Compound, method for producing the same, and single molecule and oligomer derived from the compound

Abstract

This specification relates to compounds of formula 1, methods for their preparation, and monomers and oligomers derived from said compounds.

Description

[Technical Field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0006316, filed with the Korean Intellectual Property Office on January 17, 2022, the entire contents of which are incorporated herein by reference.

[0002] The present specification relates to compounds, methods for their preparation, and molecules and oligomers derived from the compounds. [Background technology]

[0003] Triallyl isocyanurate is useful as a crosslinking agent with excellent heat resistance and chemical resistance, and is expected to be used in a wide range of fields, including electronic materials, liquid crystals, semiconductors, and solar cells. For example, it is used as an encapsulant to prevent substances such as liquids and gases from entering the interior of printed wiring boards, i.e., plate- or film-like components that form electronic circuits by fixing a large number of electronic components such as integrated circuits, resistors, and capacitors to the surface and connecting the components with wiring.

[0004] However, triallyl isocyanurate has a high dielectric constant and dissipation factor, and research is ongoing to lower these. Summary of the Invention [Problem to be solved by the invention]

[0005] The present specification provides compounds, methods for their preparation, and monomers and oligomers derived from the compounds. [Means for solving the problem]

[0006] One embodiment of the present disclosure provides a compound of Formula 1: [ka]

[0007] In the above Chemical Formula 1, At least one of X1 to X3 [ka] and the remainder is an allyl group, n is an integer from 1 to 20, [ka] is a binding site to Chemical Formula 1, X4 is a halogen group.

[0008] One embodiment of the present invention is (s1) triallylisocyanurate, C n F 2n+1 The present invention provides a method for preparing a compound of the following formula 1, comprising: (s4) adding X4, a base, and a solvent and stirring under nitrogen gas; and (s2) adding a radical initiator and stirring. [ka]

[0009] In the step (s1) and Chemical Formula 1, At least one of X1 to X3 [ka] and the remainder is an allyl group, n is an integer from 1 to 20, [ka] is a binding site to Chemical Formula 1, X4 is a halogen group.

[0010] Another embodiment herein provides a single molecule derived from the compound.

[0011] Furthermore, another embodiment of the present specification provides an oligomer comprising a monomer unit derived from the above compound. [Effects of the Invention]

[0012] The compounds according to one embodiment of the present invention, and the monomers and oligomers derived therefrom, contain good leaving groups, contain structures that allow crosslinking, and allow the preparation of a variety of derivatives.

[0013] The compound according to one embodiment of the present specification is used as a polyfunctional monomer, and can exhibit the effects of a low refractive index, a low dielectric constant, a low surface energy, and a low dielectric loss tangent.

[0014] In the method for producing a compound according to one embodiment of the present specification, the reaction proceeds under mild conditions, with fewer side reactions, and the yield of the target compound, the compound of Formula 1, is high. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 2 is a diagram illustrating the reaction mechanism of the method for producing the compound of Chemical Formula 1. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present specification will be explained in more detail below. One embodiment of the present disclosure provides a compound of Formula 1: [ka]

[0017] In the above Chemical Formula 1, At least one of X1 to X3 [ka] and the remainder is an allyl group, n is an integer from 1 to 20, [ka] is a binding site to Chemical Formula 1, X4 is a halogen group.

[0018] The compound of Chemical Formula 1 according to one embodiment of the present specification is a triallyl isocyanurate derivative that contains a perfluoroalkyl group containing fluorine, which has the effect of lowering the dielectric constant and the dielectric loss tangent, and serves as a crosslinking agent. It is used as a multifunctional monomer and can exhibit the effects of lowering the dielectric constant, the surface energy, and the dielectric loss tangent.

[0019] According to one embodiment of the present specification, any one of X1 to X3 is [ka] and the rest are allyl groups.

[0020] According to one embodiment of the present specification, any two of X1 to X3 are [ka] and the rest are allyl groups.

[0021] According to one embodiment of the present specification, X1 to X3 are each [ka] is.

[0022] According to one embodiment of the present specification, n is an integer of 4 to 12.

[0023] According to one embodiment of the present specification, n is 4, 6 or 8.

[0024] According to one embodiment of the present specification, X4 is an iodine group (-I).

[0025] According to one embodiment of the present specification, [ka] is one of the following structures: [ka]

[0026] According to one embodiment of the present specification, [ka] When n is within the above range, the chain length of the perfluoroalkyl group can be easily adjusted, and compounds with various molecular weights can be produced. In addition, when the perfluoroalkyl group is contained, the effects of a low refractive index, a low dielectric constant, a low surface energy, and a low dielectric loss tangent can be exhibited.

[0027] According to one embodiment of the present specification, the compound represented by Chemical Formula 1 is any one selected from the following compounds: [ka] [ka]

[0028] One embodiment of the present invention is (s1) triallylisocyanurate, C n F 2n+1 The present invention provides a method for preparing a compound of the following formula 1, comprising: (s4) adding X4, a base, and a solvent and stirring under nitrogen gas; and (s2) adding a radical initiator and stirring. [ka]

[0029] In the step (s1) and Chemical Formula 1, At least one of X1 to X3 [ka] and the remainder is an allyl group, n is an integer from 1 to 20, [ka] is a binding site to Chemical Formula 1, X4 is a halogen group.

[0030] According to one embodiment of the present specification, the reaction temperature in step (s1) is 0°C to room temperature. When the reaction is carried out within this reaction temperature range, the reaction conditions are mild and not strict, and side reactions that occur as the temperature increases are suppressed, resulting in a high yield of the final target compound of Chemical Formula 1. Furthermore, in step (s1), various temperature ranges can be set depending on the range of n and the molecular weight of the compound of Chemical Formula 1.

[0031] In this specification, normal temperature means 20±5° C. under atmospheric pressure.

[0032] The base according to one embodiment of the present invention may be, but is not limited to, potassium carbonate (K2CO3), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), or any mixture thereof, and any conventionally used base may be used.

[0033] According to one embodiment of the present specification, the solvent is an organic solvent.

[0034] According to one embodiment of the present specification, the solvent is selected from, but is not limited to, hexane, heptane, toluene, benzene, acetonitrile, dichloromethane, dichloroethane, trichloroethane, chloroform, dichloroform, nitromethane, dibromomethane, cyclopentanone, cyclohexanone, fluorobenzene, bromobenzene, chlorobenzene, xylene, mesitylene, ethyl acetate, or any mixture thereof, and any organic solvent used in the prior art may be used.

[0035] According to one embodiment of the present specification, the radical initiator is a water-soluble initiator.

[0036] According to one embodiment of the present specification, the radical initiator is any one of potassium persulfate (KPS), ammonium persulfate (APS), potassium hydrosulfite, sodium hydrosulfite, sodium perlactate, or hydrogen peroxide.

[0037] According to one embodiment of the present specification, the reaction temperature of step (s2) is 0° C. When step (s2) is carried out at this reaction temperature, side reactions are suppressed, and the yield of the final target compound of Formula 1 is increased.

[0038] The mechanism of the production method according to one embodiment of the present specification is shown in Figure 1 below. (1) A radical initiator dissociates under basic conditions, (2) a radical is generated, and (3) an atom transfer reaction occurs. In (3), the hydrogen of the initiator dissociates and bonds with the halogen group (iodine group) attached to the perfluoroalkyl, converting the perfluoroalkyl into a radical. Subsequently, in the radical chain reaction of (4) and (5), (4) the radicalized perfluoroalkyl group bonds with the allyl group of the triallyl isocyanurate to form a radical, and (5) the halogen group (iodine group) attached to the perfluoroalkyl binds to the radical, producing the compound of Chemical Formula 1.

[0039] In Figure 1, K a is the radical substrate R f is the addition rate constant to

[0040] According to one embodiment of the present specification, the method further comprises obtaining the compound of Formula 1 after step (s2).

[0041] According to one embodiment of the present specification, the obtaining step includes: (s31) Quench and phase separation step; (s32) Drying stage; (s33) filtration stage; (s34) concentration stage; and (s35) Includes the acquisition stage.

[0042] According to one embodiment of the present specification, the step (s31) (quenching and layer separation step) is a step of adding a reaction terminating substance to terminate the reaction and separating the layers.

[0043] According to one embodiment of the present specification, the reaction termination material in step (s31) may be, but is not limited to, distilled water, an aqueous ammonium chloride solution, an aqueous sodium bicarbonate solution, a saturated KF solution, an aqueous HCl solution, an aqueous NaCl solution, chloroform, dichloromethane, ethyl acetate, etc. Preferably, the reaction termination material is an aqueous ammonium chloride solution, an aqueous sodium bicarbonate solution, an aqueous NaCl solution, ethyl acetate, etc.

[0044] The order in which the reaction is terminated and the layer separation is carried out in step (s31) is not limited to a specific order. In one embodiment, the reaction may be terminated and the layer separation may be carried out simultaneously. In another example, the reaction may be terminated by adding a reaction terminator, and then the layer separation may be carried out. However, the order in which the reaction is carried out is not limited to the above example.

[0045] The radical initiator remaining after the reaction is water-soluble and can be removed by dissolving it in water in step (s31).

[0046] According to one embodiment of the present specification, step (s32) (drying step) is carried out by adding a desiccant to any layer of the material separated in step (s31). For example, when chloroform is used as the reaction terminator, the desiccant is added to the lower chloroform layer, i.e., the organic layer.

[0047] The desiccant may be, but is not limited to, magnesium sulfate, sodium sulfate, etc. According to a preferred embodiment, the desiccant is magnesium sulfate.

[0048] As used herein, the desiccant is added in an amount sufficient to provide the drying effect commonly known in the art.

[0049] According to one embodiment of the present specification, step (s33) (filtering step) may be performed by a method known in the art. Representative examples include a method of using an inhaler to suck air and filtering impurities, including the desiccant, separated from the target product through a filter, or a method of using a solvent that dissolves other impurities but does not dissolve the target product, utilizing the difference in solubility in a specific solvent, to remove other impurities.

[0050] According to one embodiment of the present specification, the step (s34) (concentration step) may be carried out by a method known in the art, a representative example of which is, but is not limited to, evaporating the solvent using a vacuum rotary evaporator.

[0051] According to one embodiment of the present specification, after the step (s34), a filtration and drying step may be further added.

[0052] A drying step may be included before the obtaining step (s35), which is a step of drying the compound of Formula 1. The drying step is different from (s32), and may be carried out by a method known in the art, representative examples of which include vacuum oven drying, spray drying, and flash drying, and preferably vacuum oven drying.

[0053] According to one embodiment of the present specification, the step (s35) (obtaining step) is a step of obtaining the compound of Formula 1 concentrated (dried) in the step (s34).

[0054] According to one embodiment of the present specification, in the obtaining step, the steps (s32) to (s33) may be carried out three or more times as necessary.

[0055] According to one embodiment of the present specification, there is provided a mixture containing two or more of the above compounds.

[0056] According to another embodiment of the present specification, the two or more compounds contained in the mixture may be the same or different from each other, i.e., they may have the structure of Chemical Formula 1 and may be identical to or different from each other.

[0057] According to another embodiment of the present specification, the mixture may further contain a compound different from the compound represented by Chemical Formula 1.

[0058] According to one embodiment of the present specification, there is provided a single molecule derived from the compound.

[0059] In the present specification, for example, the "monomer derived from the compound of Chemical Formula 1" may refer to a monomolecule in which an additional substituent is introduced by forming a radical from an allyl group of the compound of Chemical Formula 1, a monomolecule in which an additional substituent is introduced by using a halogen group of Chemical Formula 1 as an electron donor, or the compound of Chemical Formula 1 itself.

[0060] According to one embodiment of the present specification, there is provided an oligomer comprising a monomer unit derived from the compound.

[0061] Those skilled in the art will understand that the term "monomer unit" as used herein refers to a structural portion of a compound that is polymerized and linked to the backbone of an oligomer.

[0062] In the present specification, for example, the "monomer unit derived from the compound of Chemical Formula 1" means a repeating unit constituting the main chain in a polymer, in which the allyl group of the compound of Chemical Formula 1 can form a radical to become a monomer, and in which the halogen group can be used as an electron donor to introduce a monomer unit or a terminal group constituting the main chain of another oligomer.

[0063] Furthermore, the radicals generated by the elimination of the halogen groups in the structure can also react with other oligomers containing aryl groups or the monomers.

[0064] According to one embodiment of the present specification, the oligomer may have the following structure, but is not limited to this: The following structure is exemplified only when n in Chemical Formula 1 is 4, 6, or 8, but various oligomer structures can be shown depending on the range of n in Chemical Formula 1 from 1 to 20. [ka] [ka]

[0065] In the above structure: Each of n1 to n3 is an integer of 2 or more.

[0066] According to one embodiment of the present specification, n1 to n3 are each an integer of 2 to 10,000, preferably an integer of 2 to 5,000, more preferably an integer of 2 to 1,000, and even more preferably an integer of 2 to 100.

[0067] The compounds according to one embodiment of the present invention, and the monomers and oligomers derived therefrom, contain good leaving groups, contain structures that allow crosslinking, and can be used to prepare a variety of derivatives. [Example]

[0068] Hereinafter, the present specification will be described in detail with reference to examples in order to specifically explain the present specification. However, the examples according to the present specification can be modified into various other forms, and the scope of the present specification should not be construed as being limited to the examples detailed below. The examples of the present specification are provided to more completely explain the present specification to those skilled in the art.

[0069] Example 1 In a 250 mL two-necked round-bottom flask, 9.9 g of triallyl isocyanurate, 0.101 g of NaHCO3, and 20.7 mL of nonafluoro-1-iodobutane were dissolved in 100 mL of water and 50 mL of acetonitrile. After bubbling with N2 for 30 minutes at room temperature, Na2SO4 powder was added and the mixture was stirred at 0°C for 17 hours. The aqueous layer was then extracted three times with 200 mL of chloroform, and the organic layer was washed with water and dried over 10 g of MgSO4. After filtration and evaporation of the solvent, 44 g of a product containing perfluorobutyl iodide was obtained. The detailed composition of the product was as follows: 1 The weight ratios of Compound 1-2, Compound 1-3 and Oligomer 1 were measured by H-NMR and are shown in Table 1 below.

[0070] [ka]

[0071] [Table 1]

[0072] Example 2. In a 250 mL two-necked round-bottom flask, 9.9 g of triallyl isocyanurate, 0.101 g of NaHCO3, and 10.3 mL of nonafluoro-1-iodobutane were dissolved in 100 mL of water and 50 mL of acetonitrile. After bubbling with N2 for 30 minutes at room temperature, Na2SO4 powder was added and the mixture was stirred at 0°C for 17 hours. The aqueous layer was then extracted three times with 200 mL of chloroform, and the organic layer was washed with water and dried over 10 g of MgSO4. After filtration and evaporation of the solvent, 22 g of product containing perfluorobutyl iodide was obtained. The detailed composition of the product was as follows:1 The weight ratios of Compound 1-1, Compound 1-2 and Oligomer 1 were measured by H-NMR and are shown in Table 2 below.

[0073] [Table 2]

[0074] Oligomer 1 in Examples 1 and 2 is derived from one or more of compounds 1-1 to 1-3, and refers to a product having a molecular weight exceeding that of compound 1-3, which is the largest unit as a single molecule.

[0075] Example 3 In a 250 mL two-necked round-bottom flask, 9.97 g of triallyl isocyanurate, 0.101 g of NaHCO3, and 31.7 mL of heptadecafluoro-n-octyl iodide were dissolved in 100 mL of water and 40 mL of acetonitrile. N2 was bubbled through the solution at 0 °C for 30 minutes, and then Na2SO4 powder was added and stirred at 0 °C for 17 hours. The aqueous layer was then extracted three times with 200 mL of chloroform, and the organic layer was washed with water and dried over 10 g of MgSO4. The mixture was then filtered and the solvent evaporated to obtain 53 g of a product containing perfluorooctyl iodide. The detailed composition of the product was as follows: 1 The weight ratios of Compound 2-2, Compound 2-3 and Oligomer 2 were measured by H-NMR and are shown in Table 3 below.

[0076] [ka]

[0077] [Table 3]

[0078] Example 4. In a 250 mL two-necked round-bottom flask, 9.97 g of triallyl isocyanurate, 0.101 g of NaHCO3, and 15.8 mL of heptadecafluoro-n-octyl iodide were dissolved in 100 mL of water and 40 mL of acetonitrile. N2 was bubbled through the solution at 0 °C for 30 minutes, and then Na2SO4 powder was added and stirred at 0 °C for 17 hours. The aqueous layer was then extracted three times with 200 mL of chloroform. The organic layer was washed with water and dried over 10 g of MgSO4. The solution was then filtered and the solvent evaporated to obtain 36 g of a product containing perfluorooctyl iodide. The detailed composition of the product is shown below. 1 The weight ratios of Compound 2-1, Compound 2-2 and Oligomer 2 were measured by H-NMR and are shown in Table 4 below.

[0079] [Table 4]

[0080] The oligomer 2 in Examples 3 and 4 is derived from one or more of compounds 2-1 to 2-3, and refers to a product whose molecular weight exceeds that of compound 2-3, which is the largest unit as a single molecule.

[0081] The compounds of Formula 1 prepared in Tables 1 to 4 are triallyl isocyanurate derivatives that contain a perfluoroalkyl group containing fluorine, which has the effect of lowering the relative dielectric constant and the dielectric dissipation factor, and act as a crosslinking agent. They are used as multifunctional monomers and can exhibit the effects of lowering the refractive index, relative dielectric constant, surface energy, and dielectric dissipation factor, and can be used for various applications.

[0082] The compound of Formula 1 can be used as a material for a circuit board, and has a dielectric constant of about D k =2.5 (comparison example =2.6 or more), and from the above results, it can be predicted that the effect of non-reduction of the dielectric constant can be obtained. Comparative Example: Triallyl isocyanurate

Claims

1. A compound of the following formula 1: 【Chemical 1】 In the above Chemical Formula 1, At least one of X1 to X3 【Chemistry 2】 and the remainder is an allyl group, n is an integer from 1 to 20, 【Chemistry 3】 is a binding site to Chemical Formula 1; X4 is a halogen group.

2. The compound according to claim 1, wherein X4 is an iodine group (-I).

3. The aforementioned 【Chemistry 4】 is any of the following structures: 【Chemistry 5】 。

4. The compound according to claim 1, wherein the chemical formula 1 is any one selected from the following compounds: 【Chemistry 6】 【Chemistry 7】 。

5. (s1) triallyl isocyanurate, C ｎ F ２ｎ＋１ Adding X4, a base, and a solvent and stirring under nitrogen gas; and (s2) Adding a radical initiator and stirring A method for preparing a compound of the following formula 1, comprising: 【Chemistry 8】 In the step (s1) and formula 1, At least one of X1 to X3 【Chemistry 9】 and the remainder is an allyl group, n is an integer from 1 to 20, 【Chemistry 10】 is a binding site to Chemical Formula 1; X4 is a halogen group. (i) a radical reaction product of one or more compounds according to any one of claims 1 to 4, and (ii) radical reaction products of triallyl isocyanurate with one or more compounds according to any one of claims 1 to 4 An oligomer selected from:

7. Use of the compound according to any one of claims 1 to 4 as a material for a circuit board.

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