing rigid groups (TCM104).

[0099] II. Photosensitive insulating resin composition

[0100] Taking the oxetane compounds of the above embodiments as examples, and combining them with other compounds for photosensitive insulating film compositions, relevant performance evaluations were conducted:

[0101] The formulations of the photosensitive insulating resin compositions are shown in Table 3 below:

[0102]

[0103] Fit test

[0104] A photosensitive resin composition was coated onto a copper-silicon wafer to prepare a uniform resin coating with a thickness of 10 μm. The coating was then exposed to a high-pressure mercury lamp at a wavelength of 350 nm and a concentration of 2000 J / m. 2 Exposure was performed, followed by heating at 110°C (PEB) for 3 minutes, and then baking in a convection oven at 200°C for 1 hour to obtain a cured film. A checkerboard test (based on JIS K5400-8.5) was conducted on the insulating film / inch silicon wafer laminate obtained in the corresponding use case and comparative example.

[0105] Evaluation criteria

[0106] When no insulation film peeling was observed: good adhesion (○);

[0107] When slight or partial peeling of the insulating film was observed, poor adhesion was observed. )

[0108] When the insulating film was completely peeled off, poor adhesion was observed (×).

[0109] The test results are shown in Table 4.

[0110]

[0111] TCM104: 3-benzyloxymethyl-3-ethyloxetane;

[0112] TCM103: 3-Ethyl-3-(phenoxymethyl)oxetane;

[0113] As can be seen from the above description, the photosensitive resin compositions containing the oxetane compounds A-1, A-2, A-3, A-4, and A-5 of this application in Table 4 have better adhesion than other resin compositions containing oxetane monomers (TCM103 and TCM104) with rigid groups.

[0114] The applicant declares that this application illustrates the oxetane monomer compounds, their preparation methods, and applications through the above embodiments, but this application is not limited to the above embodiments, i.e., it does not mean that this application must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of raw materials for the products of this application, additions of auxiliary components, and selection of specific methods, all fall within the protection scope and disclosure scope of this application.

Claims

1. An oxacyclobutane monomeric compound having the structure shown in general formula I: Where A is hydrogen, hydroxyl, halogen, C1-C5 haloalkyl, C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 hydroxyalkyl; n is an integer from 0 to 5.

2. The oxobutane monomer compound according to claim 1, wherein, The oxobutane compounds are selected from any one of the following substances A-1 to A-7:

3. A method for preparing an oxacyclobutane monomer compound according to claim 1 or 2, comprising the following steps: Step S1, Synthesis of the intermediate dicyclopentadienol: Dicyclopentadiene is reacted with compound d to generate compound b, as shown in the following reaction formula: ； Step S2, synthesis of intermediate heterocyclic butane-3-p-toluenesulfonate methyl ester: Compound a reacts with p-toluenesulfonyl chloride to generate compound c, as shown in the following reaction formula: ； Step S3, Synthesis of oxetane monomers: Compound b reacts with compound c to generate oxetane monomers of general formula I, as shown in the following reaction equation: ； Where A is hydrogen, hydroxyl, halogen, C1-C5 haloalkyl, C1-C5 alkyl, C1-C5 alkoxy, or C1-C5 hydroxyalkyl; n is an integer from 0 to 5.

4. The preparation method according to claim 3, wherein, In step S1, the reaction is carried out under the catalysis of an acidic catalyst; Preferably, the acidic catalyst is selected from any one or a combination of at least two of methanesulfonic acid, sulfuric acid, or p-toluenesulfonic acid.

5. The preparation method according to claim 3 or 4, wherein, In step S1, the molar ratio of dicyclopentadiene to the acidic catalyst is 1:0.1 to 1:10; Preferably, in step S1, the molar ratio of dicyclopentadiene to compound d is 1:1 to 1:20; Preferably, in step S1, the reaction temperature is 70–120°C, and the reaction time is 1–10 h; In step S1, the reaction is carried out in a solvent selected from any one or a combination of at least two of water, toluene, xylene, or chlorobenzene.

6. The preparation method according to any one of claims 3-5, wherein, In step S2, the molar ratio of p-toluenesulfonyl chloride to compound a is 1:0.8 to 1:5; Preferably, in step S2, the reaction is carried out in an alkaline environment; Preferably, the alkaline environment is provided by an acid-binding agent, which is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine, sodium carbonate, or sodium bicarbonate.

7. The preparation method according to any one of claims 3-6, wherein, In step S2, the molar ratio of toluenesulfonyl chloride to the acid-binding agent is 1:1 to 1:5; Preferably, in step S2, the reaction is carried out in the presence of a catalyst; Preferably, the catalyst is tetrabutylammonium bromide or 18-crown-6 ether; Preferably, in step S2, the reaction temperature is 20–80°C, and the reaction time is 1–24 h; Preferably, in step S2, the reaction is carried out in an organic solvent selected from any one or a combination of at least two of acetone, DMF, dichloromethane, toluene, xylene, or chlorobenzene.

8. The preparation method according to any one of claims 3-7, wherein, In step S3, the molar ratio of compound b to compound c is 1:0.8 to 1:5; Preferably, in step S3, the reaction is carried out in the presence of an alkaline substance; Preferably, the alkaline substance is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine, sodium carbonate, sodium hydride, or sodium methoxide. Preferably, in step S3, the molar ratio of compound c to the alkaline substance is 1:1 to 1:5; Preferably, in step S3, the reaction temperature is 10–140°C and the reaction time is 1–24 h; Preferably, in step S3, the reaction is carried out in an organic solvent selected from any one or a combination of at least two of DMF, dichloromethane, toluene, xylene, or chlorobenzene.

9. A photocurable composition comprising the oxetane monomer compound of claim 1 or 2, wherein the oxetane monomer compound serves as a crosslinking agent; Preferably, the photocurable composition further includes a photosensitive resin, a photosensitizer, and a solvent.

10. The use of the oxobutane monomer compound or photocurable composition according to claim 1 or 2 in coatings, 3D printing, hard coatings, ink compositions or interlayer insulating films.

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