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

Abstract

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

Description

Technical Field

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2021-0154715, filed with the Korean Intellectual Property Office on November 11, 2021, and all of its content is incorporated herein by reference.

[0002] This specification relates to a compound, a method for producing the same, and a single molecule and a polymer derived from the compound.

Background Art

[0003] Conventionally, in order to introduce a perfluoroalkyl group into an aromatic compound, a nucleophilic aromatic substitution reaction using a Grignard reagent and a halogenated benzene or its derivative, or a nucleophilic substitution reaction using a reaction in the reverse direction thereof has been used. In this case, however, it is necessary to use a Grignard reagent that is difficult to handle, a large amount of halogen compounds must be used, and the reaction has the disadvantages of being sensitive to air and moisture, making it difficult to develop.

Summary of the Invention

Problems to be Solved by the Invention

[0004] This specification provides a compound, a method for producing the same, and a single molecule and a polymer derived from the compound.

Means for Solving the Problems

[0005] One embodiment of this specification provides a compound of Chemical Formula 1 below. [Chemical Formula 1]

Chem.

[0006] One embodiment of the present specification provides a method for producing a compound of the following Chemical Formula 1, including (s1) a step of introducing F, trialkyltinhydride, and a solvent and stirring under nitrogen gas; and (s2) a step of introducing a radical initiator and stirring. n F 2n+1 X, trialkyltinhydride, and a solvent are introduced and stirred under nitrogen gas; and (s2) a step of introducing a radical initiator and stirring. [Chemical Formula A] [Chemical formula] [Chemical Formula 1] [Chemical formula] In the step (s1), in Chemical Formula A and Chemical Formula 1, R1 is -C n F 2n+1 is, n is an integer from 1 to 20, R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, r2 is an integer from 1 to 4, when the r2 is 2 or more, the two or more R2s are the same as or different from each other, X is a halogen group.

[0007] According to one embodiment of the present specification, a mixture containing two or more of the above compounds is provided.

[0008] Another embodiment of the present specification provides a single molecule derived from the above compound.

[0009] One embodiment of the present specification provides a polymer containing monomers derived from the above compound.

Advantages of the Invention

[0010] The compound, the monomer and the polymer according to one embodiment of the present specification are used as electronic materials, organic insulating materials, and / or substrate materials.

[0011] The method for producing the compound according to one embodiment of the present specification has the advantage that it is carried out under conditions of a low reaction temperature. As a result, polymerization is suppressed and side reactions are reduced, so that the yield of the compound of the above Chemical Formula 1, which is the target compound, is increased.

[0012] The compound according to one embodiment of the present specification is used as a polyfunctional monomer and can exhibit the effects of low refractive index, low relative dielectric constant, low surface energy, and low dielectric tangent.

Brief Description of the Drawings

[0013]

Figure 1

Modes for Carrying Out the Invention

[0014] Hereinafter, the present specification will be described in more detail.

[0015] One embodiment of the present specification provides a compound of the following Chemical Formula 1. [Chemical Formula 1]

Chem.

[0016] Throughout this specification, the term "these combinations" included in the Markush-form expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-form expression, and means including one or more selected from the group consisting of the said components.

[0017] In this specification, examples of substituents are described below, but are not limited thereto.

[0018] In this specification,

Chemical formula

[0019] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted. When two or more substitutions are made, the two or more substituents may be the same as or different from each other.

[0020] In this specification, the term "substituted or unsubstituted" means being substituted by one or more substituents selected from the group consisting of deuterium; a halogen group; a hydroxy group; an ester group; an alkyl group; an alkoxy group; and an aryl group, or being substituted by a substituent in which two or more of the exemplified substituents are linked, or having no substituent at all.

[0021] In this specification, when two or more substituents are linked, it means that the hydrogen of any one substituent is linked to another substituent. For example, when two substituents are linked, it means that a phenyl group and a naphthyl group are linked,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0022] In this specification, examples of the halogen group include a fluoro group, a chloro group, a bromo group, or an iodo group.

[0023] In this specification, the ester group may have the oxygen of the ester group substituted by a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, or a cyclic alkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be any one of the following structural formulas, but is not limited thereto.

Chemical formula

[0024] In the above structure, R101 and R102 are the same as or different from each other, and each independently is a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted 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.

[0025] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include, but are not limited to, methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc.

[0026] In this specification, the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p-methylbenzyloxy group, etc. may be mentioned, but are not limited thereto.

[0027] According to one embodiment of this specification, n is an integer of 4 to 12.

[0028] According to one embodiment of this specification, R1 is -C 4 F 9 、-C 6 F 13 、-C 8 F 17 、or -C 12 F 25 .

[0029] According to one embodiment of this specification, when n is within the above range, since the chain length of the perfluoroalkyl group can be easily adjusted, compounds with various molecular weights can be produced. Further, when a perfluoroalkyl group is included, effects such as low refractive index, low relative permittivity, low surface energy, and low dielectric tangent can be exhibited. Specifically, in the case of conventional compounds containing a perfluoroalkyl group, they exhibit low dielectric constant and low refractive characteristics, but are not easy in terms of compatibility. However, when used as R1 in Chemical Formula 1 of the present application, it can maintain compatibility and exhibit effective effects of low refractive index, low relative permittivity, low surface energy, and low dielectric tangent.

[0030] The compound of Chemical Formula 1 according to one embodiment of this specification can be used as a single molecule containing both a perfluoroalkyl group and a vinyl group for various applications such as electronic materials.

[0031] Also, since the compound of Chemical Formula 1 according to one embodiment of the present specification contains a perfluoroalkyl group and a vinyl group at the same time, it can be used as a monomer for producing a polymer and can be used when producing a polymer containing a perfluoroalkyl group.

[0032] According to one embodiment of the present specification, the R2 is hydrogen; an ester group; or a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted.

[0033] According to one embodiment of the present specification, the R2 is hydrogen; an ester group; or a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with one or more substituents selected from a hydroxy group, a linear or branched alkoxy group having 1 to 10 carbon atoms, and combinations thereof.

[0034] According to one embodiment of the present specification, the R2 is hydrogen; an ester group; a methyl group substituted with a hydroxy group; or a methyl group substituted with a linear or branched alkoxy group having 1 to 10 carbon atoms which is substituted with a linear or branched alkoxy group having 1 to 10 carbon atoms.

[0035] According to one embodiment of the present specification, the R2 is hydrogen; an ester group; a methyl group substituted with a hydroxy group; or a methyl group substituted with an ethoxy group substituted with a methoxy group.

[0036] According to one embodiment of the present specification, in the R2, the ester group is

Chemical formula

[0037] The R101 is a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted 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.

[0038] According to one embodiment of the present specification, the R101 is a methyl group; an ethyl group; a tert-butyl group; a methyl group substituted with a phenyl group; or an n-decyl group.

[0039] According to one embodiment of the present specification, the r2 is 4.

[0040] According to one embodiment of the present specification, the r2 is 2.

[0041] According to one embodiment of the present specification, the r2 is 1.

[0042] According to one embodiment of the present specification, the chemical formula 1 is any one selected from the following compounds.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0043] According to one embodiment of the present specification, the chemical formula 1 includes a mixture of the compounds of the chemical formula 1.

[0044] Specifically, the mixture of the compounds of the chemical formula 1 means that two or more of the chemical formula 1 are included, and their structures may be the same or different from each other.

[0045] One embodiment of the present specification is (s1) the following chemical formulas A, C n F 2n+1A step of introducing X, trialkyltinhydride, and a solvent and stirring under nitrogen gas; and (s2) a step of introducing a radical initiator and stirring, to provide a method for producing a compound of the following Chemical Formula 1. [Chemical Formula A] [Chemical Structure] [Chemical Formula 1] [Chemical Structure] In the step (s1), in Chemical Formula A and Chemical Formula 1, R1 is -C n F 2n+1 and n is an integer from 1 to 20, R2 is hydrogen; deuterium; a halogen group; an ester group; or a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, r2 is an integer from 1 to 4, when r2 is 2 or more, the two or more R2s may be the same as or different from each other, X is a halogen group.

[0046] According to one embodiment of the present specification, Chemical Formula 1 includes a mixture of the compounds of Chemical Formula 1.

[0047] Specifically, the mixture of the compounds of Chemical Formula 1 means that Chemical Formula 1 contains two or more kinds, and their structures may be the same as or different from each other.

[0048] According to one embodiment of the present specification, the reaction temperatures of the step (s1) and the step (s2) are 20°C to 40°C, preferably 25°C to 35°C, and more preferably 30°C.

[0049] When carried out at the above reaction temperature, the reaction conditions are mild, the polymerization of styrene of Chemical Formula A is suppressed, side reactions are reduced, and the yield of the final target product, the compound of Chemical Formula 1, is increased.

[0050] According to one embodiment of the present specification, the radical initiator is an azo initiator.

[0051] According to one embodiment of the present specification, the radical initiator is any one or more selected from azobisisobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), or di-tert-butyl peroxide (DTBP).

[0052] Preferably, the radical initiator is 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0053] When the radical initiator is used, it is possible to initiate a radical reaction at a low temperature, and there is an advantage that the reaction can be carried out under the above reaction temperature and mild reaction conditions.

[0054] According to one embodiment of the present specification, the trialkyltin hydride is tributyltin hydride.

[0055] The hydrogenated trialkyltin, as a hydrogen donor with low binding energy, induces HAT (Hydrogen Atom Transfer) to radicals generated from a small amount of radical initiator, and induces the introduction of a perfluoroalkyl group into the chemical formula A by an ATRA (Atom Transfer Radical Addition) reaction. The mechanism of the ATRA (Atom Transfer Radical Addition) reaction is as shown in Figure 1.

[0056] According to one embodiment of the present specification, the solvent is an organic solvent.

[0057] According to one embodiment of the present specification, the solvent is selected from hexane, 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 only, and conventional organic solvents may be used.

[0058] According to one embodiment of the present specification, the X is an iodine (I) group.

[0059] According to one embodiment of the present specification, after the step (s2), the method further includes the step of obtaining the compound of Chemical Formula 1.

[0060] The step of obtaining according to one embodiment of the present specification includes (s31) A quench and layer separation step; (s32) A drying step; (s33) A filtration step; (s34) A concentration step; and (s35) An obtaining step.

[0061] According to one embodiment of the present specification, the step (s31) (Quench and layer separation step) is a step of adding a reaction-terminating substance to terminate the reaction and separating the layers.

[0062] According to one embodiment of the present specification, the step (s31) is a step of adding the solvent used in the step (s1) to dilute the reactants, adding a reaction-terminating substance to terminate the reaction, and separating the layers.

[0063] According to one embodiment of the present specification, as the reaction-terminating substance in the step (s31), distilled water, aqueous ammonium chloride solution, aqueous sodium hydrogen carbonate solution, KF (saturated) aqueous solution, HCl aqueous solution, NaCl (saturated) aqueous solution, dichloromethane, ethyl acetate, etc. may be used, but are not limited thereto. Preferably, as the reaction-terminating substance, aqueous ammonium chloride solution, aqueous sodium hydrogen carbonate solution, NaCl aqueous solution, and ethyl acetate are used.

[0064] In the step (s31), the order in which the reaction is terminated and the layers are separated is not limited to a specific order. As one embodiment, the reaction may be terminated and the layers may be separated simultaneously. As another example, a reaction-terminating substance may be added to terminate the reaction, and then the layers may be separated. However, the order of progress is not limited to the examples described above.

[0065] According to one embodiment of the present specification, the step (s32) (drying step) is performed by adding a drying agent to any one of the layers of the substances separated in the step (s31). For example, when dichloromethane exemplified above is used as the reaction-terminating substance, it is performed by adding a drying agent to the lower dichloromethane layer, that is, the organic layer. Examples of the drying agent include, but are not limited to, magnesium sulfate, sodium sulfate, etc. According to a preferred embodiment, the drying agent is magnesium sulfate.

[0066] In the present specification, a drying agent is usually added in a sufficient amount necessary for drying in the art.

[0067] According to one embodiment of the present specification, the step (s33) (filtration step) may be performed by a method known in the art. As a typical example, a method of sucking air using an inhaler and filtering impurities including a desiccant separated from the target product through a filter, or a method of removing other impurities using a solvent in which the target product does not dissolve and other impurities dissolve by utilizing the difference in solubility in a specific solvent may be used.

[0068] According to one embodiment of the present specification, the step (s34) (concentration step) may be performed by a method known in the art. As a typical example, it may be performed by evaporating the solvent using a vacuum rotary evaporator, but is not limited thereto.

[0069] According to one embodiment of the present specification, an additional filtration and drying step may be added after the step (s34).

[0070] Before the step of obtaining (s35), a drying step may be included, and the drying step is a step of drying the chemical formula 1. Different from (s32), the drying step may be performed by a method known in the art. Typical examples include vacuum oven drying, spray drying, flash drying, etc., and preferably, it may be dried by vacuum oven drying.

[0071] According to one embodiment of the present specification, the step (s35) (acquisition step) is a step of obtaining the compound of the chemical formula 1 concentrated (dried) in the step (s34).

[0072] According to one embodiment of the present specification, in the step of obtaining, the steps (s32) to (s33) may be performed three or more times as necessary.

[0073] According to one embodiment of the present specification, a mixture containing two or more kinds of the compounds is provided.

[0074] According to another embodiment of the present specification, two or more compounds contained in the mixture may be the same as or different from each other. That is, it means having the structure of Chemical Formula 1 and being the same as or different from each other.

[0075] According to another embodiment of the present specification, the mixture may further contain a compound different from Chemical Formula 1.

[0076] According to one embodiment of the present specification, a single molecule derived from the compound is provided.

[0077] In the present specification, for example, the "single molecule derived from the compound of Chemical Formula 1" may mean a molecule in which a vinyl group of the compound of Chemical Formula 1 forms a radical and an additional substituent is introduced, or the compound of Chemical Formula 1 itself.

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

[0079] Those having ordinary knowledge in the art can understand that the term "monomer" described in the present specification refers to a state in which a compound polymerizes and is linked to the main chain of a polymer.

[0080] In the present specification, for example, the "monomer derived from the compound of Chemical Formula 1" means that as a repeating unit constituting the main chain in a polymer, a vinyl group of the compound of Chemical Formula 1 can form a radical to become a monomer, and monomers or end groups constituting the main chain of other polymers can be introduced.

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

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

[0083] Also, in this specification, when referring to the monomers contained in the polymer, it is not limited to containing only the monomers mentioned, and within the scope not departing from the object of the present invention, in addition to the monomers mentioned above, other monomers may be further included as comonomers.

[0084] According to one embodiment of this specification, a resin composition containing the compound, the monomer and polymer derived therefrom is provided.

[0085] The compound, the monomer and polymer derived therefrom according to one embodiment of this specification are used as electronic materials, organic insulating materials, and / or substrate materials, and are not limited thereto.

[0086] The compound, the monomer and polymer derived therefrom according to one embodiment of this specification can be used as a semiconductor CCL (Copper Clad Laminate) material. Specifically, typical materials used for semiconductor CCL materials include a plurality of monomers and polymers having a styrene group, monomers and polymers having a bismaleimide group, and the like.

[0087] The bismaleimide group is similar in structure to maleic anhydride. In fact, it is generally known that the styrene group forms an alternating copolymer very effectively with the bismaleimide group and the maleimide group during polymerization. This is because the transition state of the non-bonded resonance form including electron transfer is stabilized by the polar effect charge transfer interaction.

[0088] Therefore, the compound of Chemical Formula 1 containing a perfluoroalkyl group having non-dielectric rate characteristics is expected to be able to more effectively induce a thermoset network generated during curing than conventional compounds. As a result, without the need for additional new additives, the dielectric rate of a conventional insulating layer can be effectively reduced without phase separation from conventional substances.

Example

[0089] Hereinafter, examples will be given for a specific description of this specification and will be described in detail. However, the examples according to this specification may be deformed into various different forms, and the scope of this specification is not construed as being limited to the examples described below. The examples of this specification are provided to more fully explain this specification to those having average knowledge in the industry.

[0090] Example 1 In a 100 mL two-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, and then bubbled with nitrogen at 30 °C for 30 minutes. After adding 0.37 g of V-70 (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)), the mixture was stirred for 15 hours. Then, it was diluted with 100 mL of dichloromethane, and the organic layer was washed with 100 mL of a KF saturated solution, 100 mL of a NaCl saturated solution, and 100 mL of water, and then dried over 10 g of MgSO 4 After filtration and evaporation, 7.9 g of the following Compound 1 was obtained.

Chemical formula

[0091] Example 2 In a 100 mL two-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. Then, at 30 °C, nitrogen was bubbled through the solution for 30 minutes. To this solution, 0.37 g of V-70 (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)) was added, and the mixture was stirred for 15 hours. Thereafter, the solution was diluted with 100 mL of dichloromethane, and the organic layer was washed with 100 mL of a saturated KF solution, 100 mL of a saturated NaCl solution, and 100 mL of water. Then, it was dried over 10 g of MgSO 4 and filtered and evaporated to obtain 15.4 g of the following Compound 2. [Chemical formula] [Compound 2]

[0092] Table 1 below shows the amounts of vinyl groups and perfluoroalkyl groups in Compound 1 and Compound 2 produced from Example 1 and Example 2 above. [Table 1]

[0093] According to Table 1 above, since the compound of Chemical formula 1 contains both a vinyl group and a perfluoroalkyl group in one molecule, it can be used as a monomer for producing a polymer, and thus it can be seen that it can be used when producing a polymer containing a perfluoroalkyl group.

Claims

1. A compound, which is any one selected from the following compounds: [Chemical 2]

2. (S1) The following chemical formulas A and C ｎ F ２ｎ＋１ adding a trialkyltin hydride, X, and a solvent and stirring under nitrogen gas; and A production method of any one selected from the compounds of the following Chemical Formula 1, including the step of adding a (s2) radical initiator and stirring: [Chemical Formula A] 【Chemical 8】 [Chemical Formula 1] 【Chemical Formula 9】 In the said (s1) step, in Chemical Formula A, R2 is hydrogen, r2 is 4 and.

3. A mixture containing two or more of the compounds described in Claim 1.

4. A polymer containing a monomer derived from the compound described in Claim 1.

5. The polymer according to Claim 4, further containing an additional monomer.

6. A mixture containing the compound described in Claim 1 and any one or more selected from the following compounds: 【Chemical Formula 10】

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