Compounds, methods for making the same, and monomeric and polymeric derivatives thereof

Abstract

This specification relates to compounds of Formula 1, methods for making the same, and monomers and polymers derived from the compounds.

Description

Technical Field

[0001] This application claims priority and benefit to Korean Patent Application No. 10-2021-0154715, filed on November 11, 2021, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

[0002] This specification relates to compounds, methods for their preparation, and monomers and polymers derived from said compounds. Background Technology

[0003] In related fields, the introduction of perfluoroalkyl groups into aromatic compounds is induced by the following methods: nucleophilic aromatic substitution reactions using Grignard reagents and halobenzenes or their derivatives, or nucleophilic substitution reactions using reactions that are the opposite of nucleophilic aromatic substitution reactions. However, progress is difficult in such cases due to the need for difficult-to-handle Grignard reagents, the need for large amounts of halogen compounds, and the sensitivity of the reaction to air and moisture. Summary of the Invention

[0004] Technical issues

[0005] This specification provides compounds, methods for their preparation, and monomolecules and polymers derived from said compounds.

[0006] Technical solution

[0007] An exemplary embodiment of this specification provides a compound of the following chemical formula 1.

[0008] [Chemical Formula 1]

[0009]

[0010] In chemical formula 1,

[0011] R1 is -C n F 2n+1 ,

[0012] n is an integer from 1 to 20.

[0013] R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0014] r2 is an integer from 1 to 4, and

[0015] When r2 is 2 or greater, two or more R2s are either the same or different from each other.

[0016] An exemplary embodiment of this specification provides a method for preparing a compound of chemical formula 1, the method comprising: (s1) introducing the following chemical formulas A and C. nF 2n+1 X, trialkyltin hydride and solvent, and stirring the resulting mixture under nitrogen; and (s2) adding a free radical initiator thereto and stirring the resulting mixture.

[0017] [Chemical Formula A]

[0018]

[0019] [Chemical Formula 1]

[0020]

[0021] In step (s1), in chemical formula A and chemical formula 1,

[0022] R1 is -C n F 2n+1 ,

[0023] n is an integer from 1 to 20.

[0024] R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0025] r2 is an integer from 1 to 4.

[0026] When r² is 2 or greater, two or more R² values ​​are the same or different from each other, and

[0027] X is a halogen group.

[0028] An exemplary embodiment of this specification provides a mixture comprising two or more of the said compounds.

[0029] Another exemplary embodiment of this specification provides a single molecule derived from the said compound.

[0030] Another exemplary embodiment of this specification provides a polymer comprising monomers derived from the compound.

[0031] Beneficial effects

[0032] Compounds according to an exemplary embodiment of this specification, as well as monomolecules and polymers derived therefrom, are used as electronic materials, organic insulating materials, and / or substrate materials.

[0033] The method for preparing a compound according to an exemplary embodiment of this specification has the advantage of preparing the compound at a lower reaction temperature. Therefore, since polymerization is suppressed to reduce side reactions, the yield of the compound of formula 1 is increased.

[0034] The compound according to an exemplary embodiment of the present invention can be used as a multifunctional monomer to exhibit the effects of achieving low refractive index, low relative permittivity, low surface energy and low dissipation factor. Attached Figure Description

[0035] Figure 1 A diagram illustrating the mechanism of atom transfer radical addition (ATRA) reactions. Detailed Implementation

[0036] This instruction manual will be described in more detail below.

[0037] An exemplary embodiment of this specification provides a compound of the following chemical formula 1.

[0038] [Chemical Formula 1]

[0039]

[0040] In chemical formula 1,

[0041] R1 is -C n F 2n+1 ,

[0042] n is an integer from 1 to 20.

[0043] R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0044] r2 is an integer from 1 to 4, and

[0045] When r2 is 2 or greater, two or more R2s are either the same or different from each other.

[0046] Throughout this application, the term "combinations thereof" in Markush-type expressions means a mixture or combination of one or more of the constituent elements described in the Markush-type expressions, and means including one or more of the constituent elements described above.

[0047] Examples of substituents in this specification will be described below, but are not limited thereto.

[0048] In this instruction manual, It refers to the part that is connected.

[0049] The term "substitution" means that the hydrogen atom bonded to the carbon atom of a compound is changed to another substituent, and there are no restrictions on the position to be substituted, as long as the position is where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted, the two or more substituents can be the same or different from each other.

[0050] In this specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from deuterium, halogen groups, hydroxyl groups, ester groups, alkyl groups, alkoxy groups, and aryl groups, substituted with two or more substituents linked together by the exemplified substituents, or without substituents.

[0051] In this specification, the fact that two or more substituents are linked means that the hydrogen of any one substituent is linked to another substituent. For example, when two substituents are linked to each other, phenyl and naphthyl can be linked together to form... or The substituents. Furthermore, the connection of three substituents not only includes the sequential connection of (substituent 1)-(substituent 2)-(substituent 3), but also the connection of (substituent 2) and (substituent 3) with (substituent 1). For example, phenyl, naphthyl, and isopropyl can be linked together to form... or The above definition also applies to cases where four or more substituents are connected to each other.

[0052] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine groups.

[0053] In this specification, for the ester group, the oxygen atom can be substituted by a straight-chain alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a cyclic alkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, the ester group can be any of the following structural formulas, but is not limited thereto.

[0054]

[0055] In the structure, R101 and R102 may be the same as or different from each other, and each is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0056] In this specification, alkyl groups may be straight-chain or branched, and there is no particular limitation on the number of carbon atoms, but preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0057] In this specification, the alkoxy group can be straight-chain, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably from 1 to 30. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy, etc.

[0058] According to one exemplary embodiment of this specification, n is an integer from 4 to 12.

[0059] According to an exemplary embodiment of this specification, R1 is -C4F9, -C6F 13 -C8F 17 or -C 12 F 25 .

[0060] According to an exemplary embodiment of this specification, compounds with different molecular weights can be prepared when n is within the above range because the chain length of the perfluoroalkyl group is easily adjustable. Furthermore, when perfluoroalkyl groups are included, the effects of achieving low refractive index, low relative permittivity, low surface energy, and low dissipation factor can be exhibited. In particular, although compounds containing perfluoroalkyl groups in related fields exhibit low permittivity and low refractive properties, they are not easily compatible. However, when R1 of Formula 1 of this invention is used, the effects of achieving effective low refractive index, low relative permittivity, low surface energy, and low dissipation factor can be exhibited while maintaining compatibility.

[0061] According to an exemplary embodiment of this specification, the compound of chemical formula 1 is a monomolecule comprising both perfluoroalkyl and vinyl groups, and can be used in a variety of applications such as electronic materials.

[0062] Furthermore, since the compound of Formula 1 according to an exemplary embodiment of this specification contains both perfluoroalkyl and vinyl groups, the compound can be used as a monomer for preparing polymers and can be used to prepare polymers containing perfluoroalkyl groups.

[0063] According to an exemplary embodiment of this specification, R2 is hydrogen; an ester group; or a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0064] According to an exemplary embodiment of this specification, R2 is hydrogen; an ester group; or a straight-chain or branched alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with one or more of a straight-chain or branched alkoxy group having 1 to 10 carbon atoms or combinations thereof.

[0065] According to an exemplary embodiment of this specification, R2 is hydrogen; an ester group; a methyl group substituted with a hydroxyl group; or a methyl group substituted with a straight-chain or branched alkoxy group having 1 to 10 carbon atoms.

[0066] According to an exemplary embodiment of this specification, R2 is hydrogen; an ester group; a methyl group substituted with a hydroxyl group; or a methyl group substituted with an ethoxy group substituted with a methoxy group.

[0067] According to an exemplary embodiment of this specification, in R2, the ester group is

[0068] R101 is a straight-chain or branched alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0069] According to an exemplary embodiment of this specification, R101 is methyl; ethyl; tert-butyl; phenyl-substituted methyl; or n-decyl.

[0070] According to one exemplary embodiment of this specification, r2 is 4.

[0071] According to one exemplary embodiment of this specification, r2 is 2.

[0072] According to one exemplary embodiment of this specification, r2 is 1.

[0073] According to one exemplary embodiment of this specification, chemical formula 1 is selected from any of the following compounds.

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] According to one exemplary embodiment of this specification, Chemical Formula 1 comprises a mixture of compounds of Chemical Formula 1.

[0080] Specifically, a mixture of compounds of formula 1 means that it comprises two or more of the compounds of formula 1, and their structures may be the same or different from each other.

[0081] An exemplary embodiment of this specification provides a method for preparing a compound of chemical formula 1, the method comprising: (s1) introducing the following chemical formulas A and C. n F 2n+1 X, trialkyltin hydride and solvent, and stirring the resulting mixture under nitrogen; and (s2) adding a free radical initiator thereto and stirring the resulting mixture.

[0082] [Chemical Formula A]

[0083]

[0084] [Chemical Formula 1]

[0085]

[0086] In step (s1), in chemical formula A and chemical formula 1,

[0087] R1 is -C n F 2n+1 ,

[0088] n is an integer from 1 to 20.

[0089] R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms.

[0090] r2 is an integer from 1 to 4.

[0091] When r² is 2 or greater, two or more R² values ​​are the same or different from each other, and

[0092] X is a halogen group.

[0093] According to one exemplary embodiment of this specification, Chemical Formula 1 comprises a mixture of compounds of Chemical Formula 1.

[0094] Specifically, a mixture of compounds of formula 1 means that it comprises two or more of the compounds of formula 1, and their structures may be the same or different from each other.

[0095] According to an exemplary embodiment of this specification, the reaction temperature in steps (s1) and (s2) is 20°C to 40°C, preferably 25°C to 35°C, and more preferably 30°C.

[0096] When the reaction is carried out at the stated reaction temperature, the reaction conditions are mild, the polymerization of styrene of formula A is suppressed, side reactions are reduced, and the yield of the final target product of formula 1 is increased.

[0097] According to one exemplary embodiment of this specification, the free radical initiator is an azo initiator.

[0098] According to an exemplary embodiment of this specification, the free radical initiator is selected from any one or more of azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylpentanonitrile, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide (BPO), or di-tert-butyl peroxide (DTBP).

[0099] Preferably, the free radical initiator is 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile).

[0100] When a free radical initiator is used, the free radical reaction can be initiated at low temperatures, giving it the advantage that the reaction can be carried out at the reaction temperature and under mild reaction conditions.

[0101] According to one exemplary embodiment of this specification, the trialkyltin hydride is a tributyltin hydride.

[0102] Trialkyltin hydrides are hydrogen donors with low binding energy, inducing hydrogen atom transfer (HAT) to a radical generated by a small amount of radical initiator. This HAT then induces the introduction of a perfluoroalkyl group into chemical formula A via an atom transfer radical addition (ATRA) reaction. The mechanism of the ATRA reaction is as follows: Figure 1 As shown.

[0103] According to one exemplary embodiment of this specification, the solvent is an organic solvent.

[0104] According to one exemplary embodiment of this specification, the solvent is selected from hexaalkyl, heptane, toluene, benzene, dichloromethane, dichloroethane, trichloroethane, chloroform, dichloroform, nitromethane, dibromomethane, cyclopentanone, cyclohexanone, fluorobenzene, bromobenzene, chlorobenzene, xylene, mesitylene, ethyl acetate, or any mixture thereof, but is not limited thereto, and organic solvents used in related technologies can be used.

[0105] According to one exemplary embodiment of this specification, X is an iodine (I) group.

[0106] According to an exemplary embodiment of this specification, step (s2) is followed by a step of obtaining a compound of chemical formula 1.

[0107] Obtaining a compound of formula 1 according to an exemplary embodiment of this specification includes:

[0108] (s31) Quenching and delamination steps;

[0109] (s32) Drying step;

[0110] (s33) Filtering steps;

[0111] (s34) Concentration step; and

[0112] (s35) Obtain the steps.

[0113] According to an exemplary embodiment of this specification, step (s31) (quenching and layer separation step) is a step of terminating the reaction and separating the layers by adding a reaction terminating material.

[0114] According to an exemplary embodiment of this specification, step (s31) is a step of diluting the reactants by adding the solvent used in step (s1), terminating the reaction by adding a reaction termination material, and separating the layers.

[0115] According to an exemplary embodiment of this specification, as the reaction termination material in step (s31), distilled water, ammonium chloride aqueous solution, sodium bicarbonate aqueous solution, KF (saturated) aqueous solution, HCl aqueous solution, NaCl (saturated) aqueous solution, dichloromethane, ethyl acetate, etc., can be used, but the reaction termination material is not limited to these. Preferably, ammonium chloride aqueous solution, sodium bicarbonate aqueous solution, NaCl aqueous solution, and ethyl acetate are used as the reaction termination materials.

[0116] In step (s31), the order in which the reaction termination and layer separation are performed is not limited to a specific order. As one exemplary embodiment, the reaction termination and layer separation can be performed simultaneously, and as another exemplary embodiment, the reaction can be terminated by adding a reaction termination material, after which layer separation can be performed. However, the order in which they are performed is not limited to the examples described above.

[0117] According to an exemplary embodiment of this specification, step (s32) (drying step) is performed by adding a desiccant to any of the material layers separated in step (s31). For example, when dichloromethane, as exemplified above, is used as the reaction termination material, step (s32) is performed by adding a desiccant to the dichloromethane layer, which is the lower layer, i.e., the organic layer. Examples of desiccants include, but are not limited to, magnesium sulfate, sodium sulfate, etc. According to a preferred exemplary embodiment, the desiccant is magnesium sulfate.

[0118] In this specification, the desiccant is added in sufficient quantities as is typically required for drying in the art.

[0119] According to an exemplary embodiment of this specification, step (s33) (filtration step) can be performed by methods known in the art. As a representative example, a method can be used to draw in air using an inhaler and filter out impurities containing desiccants, etc. (separated from the target product by a filter), or a method can be used to remove other impurities using a solvent that does not dissolve the target product but dissolves other impurities by utilizing differences in solubility in a particular solvent.

[0120] According to one exemplary embodiment of this specification, step (s34) (concentration step) can be performed by methods known in the art. As a representative example, this step can be performed by evaporating the solvent using a vacuum rotary evaporator, but the representative example is not limited thereto.

[0121] According to one exemplary embodiment of this specification, additional filtration and drying steps may be added after step (s34).

[0122] A drying step may be included prior to step (s35), and the drying step is the drying step of Formula 1. The drying step is different from step (s32) and can be carried out by methods known in the art, representative examples of which include vacuum oven drying, spray drying, rapid drying, etc., and preferably, the compound of Formula 1 can be dried by vacuum oven drying.

[0123] According to an exemplary embodiment of this specification, step (s35) (the obtaining step) is the step of obtaining the compound of chemical formula 1 that was concentrated (dried) in step (s34).

[0124] According to an exemplary embodiment of this specification, in the obtaining step, steps (s32) to (s33) may be performed three or more times if necessary.

[0125] According to one exemplary embodiment of this specification, a mixture comprising two or more of the said compounds is provided.

[0126] According to another exemplary embodiment of this specification, the mixture contains two or more compounds that are the same as or different from each other. That is, this means that the two or more compounds are the same as or different from each other while having the structure of Formula 1.

[0127] According to yet another exemplary embodiment of this specification, the mixture may also contain compounds different from those of Formula 1.

[0128] According to one exemplary embodiment of this specification, a single molecule derived from the compound is provided.

[0129] In this specification, for example, the phrase "monomer derived from a compound of formula 1" may mean a monomolecule in which the vinyl group of a compound of formula 1 forms a free radical and introduces additional substituents, or the compound of formula 1 itself.

[0130] According to one exemplary embodiment of this specification, a polymer comprising monomers derived from said compound is provided.

[0131] Those skilled in the art will understand the term "monomer" as described in this specification to mean the state in which a compound is polymerized to attach to the main chain of a polymer.

[0132] In this specification, for example, "monomer derived from a compound of Formula 1" is a repeating unit constituting the main chain of a polymer, and means that the vinyl group of a compound of Formula 1 can form a free radical to become a monomer, and can be introduced into monomers or end groups constituting the main chain of other polymers.

[0133] According to one exemplary embodiment of this specification, the polymer may also contain additional monomers, and there are no limitations on the additional monomers.

[0134] According to one exemplary embodiment of this specification, the polymer can be an alternating polymer or a random polymer, but is not limited thereto.

[0135] Furthermore, in this specification, even when referring to monomers contained in the polymer, the monomers are not limited to those mentioned, and may include other monomers besides those mentioned as comonomers without departing from the purpose of the invention.

[0136] According to an exemplary embodiment of this specification, a resin composition comprising the said compound and monomers and polymers derived therefrom is provided.

[0137] Compounds according to one exemplary embodiment of this specification, as well as monomolecules and polymers derived therefrom, are used as electronic materials, organic insulating materials and / or substrate materials, but are not limited thereto.

[0138] The compounds according to an exemplary embodiment of this specification, as well as the monomers and polymers derived therefrom, can be used as semiconductor copper clad laminate (CCL) materials. Specifically, representative materials used in semiconductor CCL materials include a variety of monomers and polymers having styrene groups, monomers and polymers having bismaleimide groups, etc.

[0139] The bismaleimide group has a structure similar to that of maleic anhydride, and in fact, it is well known that the styrene group forms alternating copolymers very efficiently when polymerized with the bismaleimide group. This is because the transition state, in the form of non-bonded resonance including electron transfer, is stabilized through polar effect charge transfer interactions.

[0140] Therefore, compounds of Formula 1 containing perfluoroalkyl groups with relatively high dielectric constants are expected to induce thermosetting networks more effectively during curing than compounds in the related field. For this reason, no additional new additives are needed, and the dielectric constant of existing insulating layers can be effectively reduced without separation from existing materials.

[0141] Invention Embodiments

[0142] In the following, this specification will be described in detail with reference to embodiments used to specifically describe this specification. However, modifications can be made in various forms according to embodiments of this specification, and this should not be construed as limiting the scope of this specification to the embodiments described in detail below. Embodiments of this specification are provided to explain this specification more completely to those skilled in the art.

[0143] Example 1.

[0144] In a 100 mL double-necked round-bottom flask, 20.8 g of divinylbenzene, 6.9 mL of nonafluoro-1-iodobutane, and 10.8 mL of tributyltin hydride were dissolved in 40 mL of dichloromethane. The resulting mixture was bubbled under nitrogen at 30 °C for 30 minutes. After adding 0.37 g of 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (V-70), the mixture was stirred for 15 hours. The mixture was then diluted with 100 mL of dichloromethane, and the organic layer was washed with 100 mL of saturated KF solution, 100 mL of saturated NaCl solution, and 100 mL of water, and then dried over 10 g of MgSO4. After filtration and evaporation, 7.9 g of the following compound 1 was obtained.

[0145]

[0146] [Compound 1]

[0147] Example 2.

[0148] In a 100 mL double-necked round-bottom flask, 26.0 g of divinylbenzene, 10.7 mL of heptadecafluoro-n-octyl iodide, and 10.8 mL of tributyltin hydride were dissolved in 40 mL of dichloromethane. The resulting mixture was bubbled under nitrogen at 30 °C for 30 minutes. After adding 0.37 g of 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (V-70), the mixture was stirred for 15 hours. The mixture was then diluted with 100 mL of dichloromethane, and the organic layer was washed with 100 mL of saturated KF solution, 100 mL of saturated NaCl solution, and 100 mL of water, and then dried over 10 g of MgSO4.

[0149] After filtration and evaporation, 15.4 g of the following compound 2 was obtained.

[0150]

[0151] [Compound 2]

[0152] Table 1 below describes the amounts of vinyl and perfluoroalkyl groups in compounds 1 and 2 prepared from Examples 1 and 2.

[0153] [Table 1]

[0154]

[0155] According to Table 1, compounds of Formula 1 contain both vinyl and perfluoroalkyl groups in one molecule, and therefore can be used as monomers to prepare polymers. It can be seen from this that compounds of Formula 1 can be used to prepare polymers containing perfluoroalkyl groups.

Claims

1. A method for preparing a compound selected from any of the following: The method includes: (s1) Introduce the following chemical formulas A and C n F 2n+1 X, trialkyltin hydride and solvent, and the resulting mixture was stirred under nitrogen; and (s2) Add a free radical initiator to the mixture and stir, wherein the free radical initiator is an azo initiator: [Chemical Formula A] In step (s1), in chemical formula A, -C n F 2n+1 For –C4F9, -C6F 13 or -C8F 17 , R2 is hydrogen. r2 is an integer 4, and X is a halogen group.

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