Polyfunctional epoxy compound having plural liquid crystal cores and cured product produced from the same

Abstract

To provide a polyfunctional epoxy compound which is obtained by modifying two or more epoxide functional groups on a terminal site of a liquid crystal molecule synthesized by combining plural thermotropic liquid crystal substances, and a cured product produced by reacting the compound and a curing agent.SOLUTION: A polyfunctional epoxy compound is represented by the following chemical formula (II) (wherein, n is an integer of 1 to 30). The cured product facilitates interaction between liquid crystals and has high thermal conductivity, which is usable solely or in the form of a composite material as a heat dissipation polymer, and is applicable as a base resin of a composite material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polyfunctional epoxy compound obtained by modifying the terminal sites of liquid crystal molecules synthesized by combining multiple thermotropic liquid crystal substances with two or more epoxide functional groups, and a cured product produced by reacting the compound with a curing agent.More specifically, the present invention relates to a compound and a cured product that can be used alone as a heat-dissipating polymer or in the form of a composite material because of easy interaction between liquid crystals and high thermal conductivity, and can be used as a base resin for the composite material. [Background technology]

[0002] Epoxy resin is a thermosetting resin consisting of a network polymer formed by the ring-opening of epoxy groups that occurs when an epoxy compound with two or more epoxy groups in its molecule is mixed with a curing agent. Epoxy resin has excellent resistance to chemical components, excellent durability, and low volume shrinkage upon curing, making it an essential high-performance raw material used in all industrial fields, including adhesives, paints, electronics / electrical, civil engineering / construction, etc.

[0003] Currently, the most widely used method for increasing the thermal conductivity of epoxy resin is to create a composite by mixing thermally conductive fillers such as aluminum oxide and aluminum nitride. Composites manufactured in this way retain the advantages of existing epoxy resins while exhibiting relatively high thermal conductivity. However, due to the fixed physical properties of fillers, it is difficult to achieve higher thermal conductivity by simply increasing the filler content. In this case, an excessively high filler content can cause manufacturing difficulties or unexpected disadvantages in other physical properties. Therefore, research has been conducted to create composites with improved thermal conductivity without increasing the filler content by increasing the inherent thermal conductivity of not only the filler but also the epoxy resin.

[0004] The widely used diglycidyl ether of bisphenol A (DGEBA) epoxy resin is known to form a three-dimensional network cross-linked structure after curing. This three-dimensional structure has the advantage of giving the material excellent durability and corrosion resistance, but it is disadvantageous in terms of thermal conductivity due to the dominance of phonon scattering, which is known to play a role in heat transfer within polymers. In fact, cured DGEBA epoxy resins are known to exhibit low thermal conductivity of approximately 0.2 W / mK. Therefore, liquid crystalline epoxy resins are being researched to replace this three-dimensional structure with a more ordered one- or two-dimensional structure.

[0005] Meanwhile, research has been conducted into improving the physical properties of liquid crystalline epoxy compounds and their cured resins by introducing flexible groups into them. The introduction of flexible groups increases the solubility of the compounds, making them easier to handle during processing, controls the interactions between mesogens, thereby changing the temperature range in which liquid crystallinity appears, and alters the alignment morphology in the liquid crystal state. Furthermore, the reactivity of the epoxy groups can be adjusted to control the curing speed.

[0006] However, most of these compounds have a mesogen inside the compound with epoxy groups at both ends, which may be inefficient in improving the thermal conductivity that is the goal of introducing liquid crystalline epoxy compounds. Summary of the Invention [Problem to be solved by the invention]

[0007] The object of the present invention is to synthesize liquid crystal molecules by chemically modifying them by combining thermotropic liquid crystal substances, and to provide polyfunctional epoxy compounds whose terminals are modified with two or more epoxide functional groups.

[0008] Another object of the present invention is to provide a cured product produced by reacting the polyfunctional epoxy compound with a curing agent, which has high thermal conductivity and can be used as a heat-dissipating polymer and composite material.

[0009] The technical problems that the present invention aims to achieve are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by a person having ordinary skill in the art from the description of the present invention. [Means for solving the problem]

[0010] In order to achieve the above object, the present invention provides a multifunctional epoxy compound and a cured product produced therefrom.

[0011] The present invention provides a polyfunctional epoxy compound represented by the following chemical formula (I):

[0012] [ka]

[0013] (wherein n is an integer of 1 to 30).

[0014] The present invention provides a polyfunctionalized epoxy compound represented by the following chemical formula (II):

[0015] [ka]

[0016] (wherein n is an integer of 1 to 30).

[0017] The present invention provides a polyfunctionalized epoxy compound represented by the following chemical formula (III):

[0018] [ka]

[0019] (wherein n is an integer of 1 to 30).

[0020] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (I) with a curing agent.

[0021] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (II) with a curing agent.

[0022] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (III) with a curing agent.

[0023] The present invention also provides a cured epoxy resin product represented by the following chemical formula (IV):

[0024] [ka]

[0025] (wherein X and Y may be the same or different and are selected from the compounds of the above chemical formula (I) to chemical formula (III)).

[0026] The curing agent may be selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY).

[0027] The cured epoxy resin can be used for substrates, compounds, adhesives, pads, heat spreaders, and heat sinks.

[0028] All of the statements made about the polyfunctional epoxy compounds and cured epoxy resins prepared therefrom apply equally unless they contradict each other. [Effects of the Invention]

[0029] The novel epoxy resin and its cured product according to the present invention can be used alone or in the form of a composite material as a heat-dissipating polymer because they facilitate interaction between liquid crystals and have improved thermal conductivity.

[0030] The effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims. [Brief explanation of the drawings]

[0031]

Figure 1

Figure 2

Figure 3

[0032] The terms used in this specification are currently selected as widely used and general terms as possible, taking into consideration the functions of the present invention. However, they may differ depending on the intentions of those skilled in the art, precedents, or the emergence of new technologies. In addition, in certain cases, the applicant may arbitrarily select terms, and in such cases, their meanings will be described in detail in the description of the invention. Therefore, the terms used in this specification must be defined based on the meanings of the terms and the overall content of the present invention, rather than simply by the names of the terms.

[0033] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms as defined in commonly used dictionaries should be interpreted to have a meaning consistent with the meaning they have in the context of the relevant art, and should not be interpreted as having an ideal or overly formal meaning unless expressly defined in this application.

[0034] Numerical ranges are inclusive of the numerical values ​​defined in the range. Every maximum numerical limitation given herein includes every lower numerical limitation, as if such lower numerical limitation were expressly stated. Every minimum numerical limitation given herein includes every higher numerical limitation, as if such higher numerical limitation were expressly stated. Every numerical limitation given herein includes every finer numerical range within a broader numerical range, as if such narrower numerical limitations were expressly stated.

[0035] The present invention provides a polyfunctionalized epoxy compound represented by the following formula (I):

[0036] [ka]

[0037] (wherein n is an integer of 1 to 30).

[0038] The compound of formula (I) may be prepared starting from bis(4-hydroxyphenyl) 4,4'-(alkane-1,n-diylbis(oxy))dibenzoate.

[0039] The preparation of the compound of formula (I) may be carried out under basic conditions, for example in the presence of sodium hydroxide.

[0040] The reaction for producing the compound of formula (I) may be carried out at a temperature of 80 to 105°C, preferably 85 to 95°C.

[0041] The preparation time of the compound of formula (I) may be 0.5 to 4 hours, preferably 1 to 2 hours.

[0042] The preparation of the compound of formula (I) may be carried out in the presence of water or an alcohol, and the type of the alcohol is not particularly limited as long as it is known in the art.

[0043] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (I) with a curing agent.

[0044] The curing agent may be selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY).

[0045] The cured epoxy resin can be used in the fields of substrates, compounds, adhesives, pads, heat spreaders, and heat sinks.

[0046] The molar mixing ratio of the compound to the curing agent may be 1.5:1 to 4:1, preferably 1.5:1 to 2:1.

[0047] The cured product may be produced by a method such as hot press molding, injection molding, or roll molding, but is not limited to these.

[0048] The temperature for producing the cured product may be 100 to 150°C, preferably 120 to 150°C.

[0049] The time required to produce the cured product may be 0.5 to 1.5 hours, preferably 0.5 to 1 hour.

[0050] The glass transition temperature of the cured product may be measured by a differential scanning calorimeter and may be a temperature of 79 to 127°C.

[0051] The glass transition temperature may be inversely proportional to the chain length.

[0052] The present invention provides a multifunctional epoxy compound represented by the following formula (II):

[0053] [ka]

[0054] (wherein n is an integer of 1 to 30).

[0055] The compound of formula (II) may be prepared from bis(4-(((4-hydroxyphenyl)imino)methyl)phenyl)alkanedioate, which is prepared from bis(4-formylphenyl)alkanedioate as a starting material.

[0056] The bis(4-(((4-hydroxyphenyl)imino)methyl)phenyl)alkanedioate may be prepared in the presence of an alcohol, and the alcohol may be selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, and heptanol.

[0057] The bis(4-(((4-hydroxyphenyl)imino)methyl)phenyl)alkanedioates may be produced at a temperature of 50 to 80°C, preferably at a temperature of 65 to 75°C.

[0058] The preparation of the compound of formula (II) may be carried out in the presence of a solvent such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), N,N'-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), meta-cresol (m-cresol), or a mixture thereof.

[0059] The preparation of the compound of formula (II) may be carried out at a temperature of 75 to 100°C, preferably 85 to 95°C, for 0.5 to 1.5 hours, preferably 0.5 to 1 hour.

[0060] The compound of formula (II) may be washed with an alcohol selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, and heptanol.

[0061] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (II) with a curing agent.

[0062] The curing agent may be selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY).

[0063] The cured epoxy resin can be used in the fields of substrates, compounds, adhesives, pads, heat spreaders, and heat sinks.

[0064] The molar mixing ratio of the compound to the curing agent may be 1.5:1 to 4:1, preferably 1.5:1 to 2:1.

[0065] The cured product may be produced by a method such as hot press molding, injection molding, or roll molding, but is not limited thereto.

[0066] The temperature for producing the cured product may be 100 to 150°C, preferably 120 to 150°C.

[0067] The time required to produce the cured product may be 0.5 to 1.5 hours, preferably 0.5 to 1 hour.

[0068] The glass transition temperature of the cured product may be measured by a differential scanning calorimeter and may be a temperature of 90 to 123°C.

[0069] The glass transition temperature may be inversely proportional to the chain length.

[0070] The present invention provides a polyfunctionalized epoxy compound represented by the following formula (III):

[0071] [ka]

[0072] (wherein n is an integer of 1 to 30).

[0073] The compound of formula (III) may be prepared starting from bis(4'-(allyloxy)-[1,1'-biphenyl]-4-yl) alkanedioate.

[0074] The preparation of the compound of formula (III) may be carried out at a temperature of 50 to 80°C, preferably at a temperature of 55 to 65°C.

[0075] The preparation of the compound of formula (III) may be carried out in the presence of chloroform.

[0076] The preparation of the compound of formula (III) may be carried out in the presence of a solvent selected from the group consisting of acetone, chloroform, ethanol, methanol, and methylene chloride.

[0077] The present invention provides a cured epoxy resin product obtained by reacting the polyfunctional epoxy compound represented by the above chemical formula (III) with a curing agent.

[0078] The curing agent may be selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY).

[0079] The cured epoxy resin can be used in the fields of substrates, compounds, adhesives, pads, heat spreaders, and heat sinks.

[0080] The molar mixing ratio of the compound to the curing agent may be 1.5:1 to 4:1, preferably 1.5:1 to 2:1.

[0081] The cured product may be produced by a method such as hot press molding, injection molding, or roll molding, but is not limited thereto.

[0082] The temperature for producing the cured product may be 160 to 200°C, preferably 180 to 200°C.

[0083] The production time for the cured product may be 1 to 3.5 hours, preferably 1.5 to 2.5 hours.

[0084] The glass transition temperature of the cured product may be measured by a differential scanning calorimeter and may be a temperature of 125 to 150°C.

[0085] The cured product may be a cured epoxy resin product represented by the following chemical formula (IV):

[0086] [ka]

[0087] (wherein X and Y may be the same or different and are selected from the compounds of the above chemical formulae (I) to (III).)

[0088] The curing agent may be selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY).

[0089] <Example> Examples of the present invention will be described in detail below, but it is obvious that the present invention is not limited to the following examples.

[0090] The advantages and features of the present invention, as well as methods for achieving them, will become apparent from the following examples. However, the present invention is not limited to the following embodiments, and can be realized in various different forms. These examples are provided solely for the purpose of making the disclosure of the present invention complete and fully conveying the scope of the invention to those skilled in the art. The present invention is defined by the scope of the claims.

[0091] Example 1: Synthesis of EBH-n(Bis(4-(oxiran-2-ylmethoxy)phenyl)4,4′-(alkane-1,n-diylbis(oxy))dibenzoate)

[0092] The following reaction scheme 1 shows the synthesis process of EBH-n.

[0093] [ka]

[0094] 1) Synthesis of Bis(4-hydroxyphenyl)4,4'-(alkane-1,n-diylbis(oxy))dibenzoate (BPHn) represented by the following chemical formula 1:

[0095] [ka]

[0096] A) n = 4 4-Hydroxyphenyl-4-hydroxybenzoate (2.00 g, 8.67 mmol) and butane-1,4-diylbis(4-methylbenzenesulfonate) (Tos-4) (1.38 g, 3.47 mmol) were placed in a two-neck flask, and after purging with argon, 30 mL of anhydrous DMF and NaH (0.40 g, 4.34 mmol) were added. After stirring at 90 °C for 3 days, the solvent was removed and the resulting solid material was purified by silica column chromatography using a hexane:ethyl acetate (volume ratio 7:3) solution as a developing solvent. The yield was 67%. 1 H NMR (500MHz, DMSO-d6): δ=9.46(s,2H),8.05(d,J=9Hz,4H),7.12(d,J=9Hz,4H),7. 04(d,J=8.5Hz,4H),6.80(d,J=9Hz,4H),4.07-4.09(m,4H),1.37-1.38(m,4H)ppm.

[0097] B) n = 6 The synthesis was carried out in the same manner as in A), except that Tos-6 was used instead of Tos-4. *Tos-n; Alkane-1-n-diylbis(4-methylbenzenesulfonate) 1 H NMR(500MHz,DMSO-d6):δ=8.04(d,J=9Hz,9.46(s,2H),7.10(d,J=9Hz,4H),7.03(d, J=9Hz,4H),6.80(d,J=9Hz,4H),4.11(t,J=6Hz,4H),1.79-1.80(m,4H),1.50(s,4H).

[0098] C) n = 8 The synthesis was carried out in the same manner as in A), except that Tos-8 was used instead of Tos-4. 1H NMR(500MHz,DMSO-d6):δ=9.46(s,2H),8.04(d,J=9Hz,4H),7.10(d,J=9Hz,4H),7.02(d,J=9Hz,4H) ,6.79(d,J=9Hz,4H),4.07-4.09(m,4H),1.75-1.743(m,4H),1.41-1.43(m,4H),1.37-1.38(m,4H).

[0099] 2) Synthesis of Bis(4-(oxiran-2-ylmethoxy)phenyl)4,4'-(alkane-1,n-diylbis(oxy))dibenzoate (EBH-n) represented by the following chemical formula 2:

[0100] [ka]

[0101] D) n = 4 BPH4 (3.00 g, 5.83 mmol) and benzyltrimethylammonium bromide (0.30 g) were placed in a two-neck flask, and after replacing the atmosphere with argon, 20 mL of epichlorohydrin was added. Sodium hydroxide (0.48 g, 11.66 mmol) was then dissolved in 5 mL of distilled water and added to the flask. The reaction was allowed to proceed at 90°C for 1 hour, after which the residual solvent was removed using a vacuum rotary evaporator. The resulting solid material was dissolved in acetone and purified by reprecipitation twice with distilled water, yielding EBH-4 as a white solid in 97% yield. 1H NMR(500MHz,CDCl3):δ=8.14(d,J=8.5Hz,4H),7.12(d,J,=9Hz,4H),6.96(d,J=8.5Hz,8H),4.25(dd,J=3.5Hz,1.5Hz,2H),4. 08(t,J=6.5Hz,4H),3.98(dd,J=6Hz,2Hz,2H),3.37-3.35(m,2H),2.93(t,J=4.5Hz,2H),2.78(m,2H),2.05(t,J=3Hz,4H)ppm. 13 C NMR(125MHz,CDCl3):δ=165.19,163.24,156.16,145.01,132.29,122.63,121 .93,115.38,114.28,69.28,67.71,50.13,44.72,25.87ppm.MS(+ESI):calcd for[C 36 H 34 O 10 +H] + :m / z627;found:m / z6

[0102] E) n = 6 The differences between BPH4 and BPH6 are shown in D) and in the right direction. 1 H NMR(500MHz,CDCl3):δ=8.13(d,J=8.5Hz,4H),7.11(d,J=9Hz,4H),6.96(d,J=8.5Hz,8H),4.24(dd,J=3Hz,1.5Hz,2H),4.08(t,J=6.5H). z,4H), 3.98(dd,J=5.5Hz,2Hz,2H),3.37(m,2H),2.92(t,J=4.5Hz,2H),2.77(m,2H),1.89(t,J=6.5Hz,4H),1.59(t,J=3.5Hz,4H)ppm. 13 C NMR(125MHz,CDCl3):δ=165.22,163.41,156.14,145.02,132.25,122.64,121.72 ,115.38,114.29,69.28,68.10,50.13,44.73,29.05,25.81ppm.MS(+ESI):calcd for[C 38 H 38 O 10 +H]+ :m / z655;found:m / z655.

[0103] F) n = 8 Synthesis was performed in the same manner as in D) except that BPH8 was used instead of BPH4. 1 H NMR (500MHz, CDCl3): δ=8.13(d,J=9Hz,4H),7.12(d,J=9Hz,4H),6.96(d,J=8.5,8H),4.23(dd,J=3Hz,1.5Hz,2H),4.06(t,J=6.5Hz) ,4H),3.98(dd,J=5.5Hz,2Hz,2H),3.37(m,2H),2.92(t,J=5Hz,2H),2.77(m,2H),1.85(t,J=7Hz,4H),1.50(m,4H),1.42(m,4H)ppm. 13 C NMR(125MHz,CDCl3):δ=165.23,163.23,156.13,145.03,132.24,122.64,121.68,115.37,114.29ppm.MS(+ESI):calcd for[C 40 H 42 O 10 +H] + :m / z683;found:m / z683.

[0104] Example 2: Synthesis of EIM-n(Bis(4-(((4-(oxiran-2-ylmethoxy)phenyl)imino)methyl)phenyl)alkanedioate) The following reaction scheme 2 shows the synthesis process of EIM-n.

[0105] [ka]

[0106] 1) Synthesis of Bis(4-formylphenyl)alkanedioate (EB-n) represented by the following chemical formula 3

[0107] [ka]

[0108] A) n = 4 4-Hydroxyphenylbenzaldehyde (3.05 g, 25.0 mmol) was placed in a two-neck flask. After purging with argon, 3.5 ml of triethylamine and 100 ml of anhydrous CHCl were added and stirred until a homogeneous solution was obtained. Then, 30 ml of anhydrous CHCl containing 1.82 ml (12.5 mmol) of hexanediol dichloride was added dropwise while refluxing for 3 hours. The resulting solution was extracted three times with saturated sodium bicarbonate solution to remove impurities, then concentrated and purified by silica column chromatography using a chloroform:ethyl acetate (volume ratio 11:1) solution as a developing solvent. 3.69 g of EB-4 was obtained in an 85% yield. 1 H NMR(500MHz,CDCl3):δ=10.00(s,2H(C H O-Ar)),7.92(d,J=8.6Hz,4ArH),7.28(d,J=8.6Hz,4ArH),2,69(t,J=7.4Hz,4H(-CO-C H 2-CH2-)),1.91(q,J1=3Hz,J2=4Hz,4H(-COCH2-C H 2-)).

[0109] B) n = 6 The synthesis was carried out in the same manner as in A) except that octanediol dichloride was used instead of hexanediol dichloride. The yield was 89%. 1 H NMR(500MHz,CDCl3):δ=10(s,2H(C H O-Ar)),7.92(d,J=8.6Hz,4ArH),7.27(d,J=8.6Hz,4ArH),2,62(t,J=7.4Hz,4H(-CO-C H 2-CH2-CH2)), 1.80(quintet,J 1= 7.5Hz, J2=7.5Hz, 4H(-COCH2-C H2-CH2-)),1.507(quintet,J1=4Hz,J2=4,4H(-CO-CH2-CH2-C H 2-)).

[0110] C) n = 8 The synthesis was carried out in the same manner as in A) except that decanediol dichloride was used instead of hexanediol dichloride. The yield was 86%. 1 H NMR(500MHz,CDCl3):δ=10(s,2H(C H O-Ar)),7.91(d,J=9Hz,4ArH),7.27(d,J=8.6Hz,4ArH),2,59(t,J=7.4Hz,4H(-CO-C H 2-CH2-CH2-CH2-)),1.77(quintet,J1=7.5Hz,J2=7.5Hz,4H(-CO-CH2-C H 2-CH2-CH2-)),1.41-149(m,8H(-CO-CH2-CH2-C H 2-CH2-)),1.36-1.44(m,8H(-CO-CH2-CH2-CH2-C H 2-)).

[0111] 2) Synthesis of bis(4-(((4-hydroxyphenyl)imino)methyl)phenyl)alkanedioate [Bis(4-(((4-hydroxyphenyl)imino)methyl)phenyl)alkanedioate; IM-n] of the following chemical formula 4

[0112] [ka]

[0113] D) n = 4 4-Aminophenol (4.80 g, 44 mmol) was dissolved in 250 mL of absolute ethanol in a 1 L three-neck round-bottom flask, and EB-4 (22 mmol) and 250 mL of absolute ethanol were added to a separate 500 mL round-bottom flask to prepare a homogeneous solution. The two solutions were then mixed and reacted under reflux for 30 minutes, then cooled to room temperature. The resulting crystals were washed three times with cold ethanol and then recovered. The recovered amount was 10.9 g, representing a yield of 92%. 1 H NMR(500MHz,DMSO-d6):δ=9.52(s,2H(O H -Ar), 8.61(s, 2H(Ar-C H =N-Ar)),7.94(d,J=9Hz,4ArH),7.27(d,J=8.6Hz,4ArH),7.20(d,J=9Hz,4ArH),6.80(d,J=8.6Hz,4ArH),2.70(t,J=6Hz,4H(-CO-C H 2-CH2-)),1.74-1.82(m,4H(-CO-CH2-C H 2-)).

[0114] E) n = 6 The synthesis was carried out in the same manner as in D), except that EB-6 was used instead of EB-4. The yield was 95%. 1 H NMR(500MHz,DMSO-d6):δ=9.55(s,2H(O H -Ar), 8.61(s, 2H(Ar-C H =N-Ar)),7.94(d,J=9Hz,4ArH),7.26(d,J=8.6Hz,4ArH),7.20(d,J=8.6Hz,4ArH),6.80(d,J=9Hz,4ArH),2.64(t,J=7.5Hz,4H(-CO-C H 2-CH2-CH2-)),1.65-1.73(m,4H(-CO-CH2-C H 2-CH2-)),1.41-1.48(m,4H(-CO-CH2-CH2-C H 2-)).

[0115] F) n = The synthesis was carried out in the same manner as in D) except that EB-8 was used instead of EB-4. The yield was 94%. 1 H NMR(500MHz,DMSO-d6):δ=9.55(s,2H(O H -Ar), 8.61(s, 2H(Ar-C H =N-Ar)),7.93(d,J=9Hz,4ArH),7.25(d,J=8.6Hz,4ArH),7.20(d,J=8.6Hz,4ArH),6.80(d,J=8.6Hz,4ArH),2.61(t,J=7.5Hz,4H(-CO-C H 2-CH2-CH2-CH2-)),1.67(quintet,J1=7.3Hz,J2=7.3Hz,4H(-CO-CH2-C H 2-CH2-CH2-)),1.39-1.44(m,4H(-CO-CH2-CH2-C H 2-CH2-)),1.32-1.35(m,4H(-CO-CH2-CH2-CH2-C H 2-)).

[0116] 3) Synthesis of (Bis(4-(((4-(oxiran-2-ylmethoxy)phenyl)imino)methyl)phenyl)alkanedioate; EIM-n) represented by the following chemical formula 5

[0117] [ka]

[0118] ​ IM-4 (4.02 g, 7.5 mmol) and benzyltrimethylammonium bromide (0.4 g) were dissolved in 40 ml of anhydrous DMF, and 55 ml of epichlorohydrin was added. The mixture was then reacted at 90°C for 1 hour. After cooling to room temperature, the resulting solution was precipitated in 300 ml of methanol, and the resulting white solid was collected by filtration. The resulting solid was washed several times with methanol and distilled water, and after drying, its weight was 2.04 g, giving a yield of 42%. 1 H NMR(500MHz,CDCl3):δ(ppm)=8.38(s,2H(Ar-C H =N-Ar)),7.84(d,J=8.6Hz,4ArH),7.20(d,J=9.0Hz,4ArH),7.10(d,J=9.0Hz,4ArH),7.0 0(d,J=8.6Hz,4ArH),4.31(dd,J1=11.0Hz,J2=3.1Hz,2H),4.02(dd,J1=11.0Hz,J2=5.8Hz ,2H),3.39(ddt,J1=5.8Hz,J2=4.1Hz,J3=2.9Hz,2H),2.94(dd,J1=4.9Hz,J2=4.1Hz,2H), 2.79(dd,J1=4.9Hz,J2=2.6Hz,2H),2.66(q,J1=6.1Hz,J2=4.2Hz,4H),1.88-1.94(m,4H). 13 C NMR(500MHz,CDCl3):δ(ppm):171.86( C =O),161.11(- C =N),159.70,148.51,121.73,114.80(-O- Ar -N=)149.85,130.56,129.60,122.12( Ar O-), 68.82(- C H2-O), 49.96 (oxirane ring C H), 44.61 (oxirane ring C H2), 33.96(-CO- C H2- C H2-), 24.29(-CO-CH2- C H2-).MS(+ESI):calcd for[C 38 H 36 N2O8+2H] 2+ :m / z650;found:m / z650.

[0119] ​ The synthesis was carried out in the same manner as in G), except that IM-6 was used instead of IM-4. The yield was 44%. 1 H NMR(500MHz,CDCl3):δ(ppm)=8.37(s,2H(Ar-C H=N-Ar)),7.84(d,J=9.0Hz,4ArH),7.20(d,J=9.0Hz,4ArH),7.09(d,J=9.0Hz,4ArH),7.00(d, J=8.6Hz,4ArH),4.31(dd,J1=11.0,J2=3.0Hz,2H),4.01(dd,J1=11.0Hz,J2=5.7Hz,2H),3.39 (ddt,J1=5.7Hz,J2=4.2Hz,J3=2.9Hz,1H),2.93(dd,J1=4.9Hz,J2=4.1Hz,1H),2.79(dd,J1=4 .9Hz,J2=2.6Hz,1H),2.59(t,J=7.4Hz,2H),1.81(dq,J1=11.5Hz,J2=7.1Hz,2H),1.51(m,4H). 13 CNMR(500MHz,CDCl3):δ(ppm):172.25( C =O),161.09(- C =N),159.69,148.57,121.71,114.79(-O- Ar -N=),149.73,130.55,129.55,122.13( Ar O-), 68.80(- C H2-O), 49.95 (oxirane ring C H), 44.58 (oxirane ring C H2), 34.22(-CO- C H2-), 28.68(-CO-CH2- C H2-), 24.68(-CO-CH2-CH2- C H2-).MS(+ESI):calcd for[C 40 H 40 N2O8+2H] 2+ :m / z678;found:m / z678.

[0120] ​

[0121] The synthesis was carried out in the same manner as in G), except that IM-8 was used instead of IM-4. The yield was 45%. 1 H NMR(500MHz,CDCl3):δ(ppm)=8.37(s,2H(Ar-C H=N-Ar)),7.84(d,J=9.0Hz,4ArH),7.19(d,J=9.0Hz,4ArH),7.09(d,J=9.0Hz,4ArH),7.00(d ,J=8.6Hz,4ArH),4.31(dd,J1=11.1Hz,J2=3.1Hz,2H),4.02(dd,J1=11.0Hz,J2=5.7Hz,2H), 3.39(ddt,J1=5.8Hz,J2=4.2Hz,J3=2.8Hz,2H),2.93(dd,J1=4.9Hz,J2=4.1Hz,2H),2.79(dd ,J1=4.9Hz,J2=2.6Hz,2H),2.57(t,J=7.5Hz,4H),1.77(q,J=7.4Hz,4H),1.38-1.48(m,8H). 13 CNMR(500MHz,CDCl3):δ(ppm):172.36( C =O),161.08(- C =N),159.62,148.60,121.70,114.79(-O- Ar -N=),149.74,130.54,129.59,122.13( Ar O-), 68.80(- C H2-O), 49.95 (oxirane ring C H), 44.59 (oxirane ring C H2), 34.33(-CO- C H2-), 29.03(-CO-CH2- C H2-), 28.99(-CO-CH2-CH2- C H2-), 24.87(-CO-CH2-CH2-CH2- C H2-).MS(+ESI):calcd for[C 42 H 44 N2O8+2H] 2+ :m / z706;found:m / z706.

[0122] Example 3: Synthesis of EBP-n (Bis(4'-(oxiran-2-ylmethoxy)-[1,1'-biphenyl]-4-yl) alkanedioate) The following reaction scheme 3 shows the synthesis process of EBP-n.

[0123] [ka]

[0124] 1) Synthesis of Bis(4'-(allyloxy)-[1,1'-biphenyl]-4-yl) alkanedioate (ABP-n) of the following formula 6

[0125] [ka]

[0126] ​ 4'-(allyloxy)-[1,1'-biphenyl]-4-ol (3.00 g, 13.3 mmol) was placed in a two-neck flask. After purging with argon, 5 mL of triethylamine and 100 mL of anhydrous CHCl3 were added and stirred until a homogeneous solution was obtained. Then, 0.97 mL (6.65 mmol) of hexanediol dichloride was added dropwise and the mixture was refluxed at 60°C for 5 hours. The resulting solution was extracted three times with saturated sodium bicarbonate solution to remove impurities, then concentrated and purified by silica column chromatography using a chloroform:ethyl acetate (volume ratio 19:1) solution as a developing solvent. 1.6 g of ABP-4 was obtained in a 43% yield. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=8.5Hz,4Ar H ), 7.48(d, J=9.0Hz, 4Ar H ), 7.14(d, J=8.5Hz, 4Ar H ), 6.98(d, J=9Hz, 4Ar H ),6.08(ddt,J1=17.3,J2=10.6Hz,J3=5.3Hz,2H,CH2=C H -O-),5.44(dq,J1=17.2Hz,J2=1.7Hz,2H,C H 2=CH-O-),5.31(dq,J1=10.5,J2=1.4Hz,2H,C H2=CH-O-),4.58(dt,J1=5.3,J2=1.6Hz,4H,Ar-OC H 2-), 2.63-2.70(m,4H,-CO-C H 2-), 1.89-1.95(m,4H,-COCH2-C H 2-).

[0127] ​ The synthesis was carried out in the same manner as in A) except that octanediol dichloride was used instead of hexanediol dichloride. The yield was 46%. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=8.5Hz,4Ar H ), 7.48(d, J=9.0Hz, 4Ar H ), 7.12(d, J=8.5Hz, 4Ar H ), 6.98(d, J=9Hz, 4Ar H ),6.08(ddt,J1=17.3,J2=10.5Hz,J3=5.3Hz,2H,CH2=C H -O-),5.44(dq,J1=17.2Hz,J2=1.6Hz,2H,C H 2=CH-O-),5.31(dq,J1=10.5,J2=1.4Hz,2H,C H 2=CH-O-),4.58(dt,J1=5.3,J2=1.6Hz,4H,Ar-OC H 2-), 2.60(t, J=7.4Hz, 4H, -CO-C H 2-), 1.79-1.84(m,4H,-CO-CH2-C H 2-),1.48-1.55(m,4H,-CO-CH2-CH2-C H 2-).

[0128] ​ The synthesis was carried out in the same manner as A) except that nonanediol dichloride was used instead of hexanediol dichloride. The yield was 81%. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=8.5Hz,4Ar H), 7.47(d, J=8.5Hz, 4Ar H ), 7.12(d, J=8.5Hz, 4Ar H ), 6.98(d, J=8.5Hz, 4Ar H ),6.08(ddt,J1=17.3,J2=10.5Hz,J3=5.3Hz,2H,CH2=C H -O-),5.44(dq,J1=17.2Hz,J2=1.6Hz,2H,C H 2=CH-O-),5.31(dq,J1=10.5,J2=1.4Hz,2H,C H 2=CH-O-),4.58(dt,J1=5.3,J2=1.5Hz,4H,Ar-OC H 2-), 2.59(t, J=7.4Hz, 4H, -CO-C H 2-),1.79(q,J=7.3Hz,4H,-CO-CH2-C H 2-),1.44-1.53(m,6H,-CO-CH2-CH2-C H 2-C H 2-).

[0129] ​ The synthesis was carried out in the same manner as in A) except that decanediol dichloride was used instead of hexanediol dichloride. The yield was 44%. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=8.5Hz,4Ar H ), 7.48(d, J=8.5Hz, 4Ar H ), 7.12(d, J=9.0Hz, 4Ar H ), 6.98(d, J=8.5Hz, 4Ar H ),6.08(ddt,J1=17.2,J2=10.5Hz,J3=5.3Hz,2H,CH2=C H -O-),5.44(dq,J1=17.3Hz,J2=1.7Hz,2H,C H 2=CH-O-),5.31(dq,J1=10.5,J2=1.4Hz,2H,C H 2=CH-O-),4.58(dt,J1=5.3,J2=1.5Hz,4H,Ar-OC H2-), 2.58(t, J=7.5Hz, 4H, -CO-C H 2-),1.78(q,J=7.4Hz,4H,-CO-CH2-C H 2-),1.38-1.46(m,8H,-CO-CH2-CH2-C H 2-C H 2-).

[0130] 2) Synthesis of Bis(4'-(oxiran-2-ylmethoxy)-[1,1'-biphenyl]-4-yl)alkanedioate (EBP-n) represented by the following formula 7:

[0131] [ka]

[0132] ​ ABP-4 (2.0 g, 3.56 mmol) was placed in a 500 mL three-necked round-bottom flask, and 100 mL of anhydrous CHCl3 was added and stirred to produce a homogeneous solution. Next, 4.92 g of m-CPBA was added and the mixture was refluxed for 10 hours. The organic phase was washed three times each with saturated aqueous NaHSO3 and NaHCO3, then concentrated. The resulting solid was purified by silica column chromatography using a chloroform:ethyl acetate (volume ratio 13:1) solution as a developing solvent. 1.28 g of EBP-4 was obtained, a yield of 60%. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=8.5Hz,4Ar H ), 7.49(d, J=9Hz, 4Ar H ), 7.14(d, J=9.0Hz, 4Ar H ), 6.99(d, J=8.5Hz, 4Ar H ),4.26(dd,J1=11.0Hz,J2=3.2Hz,2H,ArO-C H 2),4.01(dd,J1=11.0Hz,J2=5.6Hz,2H,ArO-C H2), 3.38 (ddt, J1 = 5.8, J2 = 4.1 Hz, J3 = 2.9 Hz, 2H, C of oxirane ring H ), 2.93 (dd, J1 = 4.9 Hz, J2 = 4.1 Hz, 2H, C of oxirane ring H 2), 2.78 (dd, J1 = 4.9 Hz, J2 = 2.7 Hz, 2H, C of oxirane ring H 2), 2.63-2.71(m,4H,-CO-C H 2-),1.92(q,J=3.7Hz,4H,-CO-CH2-C H 2-).

[0133] ​ The synthesis was carried out in the same manner as in E), except that ABP-6 was used instead of ABP-4. The yield was 62%. 1 H NMR(500MHz, CDCl3):δ(ppm)=7.53(d,J=9.0Hz,4Ar H ), 7.48(d, J=8.5Hz, 4Ar H ), 7.12(d, J=8.5Hz, 4Ar H ), 6.99(d, J=8.5Hz, 4Ar H ),4.26(dd,J1=11.0Hz,J2=3.2Hz,2H,ArO-C H 2),4.01(dd,J1=11.0Hz,J2=5.6Hz,2H,ArO-C H 2), 3.38 (ddt, J1 = 5.8, J2 = 3.8 Hz, J3 = 2.7 Hz, 2H, C of oxirane ring H ), 2.93 (dd, J1 = 4.9 Hz, J2 = 4.1 Hz, 2H, C of oxirane ring H 2), 2.78 (dd, J1 = 4.9 Hz, J2 = 2.6 Hz, 2H, C of oxirane ring H 2), 2.60(t, J=7.5Hz, 4H, -CO-C H 2-), 1.48-1.55(m,8H,-CO-CH2-C H 2-C H 2-).

[0134] Test Example 1 - Phase transition characteristics The phase transition phenomena were investigated using a PerkinElmer DSC4000 differential scanning calorimeter and an Olympus BX53-P polarizing microscope.

[0135] Tables 1 to 3 show the DSC measurement results for EBH-n, EIM-n, and EBP-n, respectively. Referring to these, they show typical thermotropic liquid crystal phase transition phenomena on both heating and cooling, and the transition temperature decreases as the chain length increases, except for EBP-7.

[0136] [Table 1]

[0137] [Table 2]

[0138] [Table 3]

[0139] Production Example 1 - Production of EBH-n cured product of Example 1

[0140] [ka]

[0141] The molar ratio of epoxy resin to curing agent 4,4'-diaminodiphenylmethane was set to 2:1 to make the epoxide equivalent and amine equivalent equal, and the two solid materials were ground and mixed at room temperature. The curing temperature was 130°C and the curing time was 1 hour.

[0142] Test Example 2: Physical properties of EBH-n cured product The glass transition temperatures of the cured materials were measured using a differential scanning calorimeter, the decomposition temperatures using a TA Q500 thermogravimetric analyzer, and the thermal conductivity using a Hotdisk TPS2500S thermal conductivity analyzer. The results are shown in Table 4. The glass transition temperatures of the cured materials ranged from 79 to 127°C and tended to decrease with increasing chain length. The 5% weight loss temperatures ranged from 329 to 337°C, and the 10% weight loss temperatures ranged from 339 to 346°C. There was no significant difference, but they increased slightly with increasing chain length. Thermal conductivities ranged from 0.38 to 0.48 W / m·K, with no particular trends observed. However, the highest thermal conductivity was observed for EBH-8, which has a liquid crystal phase at the curing temperature within the liquid crystal temperature range of the monomer. This confirmed a correlation between the formation of a liquid crystal phase and thermal conductivity values.

[0143] [Table 4]

[0144] Preparation Example 2: Preparation of cured EIM-n product of Example 2

[0145] [ka]

[0146] The molar ratio of epoxy resin to 4,4'-diaminodiphenylmethane was set to 2:1 to ensure equal epoxide and amine equivalents. The two solid materials were ground and mixed at room temperature, and then the cured product was produced using a hot press molding method. The curing temperature was 130°C and the curing time was 1 hour.

[0147] Test Example 3: Physical properties of cured EIM-n The glass transition temperatures of the cured materials were measured using a differential scanning calorimeter, the decomposition temperatures using a thermogravimetric analyzer, and the thermal conductivities using a thermal conductivity meter. The results are shown in Table 5. The glass transition temperatures of the cured materials ranged from 90 to 123°C and tended to decrease with increasing chain length. The 5% weight loss temperatures ranged from 290 to 307°C, and the 10% weight loss temperatures ranged from 333 to 355°C. There was no significant difference, but they increased slightly with increasing chain length. The thermal conductivities ranged from 0.33 to 0.53 W / mK, decreasing with increasing chain length. EIM-8, which had the lowest liquid crystal transition temperature, had the highest thermal conductivity.

[0148] [Table 5]

[0149] Preparation Example 3 - Preparation of cured EBP-n product of Example 3

[0150] [ka]

[0151] The molar ratio of epoxy resin to 4,4'-diaminodiphenyl sulfone was set to 2:1 to ensure equal epoxide and amine equivalents. The two solid materials were ground and mixed at room temperature, and then the cured product was produced using a hot press molding method. The curing temperature was 190°C and the curing time was 2 hours.

[0152] Test Example 4: Physical properties of cured EBP-n The glass transition temperatures of the cured EBP-n / DDS materials were measured using a differential scanning calorimeter, the decomposition temperatures using a thermogravimetric analyzer, and the thermal conductivities using a thermal conductivity meter. The results are shown in Table 6. The glass transition temperatures of the cured materials were observed in the range of 125–150°C, and tended to decrease with increasing chain length, except for EBP-7. The 5% weight loss temperatures were in the range of 349–361°C, and the 10% weight loss temperatures were in the range of 368–380°C, confirming the high level of thermal stability due to the rigid biphenol structure. The thermal conductivities were observed in the range of 0.40–0.55 W / mK, with the highest thermal conductivity being observed for EBP-6, which had the best match between the liquid crystal phase onset temperature and the curing temperature.

[0153] [Table 6]

[0154] Comparative Example 1 Preparation of cured diglycidyl ether of bisphenol A The difunctional epoxy resin, diglycidyl ether of bisphenol A, YD-128, was purchased from Kukdo Chemical (Korea). The epoxy equivalent weight (EEW) was 187 g / eq, and the amine equivalent weight was equal. The two substances were mixed at room temperature and then heated in a general-purpose convection oven to prepare test specimens. The system using DDM as the curing agent had a curing temperature of 130°C and a curing time of 1 hour, while the system using DDS as the curing agent had a curing temperature of 190°C and a curing time of 2 hours.

[0155] Test Example 5: Physical properties of cured diglycidyl ether of bisphenol A The glass transition temperatures of two cured products of diglycidyl ether of bisphenol A were measured using a differential scanning calorimeter, the decomposition temperatures using a thermogravimetric analyzer, and the thermal conductivity using a thermal conductivity meter. The measurement results are shown in Table 7. The 4,4'-diaminodiphenylmethane cured product had a glass transition temperature of 144°C, a 10% weight loss temperature of 364°C, and a thermal conductivity of 0.24 W / mK. The DDS cured product had a glass transition temperature of 174°C, a 10% weight loss temperature of 404°C, and a thermal conductivity of 0.27 W / mK. Compared to Examples 1 to 3, the cured product of Comparative Example 1 had a slightly higher glass transition temperature and no significant difference in decomposition temperature, but was significantly lower in thermal conductivity.

[0156] [Table 7]

[0157] Comparative Example 2 Production of 4,4'-diglycidyloxybiphenyl cured material 4,4'-Diglycidyloxybiphenyl epoxy was synthesized using biphenol as the starting material by reacting it with epichlorohydrin in the presence of a base. By adjusting the base equivalent, it was produced in the form of an oligomer, with an epoxy equivalent weight of 190 g / eq. The synthesized 4,4'-diglycidyloxybiphenyl epoxy was prepared by grinding and mixing the two solid materials at room temperature, followed by hot-press molding to produce a cured product. The system using 4,4'-diaminodiphenylmethane as the curing agent had a curing temperature of 130°C and a curing time of 1 hour, while the system using 4,4'-diaminodiphenylsulfone as the curing agent had a curing temperature of 190°C and a curing time of 2 hours.

[0158] Test Example 6: Physical properties of cured 4,4'-diglycidyloxybiphenyl The glass transition temperatures of two types of 4,4'-diglycidyloxybiphenyl cured products were determined by differential scanning calorimetry, the decomposition temperatures by thermogravimetric analysis, and the thermal conductivities by thermal conductivity measurements. The results are shown in Table 8. The DDM cured product had a glass transition temperature of 160°C, a decomposition temperature at 10% weight loss of 356°C, and a thermal conductivity of 0.30 W / m K. The DDS cured product had a glass transition temperature of 208°C, a decomposition temperature at 10% weight loss of 393°C, and a thermal conductivity of 0.34 W / m K. Compared to Examples 1 to 3, the cured product of Comparative Example 1 had a higher glass transition temperature and a slightly higher decomposition temperature due to its rigid structure, but there was a significant difference in thermal conductivity. The glass transition temperatures of two types of cured 4,4'-diglycidyloxybiphenyl products were measured using a differential scanning calorimeter, the decomposition temperatures using a thermogravimetric analyzer, and the thermal conductivity using a thermal conductivity meter. The measurement results are shown in Table 8. The DDM cured product had a glass transition temperature of 160°C, a 10% weight loss temperature of 356°C, and a thermal conductivity of 0.30 W / m K. The DDS cured product had a glass transition temperature of 208°C, a 10% weight loss temperature of 393°C, and a thermal conductivity of 0.34 W / m K. Compared to Examples 1 to 3, the cured product of Comparative Example 1 had a higher glass transition temperature and a slightly higher decomposition temperature due to its rigid structure, but a significant difference in thermal conductivity was confirmed.

[0159] [Table 8]

[0160] From the above description, it will be apparent to those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential characteristics of the present invention. In this regard, the above-described embodiments are illustrative in all respects and are not limiting.

Claims

1. A compound of the following chemical formula (II): 【Chemistry 2】 (wherein n is an integer from 1 to 30) is expressed as A polyfunctional epoxy compound characterized by:

2. A compound obtained by reacting the compound according to claim 1 with a curing agent. A cured epoxy resin product characterized by:

3. The cured product has the following chemical formula (IV): 【Chemistry 4】 (wherein X and Y may be the same or different and are selected from the compounds of the chemical formula (I) to the compounds of the chemical formula (III)). is expressed as The cured epoxy resin product according to claim 2.

4. The curing agent is selected from the group consisting of 4,4'-diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), m-phenylenediamine (mPDA), and dicyandiamide (DICY). The cured epoxy resin product according to claim 2.

5. The cured product can be used in substrates, compounds, adhesives, pads, heat spreaders, and heat sinks. The cured epoxy resin product according to claim 2.

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