Compound, its production method, and monomolecules, oligomers, and polymers derived from the compound

Abstract

This specification relates to compounds, methods for their preparation, and monomers, oligomers, and polymers derived from the compounds.

Description

[Technical Field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0006320, filed with the Korean Intellectual Property Office on January 17, 2022, the entire contents of which are incorporated herein by reference.

[0002] This specification relates to compounds, methods for their preparation, and monomers, oligomers, and polymers 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 the binding site to Chemical Formula 1.

[0008] One embodiment of the present invention is (s1) triallyl isocyanurate, C n F 2n+1 The present invention provides a method for preparing a compound of Formula 1, the method comprising: (s4) adding X4, a first base, and a first solvent and stirring under nitrogen gas; (s2) adding a radical initiator and stirring; and (s3) adding a second solvent and a second base. [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] One embodiment of the present invention provides a mixture comprising at least two of the above compounds.

[0011] Another embodiment herein provides a single molecule derived from the compound.

[0012] Furthermore, another embodiment of the present specification provides an oligomer comprising a monomer unit derived from the above compound.

[0013] Yet another embodiment of the present specification provides a polymer comprising monomer units derived from the above compound. [Effects of the Invention]

[0014] The compounds according to one embodiment of the present invention, and the monomers, oligomers, and polymers derived therefrom, contain good leaving groups, contain structures that allow crosslinking, and can be used to prepare a variety of derivatives.

[0015] 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.

[0016] 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]

[0017] [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

[0018] The present specification will be explained in more detail below. One embodiment of the present disclosure provides a compound of Formula 1: [ka]

[0019] 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 the binding site to Chemical Formula 1.

[0020] The compound of Chemical Formula 1 according to one embodiment of the present specification is a triallyl isocyanurate derivative that serves as a crosslinker and contains a fluorine-containing perfluoroalkyl group having the effects of lowering the refractive index, the dielectric constant, and the dielectric loss tangent, and a double bond that reduces the degree of freedom. It is used as a multifunctional monomer and can exhibit the effects of lowering the refractive index, the dielectric constant, the surface energy, and the dielectric loss tangent.

[0021] According to one embodiment of the present specification, any one of X1 to X3 is [ka] and the remainder is an allyl group.

[0022] According to one embodiment of the present specification, any two of X1 to X3 are [ka] and the rest are allyl groups.

[0023] According to one embodiment of the present specification, X1 to X3 are each [ka] is.

[0024] According to one embodiment of the present specification, n is an integer of 4 to 12.

[0025] According to one embodiment of the present specification, n is 4, 6 or 8.

[0026] According to one embodiment of the present specification, [ka] is one of the following structures: [ka]

[0027] 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.

[0028] According to one embodiment of the present specification, the compound represented by Chemical Formula 1 is any one selected from the following compounds:

[0029] [ka]

[0030] [ka]

[0031] One embodiment of the present invention is (s1) triallyl isocyanurate, C n F 2n+1The present invention provides a method for preparing a compound of Formula 1, the method comprising: (s4) adding X4, a first base, and a first solvent and stirring under nitrogen gas; (s2) adding a radical initiator and stirring; and (s3) adding a second solvent and a second base. [ka]

[0032] In the step (s1) and Chemical Formula 1,

[0033] 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.

[0034] According to one embodiment of the present specification, the chemical X4 is an iodine group (-I).

[0035] 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.

[0036] In this specification, normal temperature means 20±5° C. under atmospheric pressure.

[0037] According to one embodiment of the present specification, the first base is a non-nucleophilic base.

[0038] The first base according to one embodiment of the present specification may be, but is not limited to, potassium carbonate (K2CO3), sodium bicarbonate (NaHCO3), potassium bicarbonate (KHCO3), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), or any mixture thereof, and any conventionally used base may be used.

[0039] According to one embodiment of the present specification, the first solvent is an organic solvent.

[0040] According to one embodiment of the present specification, the first solvent is selected from, but is not limited to, hexane, heptane, toluene, benzene, acetonitrile, dichloromethane (methylene chloride), 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.

[0041] According to one embodiment of the present specification, the radical initiator is a water-soluble initiator.

[0042] 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.

[0043] According to one embodiment of the present specification, the reaction temperature in step (s2) is 0° C. or higher. Specifically, the reaction temperature in step (s2) is 0° C.

[0044] When the step (s2) is carried out at the reaction temperature, side reactions are suppressed, and the yield of the compound of Formula 1, which is the final target, is increased.

[0045] According to one embodiment of the present specification, the second solvent is an organic solvent.

[0046] According to one embodiment of the present specification, the second solvent is selected from, but is not limited to, hexane, heptane, toluene, benzene, acetonitrile, dichloromethane (methylene chloride), dichloroethane, trichloroethane, chloroform, dichloroform, nitromethane, dibromomethane, cyclopentanone, cyclohexanone, fluorobenzene, bromobenzene, chlorobenzene, xylene, mesitylene, ethyl acetate, or any mixture thereof, and any conventionally used organic solvent may be used.

[0047] According to one embodiment of the present specification, the second base is a non-nucleophilic base.

[0048] The second base according to one embodiment of the present specification may be, but is not limited to, potassium carbonate (KCO), sodium bicarbonate (NaHCO), potassium bicarbonate (KHCO), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), or any mixture thereof, and any conventionally used base may be used.

[0049] According to one embodiment of the present specification, the second base may be added in step (s3) by dropwise addition, dropping, or by a conventional method.

[0050] According to one embodiment of the present specification, the reaction temperature in step (s3) 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, various temperature ranges can be set in step (s3) depending on the range of n and the molecular weight of the compound of Chemical Formula 1.

[0051] The reaction 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) a first atom transfer reaction occurs. In (3), the hydrogen of the initiator dissociates and bonds with the halogen (iodine) group attached to the perfluoroalkyl group, converting the perfluoroalkyl group 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, (5) the halogen (iodine) group attached to the perfluoroalkyl group bonds with the radical to produce an intermediate compound with a halogen (iodine) group attached, and (6) the halogen group of the intermediate compound dissociates through a second atom transfer reaction, and an elimination reaction occurs to produce a compound of Formula 1 containing a perfluoroalkyl group with a double bond. Furthermore, (7) oligomerization by the radical generated by the reaction (6) can also occur.

[0052] In Figure 1, K a is the radical substrate R f is the addition rate constant to p is the oligomerization rate constant of the substrate.

[0053] According to one embodiment of the present specification, the method further comprises a step of obtaining an intermediate compound after step (s2) and a step of obtaining the compound of Formula 1 after step (s3).

[0054] According to one embodiment of the present specification, the obtaining step includes: (s41) Quench and phase separation step; (s42) Drying stage; (s43) filtration stage; (s44) concentration stage; and (s45) Includes the acquisition stage.

[0055] According to one embodiment of the present specification, the step (s41) (quenching and layer separation step) is a step of adding a reaction terminating substance to terminate the reaction and separating the layers.

[0056] According to one embodiment of the present specification, the reaction termination material in step (s41) 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.

[0057] The order in which the reaction is terminated and the layer separation is carried out in step (s41) 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.

[0058] The radical initiator remaining after step (s2) is water-soluble and can be removed by dissolving it in water in step (s41).

[0059] According to one embodiment of the present specification, step (s42) (drying step) is carried out by adding a desiccant to any layer of the material separated in step (s41). For example, when chloroform is used as the reaction terminator, the desiccant is added to the lower chloroform layer, i.e., the organic layer.

[0060] The desiccant may be, for example, but is not limited to, magnesium sulfate, sodium sulfate, etc. According to a preferred embodiment, the desiccant is magnesium sulfate.

[0061] As used herein, the desiccant is added in an amount sufficient for drying as is conventional in the art.

[0062] According to one embodiment of the present specification, step (s43) (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.

[0063] According to one embodiment of the present specification, the step (s44) (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.

[0064] According to one embodiment of the present specification, after the step (s44), a filtration and drying step may be further added.

[0065] A drying step may be included before the obtaining step (s45), which is a step of drying the intermediate compound or the compound of Formula 1. The drying step is different from (s42), and the drying step 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.

[0066] According to one embodiment of the present specification, the step (s45) (obtaining step) is a step of obtaining the intermediate compound or the compound of Formula 1 concentrated (dried) in the step (s44).

[0067] According to one embodiment of the present specification, in the obtaining step, the steps (s42) and (s43) may be carried out three or more times as necessary.

[0068] According to one embodiment of the present specification, there is provided a mixture containing two or more of the above compounds.

[0069] According to another embodiment of the present specification, the two or more compounds contained in the mixture are the same or different from each other, that is, they have the structure of Chemical Formula 1 and are the same or different from each other.

[0070] According to another embodiment of the present specification, the mixture may further contain a compound different from the compound represented by Chemical Formula 1.

[0071] According to one embodiment of the present specification, there is provided a single molecule derived from the compound.

[0072] 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.

[0073] According to one embodiment of the present specification, there is provided an oligomer comprising a monomer unit derived from the compound.

[0074] 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.

[0075] 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.

[0076] Furthermore, the radical generated by the elimination of the halogen group used as the electron donor can also react with other oligomers containing an allyl group or the monomer.

[0077] 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.

[0078] According to one embodiment of the present specification, there is provided a polymer comprising a monomer unit derived from the compound.

[0079] Those skilled in the art will understand the term "monomer unit" as used herein to mean a compound that is polymerized and linked to the main chain of a polymer.

[0080] 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, and a vinyl group of the compound of Chemical Formula 1 can form a radical to become a monomer, and a monomer unit or terminal group constituting the main chain of another polymer can be introduced.

[0081] According to one embodiment of the present specification, the polymer may further comprise an additional monomer unit, and the additional monomer unit is not limited.

[0082] According to one embodiment of the present specification, the polymer may be, but is not limited to, an alternating polymer or a random polymer.

[0083] In this specification, even when a monomer unit contained in a polymer is mentioned, it is not limited to a polymer containing only the mentioned monomer unit, and the polymer may further contain other monomer units as comonomer units in addition to the mentioned monomer units, within the scope of the present invention.

[0084] The compounds according to one embodiment of the present disclosure, and the molecules, oligomers, and polymers derived therefrom, may be used as, but are not limited to, electronic materials, organic insulating materials, and / or substrate materials. [Example]

[0085] 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.

[0086] Example 1 In a 250 mL two-neck 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. The mixture was then filtered and the solvent evaporated to yield 44 g of the intermediate compound containing perfluorobutyl iodide.

[0087] In a 100 mL two-necked round-bottom flask, 14.38 g of the intermediate compound was dissolved in 13 mL of dichloromethane (methylene chloride), and then 5.2 mL of DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) was added dropwise over 1 minute. After 1 hour, 30 mL of 1N HCl was added, and the mixture was stirred for 30 minutes. After that, the mixture was transferred to a separatory funnel and washed with 100 mL of HCl, 100 mL of saturated NaHCO3 solution, and 200 mL of water. The organic layer was then dried by adding 10 g of MgSO4. The mixture was then filtered and the solvent was evaporated to obtain 10 g of the final product. 1 The mass ratio of Compounds 1-1, 1-2, and Oligomer 1 in the final product measured by H-NMR, and the weight average molecular weight measured by GPC (gel permeation chromatography) are shown in Table 1 below.

[0088] [ka]

[0089] [Table 1]

[0090] Oligomer 1 in Example 1 refers to a product derived from one or more of compounds 1-1 and 1-2, and having a molecular weight exceeding that of compound 1-2, which is the largest unit as a single molecule.

[0091] Example 2. In a 250 mL two-neck 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, followed by the addition of powdered Na2SO4 and stirring 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 mixture was then filtered and the solvent evaporated to yield 53 g of the perfluorooctyl iodide-incorporated intermediate product.

[0092] In a 100 mL two-necked round-bottom flask, 13.20 g of the intermediate compound was dissolved in 10 mL of methylene chloride, and then 3.2 mL of DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) was added dropwise over 1 minute. After 1 hour, 30 mL of 1N HCl was added, and the mixture was stirred for 30 minutes. After that, the mixture was transferred to a separatory funnel and washed with 100 mL of HCl, 100 mL of saturated NaHCO3 solution, and 200 mL of water. The organic layer was then dried by adding 10 g of MgSO4. The mixture was then filtered and the solvent was evaporated to obtain 10 g of the final product. 1The mass ratio of Compound 2-1, 2-2, and Oligomer 2 in the final product measured by H-NMR, and the weight average molecular weight measured by GPC (gel permeation chromatography) are shown in Table 2 below.

[0093] [ka]

[0094] [Table 2]

[0095] Oligomer 2 in Example 2 is derived from one or more of compounds 2-1 and 2-2, and refers to a product whose molecular weight exceeds that of compound 2-2, which is the largest unit as a single molecule.

[0096] As shown in Tables 1 and 2, the compound of Chemical Formula 1 is a triallyl isocyanurate derivative that contains a perfluoroalkyl group containing fluorine and a double bond that reduces the degree of freedom, and serves as a crosslinking agent. It is used as a multifunctional monomer, and can provide the effects of low refractive index, low dielectric constant, low surface energy (low surface tension), and low dielectric tangent, and can be used as an electronic material, organic insulating material, and / or substrate material.

[0097] Evaluation example: Refractive index and surface tension measurements The refractive indexes of the final products prepared in Examples 1 and 2 and triallyl isocyanurate, which is the substance of Comparative Example 1, were measured at 25°C using RX-5000α (ATAGO).

[0098] In addition, Tensiometer K11 (KRUSS) was used to measure the surface tension of the final products prepared in Examples 1 and 2 and triallyl isocyanurate, which is the substance of Comparative Example 1. The surface tension was measured by preparing a 0.5 wt% PGMEA solution at 27.8°C to 28.1°C.

[0099] The triallyl isocyanurate used in Comparative Example 1 was a product of TCI.

[0100] [Table 3]

[0101] From Table 3, it can be seen that the compounds of the present invention have lower refractive indexes and surface tensions than the conventional substance triallyl isocyanurate of Comparative Example 1. Therefore, the compounds of the present invention can be used as electronic materials, organic insulating materials, and / or substrate materials.

[0102] Evaluation example: Measurement of dielectric properties A coating composition was prepared by mixing triallyl isocyanurate (Comparative Example 1) with OPE-2st (Mitsubishi Gas Chemical Co., Inc.) and a solvent such as toluene. The prepared coating composition was coated on copper foil and dried. The dried film was vacuum pressed at 225°C, and then the dielectric properties were measured. The measured relative dielectric constant (Dk) was 2.60.

[0103] Instead of triallyl isocyanurate in Comparative Example 1, the final products of Examples 1 and 2 were mixed in a 1:1 ratio to prepare a coating composition, and the dielectric properties were measured in the same manner. As a result, it was confirmed that the relative dielectric constant (Dk) was as low as 2.525.

[0104] Based on the above results, the compound of Formula 1 can be used to lower the dielectric constant when it is prepared into a substrate material composition and applied to a copper clad laminate (CCL), etc.

Claims

1. A compound of the following formula 1: 【Chemistry 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 4 to 12, 【Transformation 3】 is the binding site to Formula 1.

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

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

4. (s1) triallyl isocyanurate, C ｎ F ２ｎ＋１ adding X4, a first base, and a first solvent and stirring under nitrogen gas; (s2) adding a radical initiator and stirring; and (s3) Adding a second solvent and a second base A method for preparing a compound of the following formula 1, comprising: 【Transformation 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 4 to 12, 【Chemistry 10】 is a binding site to Chemical Formula 1; X4 is a halogen group.

5. A mixture comprising two or more compounds according to any one of claims 1 to 3. (i) one or more radical reaction products of the compound of any one of claims 1 to 3, or (ii) a radical reaction product of triallyl isocyanurate and one or more of the compounds of any one of claims 1 to 3 That is, oligomers. (i) one or more radical reaction products of the compound of any one of claims 1 to 3, or (ii) a radical reaction product of triallyl isocyanurate and one or more of the compounds of any one of claims 1 to 3 That is, a polymer.

8. A coating composition comprising one or more compounds according to any one of claims 1 to 3.

9. A composition for substrate materials, comprising one or more compounds according to any one of claims 1 to 3.

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