Refractory phenolic resin, method for producing refractory phenolic resin, and refractory containing same

Abstract

The present invention relates to a phenolic resin for refractories, which comprises a repeating unit (a) derived from a phenolic compound; a repeating unit (b) derived from an aldehyde compound; and a repeating unit (c) derived from a lignin compound, and in which the ratio (mol %) of the number of moles of the repeating unit (c) derived from a lignin compound to the number of moles of the repeating unit (a) derived from a phenolic compound is 1 to 23 mol %, and a method for producing the same. The phenolic resin for refractories can be used more suitably for refractories that require improved heat resistance, processability, and strength.

Description

[Technical Field]

[0001] The present invention relates to a phenolic resin for refractories, a method for producing the phenolic resin for refractories, and a refractory containing the same. [Background technology]

[0002] Until now, wood waste (biomass) such as bark, thinned wood, and construction waste has been disposed of. However, as environmental pollution issues have recently become an important issue, methods for reusing and recycling such biomass have begun to be investigated.

[0003] The main components of biomass include cellulose, hemicellulose, and lignin. Of these, lignin, which accounts for approximately 30% by weight, has a structure rich in aromatic rings, phenolic hydroxyl groups, and alcoholic hydroxyl groups, and therefore its use as a resin raw material is being investigated.

[0004] Related to this, chemical products such as resins have traditionally been made from fossil resources such as petroleum. However, with the recent introduction of the concept of carbon neutrality, there has been a growing demand for using biomass as a raw material. As a result, there has been an active movement to replace plastic products such as packaging materials, home appliance components, and automotive components with plant-derived resins (bioplastics).

[0005] In particular, trees form an interpenetrating polymer network (IPN) structure consisting of hydrophilic linear polymeric polysaccharides (cellulose and hemicellulose) and hydrophobic cross-linked lignin. Among these, lignin has attracted attention as a raw material for plant-derived heat-resistant resin materials in biomass. Lignin is a cross-linked polymer with a basic skeleton of hydroxyphenylpropane units. Lignin accounts for approximately 25% by mass of trees and has the chemical structure of polyphenols, making it a promising alternative to petroleum-derived phenolic resins.

[0006] However, resins produced from conventional plant-derived raw materials for heat-resistant resins have the problem of being difficult to simultaneously satisfy sufficient heat resistance, processability, and strength. Although lignin is expected to have superior heat resistance compared to other bioplastics, such as polylactic acid, its softening and melting points are higher than those of conventional phenolic resins due to the presence of alcoholic and phenolic hydroxyl groups, resulting in poor processability. Therefore, there are limitations to its application in automotive parts, office automation (OA)-related parts, refractories, and cast products. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, the technical problem to be solved by the present invention is to provide a phenolic resin for refractories, which can provide refractories having improved heat resistance, processability and strength, and a method for producing the same, and to provide a refractory containing the phenolic resin for refractories. [Means for solving the problem]

[0008] One aspect of the present invention relates to a phenolic resin for refractories, which comprises a repeating unit (a) derived from a phenolic compound, a repeating unit (b) derived from an aldehyde compound, and a repeating unit (c) derived from a lignin compound, wherein the ratio (mol %) of the number of moles of the repeating unit (c) derived from the lignin compound to the number of moles of the repeating unit (a) derived from the phenolic compound is about 1 to 23 mol %.

[0009] Another aspect of the present invention relates to a method for producing a phenolic resin for refractories, comprising the step of (a) reacting a phenolic compound, an aldehyde compound, and a lignin compound in the presence of a catalyst to obtain a phenolic resin composition, wherein in the step (a) of obtaining the phenolic resin composition, the ratio (%) of the number of moles of the lignin compound to the number of moles of the phenolic compound is 1 mol % to 23 mol %.

[0010] Yet another aspect of the present invention relates to a refractory containing the phenolic resin for refractories. [Effects of the Invention]

[0011] The phenolic resin for refractories according to the present invention can have improved heat resistance and processability. Furthermore, the method for producing a phenolic resin for refractories according to the present invention can easily produce a phenolic resin for refractories having improved heat resistance and processability. As a result, a refractory containing the phenolic resin for refractories can have improved processability, heat resistance, and strength. DETAILED DESCRIPTION OF THE INVENTION

[0012] Various aspects and various embodiments of the present invention will be described in more detail below.

[0013] The terms and words used in this specification and the claims should not be construed as being limited to their common or dictionary meanings, but should be construed in accordance with the meanings and concepts that correspond to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concepts of terms in order to explain his / her invention in the best possible way.

[0014] The terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly dictates otherwise. In the present invention, terms such as "comprise" or "have" specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, and should be understood not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0015] Specifically, one aspect of the present invention relates to a phenolic resin for refractories, which comprises a repeating unit (a) derived from a phenolic compound, a repeating unit (b) derived from an aldehyde compound, and a repeating unit (c) derived from a lignin compound, wherein the ratio (mol %) of the number of moles of the repeating unit (c) derived from the lignin compound to the number of moles of the repeating unit (a) derived from the phenolic compound is about 1 to 23 mol %.

[0016] For example, in the phenolic resin, the ratio (mol %) of the number of moles of repeating units (c) derived from the lignin compound to the number of moles of repeating units (a) derived from the phenolic compound may be about 1 to 23 mol %, about 3 to 23 mol %, about 5 to 23 mol %, about 1 to 21 mol %, about 1 to 20 mol %, about 1 to 17 mol %, about 3 to 23 mol %, about 5 to 23 mol %, or about 5 to 17 mol %.

[0017] For example, when the ratio (%) of the total number of moles of the repeating units (a) derived from the phenolic compound to the total number of moles of the repeating units (c) derived from the lignin compound in the phenolic resin satisfies the above range, the viscosity of a composition containing the phenolic resin can be reduced, thereby improving the processability of the phenolic resin, reducing the porosity of a refractory produced therefrom, and improving the strength of the refractory.

[0018] For example, the lignin compound may refer to a polymeric phenolic compound having a basic skeleton such as guaiacyl lignin (G type), syringyl lignin (S type), or P-hydroxyphenyl lignin (H type).

[0019] For example, the lignin compound may refer to a polymeric phenolic compound having a basic skeleton such as guaiacyl lignin (G type), syringyl lignin (S type), or P-hydroxyphenyl lignin (H type).

[0020] The lignin compounds are compounds found in plants in general and may refer to compounds derived from any one of broadleaf, coniferous, and herbaceous woods. For example, lignin derived from broadleaf woods may include G-type lignin and S-type lignin. For example, lignin derived from coniferous woods may include G-type lignin. For example, lignin derived from herbaceous woods may include H-type lignin, G-type lignin, and S-type lignin.

[0021] The lignin-based compounds may be extracted natural lignin contained in wood. For example, the lignin-based compounds may be compounds contained in a solution discharged during the process of converting wood into pulp using an industrial method. For example, the lignin-based compounds may refer to alkaline lignin, soda lignin, sulfite lignin, kraft lignin, etc. contained in wastewater discharged during the process of converting wood into pulp using a soda process, sulfite process, kraft process, etc.

[0022] For example, the lignin-based compound may include kraft lignin, alkaline lignin, or a combination thereof.

[0023] The lignin-based compound may contain sulfur (S), and the weight of sulfur (S) contained in the lignin-based compound may be about 3.0 parts by weight or less based on 100 parts by weight of the lignin-based compound.

[0024] According to one embodiment, the weight of sulfur (S) contained in the lignin-based compound may be about 0 to 3.0 parts by weight based on 100 parts by weight of the lignin-based compound. For example, the weight of sulfur (S) contained in the lignin-based compound may be about 0 to 2.9 parts by weight, about 0 to 2.8 parts by weight, about 0 to 2.0 parts by weight, or about 0 to 1.5 parts by weight based on 100 parts by weight of the lignin-based compound.

[0025] For example, the weight of sulfur (S) contained in the lignin-based compound may be about 1 to 3.0 parts by weight based on 100 parts by weight of the lignin-based compound, or about 1 to 2.5 parts by weight, or about 1.5 to 2.5 parts by weight based on 100 parts by weight of the lignin-based compound.

[0026] For example, the sulfur (S) content in lignin-based compounds can be measured by organic elemental analysis (OEA), for example, using a Flash EA 1112 Elemental Analyzer (Thermo Fisher).

[0027] When the sulfur (S) content of the lignin-based compound satisfies the above range, the viscosity and carbon content of the phenolic resin containing the repeating unit (C) derived from the lignin-based compound can be easily adjusted to a specific range, and the heat resistance and strength of the refractory produced therefrom can be improved at the same time.

[0028] According to one embodiment, the number average molecular weight (Mn) of the lignin-based compound may be about 2,200 to 15,000 g / mol. For example, the number average molecular weight (Mn) of the lignin-based compound may be about 2,500 to 15,000 g / mol, about 5,000 to 15,000 g / mol, about 8,000 to 15,000 g / mol, about 2,500 to 14,000 g / mol, or about 2,500 to 12,000 g / mol.

[0029] For example, the weight-average molecular weight (Mw) of the lignin-based compound may be about 5,000 to 33,000 g / mol, about 10,000 to 33,000 g / mol, about 12,000 to 33,000 g / mol, about 15,000 to 33,000 g / mol, about 5,000 to 30,000 g / mol, about 5,000 to 28,000 g / mol, or about 5,000 to 25,000 g / mol.

[0030] For example, the PDI (polydispersity index) of the lignin-based compound may be about 1 to 6. For example, the PDI (polydispersity index) of the lignin-based compound may be about 1.5 to 6, about 2 to 6, about 1.5 to 5, about 1.5 to 3, or about 1.5 to 2.5.

[0031] For example, when the average molecular weight and polydispersity index (PDI) of the lignin-based compound satisfy the above ranges, the viscosity and residual carbon content of the phenolic resin containing the repeating unit (C) derived from the lignin-based compound can be easily adjusted to specific ranges, thereby further improving the strength and heat resistance of the refractory containing the same.

[0032] The phenolic compound may be a compound represented by the following Chemical Formula 1:

[0033] [Chemical formula 1] JPEG0007729990000001.jpg45170

[0034] In the above Chemical Formula 1, R1 is hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, or a nitro group;

[0035] Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C6-C 60Aryl groups, or any combination thereof, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, or n-decyl , isodecyl, sec-decyl, tert-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, tert-pentoxy, neopentoxy, isopentoxy, sec-pentoxy, 3-pentoxy, sec-isopentoxy, n-hexoxy, isohexoxy, sec-hexoxy, tert-hexoxy, n-heptoxy, isoheptoxy, sec-heptoxy, tert-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonoxy; nonyloxy group, isononoxy group, sec-nonoxy group, tert-nonoxy group, n-decoxy (decoxy; decyloxy) group, isodecoxy group, sec-decoxy group or tert-decoxy group;

[0036] Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy groups, C6-C 60phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, perylenyl, pentaphenyl, heptalenyl, naphthacenyl, picenyl, hexacenyl, pentacenyl, rubicenyl, coronenyl, or ovalenyl groups, substituted or unsubstituted with aryl groups, or any combination thereof; or

[0037] -Si(Q1)(Q2)(Q3), -N(Q1)(Q2), -C(=O)(Q1) or -S(=O)2(Q1),

[0038] Q1 to Q3 are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy group or C6-C 60 It may be an aryl group.

[0039] a1 can be an integer from 0 to 5. For example, a1 can be 0 or 1.

[0040] For example, a1 means the number of R1, and when a1 is 2 or more, the two or more R1 may be the same or different from each other.

[0041] For example, the phenolic compound may include phenol, cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, phenylphenol, octylphenol, catechol, resorcinol, cardanol, bisphenolic compounds, or combinations thereof.

[0042] For example, the bisphenol compound may include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, dinitrobisphenol A, or a combination thereof.

[0043] The aldehyde compound may be a compound represented by the following Chemical Formula 2:

[0044] [Chemical formula 2] JPEG0007729990000002.jpg24170

[0045] In the above Chemical Formula 2, R2 is hydrogen, deuterium or -C(=O)(Q 14 );

[0046] Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C6-C 60Aryl groups, or any combination thereof, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, t ert-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, tert-pentoxy, neopentoxy, isopentoxy, sec-pentoxy, 3-pentoxy, sec-isopentoxy, n-hexoxy, isohexoxy, sec-hexoxy, tert-hexoxy, n-heptoxy, isoheptoxy, sec-heptoxy, tert-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonoxy, isononoxy, sec-nonoxy, tert-nonoxy, n-decoxy; decyloxy), isodecoxy, sec-decoxy, or tert-decoxy; or

[0047] Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy groups, C6-C 60phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, perylenyl, pentaphenyl, heptalenyl, naphthacenyl, picenyl, hexacenyl, pentacenyl, rubicenyl, coronenyl, or ovalenyl groups, which may be substituted or unsubstituted with an aryl group or any combination thereof;

[0048] Q 14 represents hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy group or C6-C 60 It may be an aryl group.

[0049] For example, R2 can be hydrogen, deuterium, methyl, ethyl, propyl, methylethyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, phenyl, or -C(=O)(Q 14 );or

[0050] C1-C substituted with deuterium, methyl, ethyl, propyl, methylethyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl or phenyl groups 20 It may be an alkyl group, a phenyl group, a biphenyl group, a naphthyl group, or a furan group.

[0051] For example, the aldehyde compound may include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, glyoxal, furfural, or a combination thereof.

[0052] According to one embodiment, in the phenolic resin, the mole ratio (mol %) of the repeating unit (c) derived from the lignin-based compound may be about 0.5 mol % to 20 mol % based on the total moles of repeating units contained in the phenolic resin.

[0053] For example, the number of moles of the repeating unit (c) derived from the lignin-based compound may refer to the total weight of the repeating units (c) derived from all lignin-based compounds divided by the average (179 g / mol) of the molecular weights of guaiacyl lignin (G-type), syringyl lignin (S-type), and p-hydroxyphenyl lignin (H-type). For example, the molecular weight of guaiacyl lignin (G-type) may be 179 g / mol, the molecular weight of syringyl lignin (S-type) may be 209 g / mol, and the molecular weight of p-hydroxyphenyl lignin (H-type) may be 149 g / mol.

[0054] For example, in the phenolic resin, the ratio (mol %) of the number of moles of repeating unit (c) derived from the lignin-based compound to the total number of moles of repeating units contained in the phenolic resin may be about 0.5 mol % to 20 mol %, about 0.5 mol % to 15 mol %, about 0.5 mol % to 12 mol %, about 0.5 mol % to 11.5 mol %, about 0.5 mol % to 11 mol %, about 1 mol % to 20 mol %, about 1.5 mol % to 20 mol %, about 2 mol % to 20 mol %, about 2.1 mol % to 20 mol %, about 2 mol % to 11 mol %, about 2.1 mol % to 11 mol %, or about 2 mol % to 11 mol %.

[0055] For example, when the ratio of the repeating unit (c) derived from the lignin compound in the phenolic resin satisfies the above range, the viscosity of a composition containing the phenolic resin for refractories can be reduced, the processability thereof can be improved, and the strength of a refractory containing the phenolic resin for refractories can be improved.

[0056] According to one embodiment, in the phenolic resin, the ratio of the number of moles of repeating units (b) derived from the aldehyde compound to the number of moles of repeating units (a) derived from the phenolic compound may be about 1 to 7. For example, in the phenolic resin, the ratio of the number of moles of repeating units (b) derived from the aldehyde compound to the number of moles of repeating units (a) derived from the phenolic compound may be about 1.5 to 7, about 1.6 to 7, about 1.61 to 7, about 1 to 5, about 1 to 3, about 1 to 2.9, about 1 to 1.8, about 1 to 1.75, about 1 to 1.71, or about 1.51 to 1.7.

[0057] According to one embodiment, the molar ratio (mol %) of the repeating unit (a) derived from a phenolic compound in the phenolic resin may be about 10 mol % to 70 mol % based on the total number of moles of repeating units contained in the phenolic resin.

[0058] For example, in the phenolic resin, the ratio (%) of the number of moles of repeating units (a) derived from a phenolic compound to the total number of moles of repeating units contained in the phenolic resin may be about 20 to 60 mol%, about 20 to 50 mol%, about 20 to 40 mol%, about 24 to 70 mol%, about 25 to 70 mol%, about 33 to 70 mol%, about 35 to 70 mol%, about 20 to 50 mol%, about 20 to 41 mol%, about 24 to 38 mol%, about 28 to 38 mol%, about 33 to 38 mol%, or about 33 to 37 mol%.

[0059] For example, when the molar ratio of the repeating units contained in the phenolic resin for refractories satisfies the above range, the viscosity of a composition containing the phenolic resin for refractories may be reduced, thereby improving the processability of the phenolic resin for refractories, reducing the porosity of a refractory manufactured therefrom, and improving the strength of the refractory.

[0060] According to one embodiment, the carbon content of the phenolic resin may be about 20% to 50%.

[0061] For example, the residual carbon ratio can mean the ratio of the weight of the phenolic resin after carbonization to the weight of the phenolic resin before carbonization when the phenolic resin is carbonized by heating at 1,200° C. for 1 hour.

[0062] For example, the residual carbon ratio can be calculated using the following Equation 1.

[0063] [Formula 1] JPEG0007729990000003.jpg24153

[0064] For example, the carbon content indicates the weight of the phenolic resin remaining after carbonization, and the higher the carbon content, the greater the weight of the remaining phenolic resin. Therefore, the higher the carbon content, the greater the weight of the remaining phenolic resin, thereby improving the heat resistance of the phenolic resin. However, if the carbon content is below the above range, it is difficult to expect sufficient strength and heat resistance improvement effects. If the carbon content exceeds the above range, the viscosity of the phenolic resin for refractories increases excessively, reducing the processability of the phenolic resin for refractories. The porosity of the refractory containing the phenolic resin may increase, reducing the strength of the refractory. Therefore, the phenolic resin for refractories of the present application satisfies a specific carbon content range, and the heat resistance and strength of the refractory containing the phenolic resin may be further improved.

[0065] According to other embodiments, the residual carbon ratio of the phenolic resin for refractories may be about 21% to 50%, about 32% to 50%, about 34% to 50%, about 21% to 43%, about 32% to 43%, about 34% to 43%, about 21% to 38%, about 32% to 38%, or about 34% to 38%.

[0066] According to an embodiment, the number average molecular weight (Mn) of the phenolic resin for refractories may be about 300 g / mol to 800 g / mol. For example, the number average molecular weight (Mn) of the phenolic resin for refractories may be about 300 g / mol to 600 g / mol, about 300 g / mol to 510 g / mol, about 300 g / mol to 480 g / mol, about 300 g / mol to 475 g / mol, or about 300 g / mol to 445 g / mol.

[0067] According to one embodiment, the PDI (polydispersity index) of the phenolic resin for refractories may be about 2 to 5. For example, the PDI (polymer density index) of the phenolic resin for refractories may be about 3 to 4, about 3.1 to 4, about 3.1 to 3.8, or about 3.2 to 3.8.

[0068] According to one embodiment, the weight average molecular weight (Mw) of the phenolic resin for refractories may be about 500 to 2,000 g / mol. For example, the weight average molecular weight (Mw) of the phenolic resin for refractories may be about 700 to 1,700 g / mol, about 900 to 1,700 g / mol, about 1,050 to 1,700 g / mol, about 500 to 1,650 g / mol, about 500 to 1,600 g / mol, or about 700 to 1,600 g / mol.

[0069] For example, when the average molecular weight and PDI (polymer density index) of the phenolic resin for refractories satisfy the above ranges, the heat resistance and strength of the refractory containing the phenolic resin for refractories can be improved at the same time.

[0070] According to one embodiment, the viscosity of the phenolic resin for refractories may be about 400 cps to 3,000 cps. For example, the viscosity of the phenolic resin for refractories may be about 800 cps to 3,000 cps, about 120 cps to 3,000 cps, about 400 to 2,000 cps, about 400 to 1,700 cps, about 400 to 1,650 cps, about 1,200 to 1,650 cps, about 1,400 to 1,650 cps, 1,200 to 1,600 cps, or 1,200 to 1,535 cps.

[0071] Another aspect of the present invention may provide a method for producing a phenolic resin for refractories, comprising the step of (a) reacting a phenolic compound, an aldehyde compound, and a lignin compound in the presence of a catalyst to obtain a phenolic resin composition, wherein in the step (a) of obtaining the phenolic resin, a ratio (%) of the weight of the lignin compound to the weight of the phenolic compound is 1 wt % to 45 wt %.

[0072] For example, the types and properties of the phenolic compounds, aldehyde compounds, and lignin compounds, and the properties of the phenolic resin for refractories are described above.

[0073] According to one embodiment, in the step of obtaining the phenolic resin, the weight ratio (wt%) of the lignin-based compound to the weight of the phenolic compound may be about 1 wt% to 45 wt%. For example, in the step of obtaining the phenolic resin, the weight ratio (wt%) of the lignin-based compound to the weight of the phenolic compound may be about 1 wt% to 43 wt%, about 1 wt% to 32 wt%, about 2 wt% to 45 wt%, about 7 wt% to 45 wt%, about 10 wt% to 45 wt%, about 10 wt% to 43 wt%, or about 10 wt% to 32 wt%.

[0074] Another aspect of the present invention may provide a method for producing a phenolic resin for refractories, comprising: (a) reacting a phenolic compound, an aldehyde compound, and a lignin compound in the presence of a catalyst to obtain a phenolic resin composition, wherein in the step (a) of obtaining the phenolic resin composition, a ratio (mol %) of the number of moles of repeating units (c) derived from the lignin compound to the weight of the phenolic compound is about 1 to 23 mol %.

[0075] For example, in the step of obtaining the phenolic resin composition, the ratio (mol %) of the number of moles of the lignin-based compound to the number of moles of the phenol-based compound may be about 1 to 23 mol %, about 3 to 23 mol %, about 5 to 23 mol %, about 1 to 21 mol %, about 1 to 17 mol %, about 3 to 17 mol %, or about 5 to 17 mol %.

[0076] For example, the number of moles of the lignin-based compound may refer to the value obtained by dividing the total weight of the repeating units (c) derived from the entire lignin-based compound by the average value (179 g / mol) of the molecular weight of guaiacyl lignin (G-type), the molecular weight of syringyl lignin (S-type), and the molecular weight of p-hydroxyphenyl lignin (H-type).

[0077] For example, when the ratio (wt % or mol %) of the weight of the lignin-based compound to the weight of the phenol-based compound satisfies the above range, the viscosity and residual carbon content of the phenolic resin for refractories produced can be easily adjusted to specific ranges. As a result, the produced phenolic resin for refractories has excellent heat resistance and processability, and the heat resistance and strength of the refractories containing the same can be further improved.

[0078] For example, in the step (a) of obtaining the phenolic resin composition, a phenolic compound, an aldehyde compound, and a lignin compound may be reacted in the presence of a catalyst to produce the phenolic resin composition containing a phenolic resin.

[0079] For example, step (a) of obtaining the phenolic resin composition may be carried out at a temperature ranging from about 70 to 100° C. for about 1 to 5 hours.

[0080] For example, in step (a) of obtaining the phenolic resin composition, a phenolic compound, an aldehyde compound, and a lignin compound may be reacted in the presence of a catalyst to produce a phenolic resin composition, which may then be cooled, for example, to about 30 to 50°C.

[0081] According to one embodiment, in step (a) of obtaining the phenolic resin composition, the ratio of the number of moles of the aldehyde compound to the number of moles of the phenolic compound may be about 1 to 7. More preferably, in the step of obtaining the phenolic resin composition, the ratio of the number of moles of the aldehyde compound to the number of moles of the phenolic compound may be about 1.5 to 7, about 1.6 to 7, about 1.61 to 7, about 1 to 5, about 1 to 3, about 1 to 2.9, about 1 to 1.8, about 1 to 1.75, about 1 to 1.71, or about 1.51 to 1.7.

[0082] According to one embodiment, in step (a) of obtaining the phenolic resin composition, the weight ratio (wt%) of the phenolic compound may be about 10 to 70 wt% of the total weight of the phenolic compound, the aldehyde compound, and the lignin compound contained in the phenolic resin composition.

[0083] For example, in step (a) of obtaining the phenolic resin composition, the weight ratio (wt%) of the phenolic compound may be about 20 to 60 mol%, about 20 to 50 mol%, about 20 to 40 mol%, about 24 to 70 mol%, about 25 to 70 mol%, about 33 to 70 mol%, about 35 to 70 mol%, about 20 to 50 mol%, about 20 to 41 mol%, about 20 to 38 mol%, about 32 to 38 mol%, about 33 to 38 mol%, or about 33 to 37 mol% of the total weight of the phenolic compound, the aldehyde compound, and the lignin compound contained in the phenolic resin composition.

[0084] According to one embodiment, in step (a) of obtaining the phenolic resin, the weight ratio (wt%) of the catalyst to the total weight of the phenolic compounds may be about 0.5 to 5 wt%. For example, in step (a) of obtaining the phenolic resin, the weight ratio (wt%) of the catalyst to the total weight of the phenolic compounds may be about 1 to 5 wt%, about 1.5 to 5 wt%, about 3 to 5 wt%, about 0.5 to 4 wt%, about 0.5 to 3 wt%, or about 1 to 3 wt%.

[0085] For example, the catalyst may include a basic catalyst or an acid catalyst. For example, when the catalyst includes a basic catalyst, the phenolic resin for the refractory material may be a resol resin. For example, when the catalyst includes an acid catalyst, the phenolic resin for the refractory material may be a novolac resin.

[0086] According to one embodiment, the basic catalyst may include NaOH, Ba(OH)2, Ca(OH)2, Mg(OH)2, KOH, NH4OH, N(CH2CH2OH)3, N(CH2CH3)3, hexamine, tetraethylamine, tetraamine, tetraethylenepentamine, or a combination thereof.

[0087] According to other embodiments, the acid catalyst may include hydrochloric acid, nitric acid, sulfuric acid, ethanesulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, chlorobenzenesulfonic acid, 3,4-dichlorobenzenesulfonic acid, cresolsulfonic acid, phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, octylphenolsulfonic acid, naphthalenesulfonic acid, 1-naphthol-4-sulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid, oxalic acid, formic acid, or a combination thereof.

[0088] According to an embodiment, the method for preparing a phenolic resin for a refractory material may further include (b) adding a thickener and a neutralizer to the phenolic resin composition.

[0089] For example, the step of adding a thickener and a neutralizer to the phenolic resin composition may include performing a degassing process on the phenolic resin composition using the thickener and the neutralizer, thereby obtaining a phenolic resin for refractories.

[0090] For example, adding a thickener and a neutralizer to the phenolic resin composition can adjust the physical properties of the phenolic resin composition and improve the strength and heat resistance of the resulting refractory containing the phenolic resin for use in refractories. For example, adding a thickener and a neutralizer to the phenolic resin composition can adjust the viscosity, residual carbon content, number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (PDI) of the phenolic resin composition and improve the strength and heat resistance of the resulting refractory containing the phenolic resin for use in refractories.

[0091] For example, the ratio of moles of the thickening agent to moles of the neutralizing agent added can be about 1 to 15. For example, the ratio of moles of the thickening agent to moles of the neutralizing agent can be about 1 to 13, about 1 to 12.5, about 1 to 12, about 5 to 15, about 9 to 15, about 9.5 to 15, about 9.5 to 13, or about 9.7 to 13.

[0092] When the ratio of the number of moles of the thickener to the number of moles of the neutralizing agent satisfies the above range, the residual carbon content of the phenolic resin for refractories can be easily adjusted to a specific range, thereby further improving the strength and heat resistance of the refractory containing the phenolic resin for refractories.

[0093] According to one embodiment, the thickener may include natural polysaccharides, carboxymethyl cellulose, methyl cellulose, an ester-based thickener, or a glycol-based thickener. For example, the thickener may include a glycol-based thickener.

[0094] According to one embodiment, the thickener may include a compound having an —O— group and a boiling point of 150° C. to 300° C. For example, the thickener may include a glycol compound having an —O— group and a boiling point of 150° C. to 300° C.

[0095] For example, the thickening agent can include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, or combinations thereof.

[0096] According to one embodiment, the neutralizing agent may include NaOH, Ba(OH)2, Ca(OH)2, Mg(OH)2, KOH, NH4OH, N(CH2CH2OH)3, N(CH2CH3)3, hexamine, tetraethylamine, tetraamine, tetraethylenepentamine, hydrochloric acid, nitric acid, sulfuric acid, ethanesulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, chlorobenzenesulfonic acid, 3,4-dichlorobenzenesulfonic acid, cresolsulfonic acid, phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, octylphenolsulfonic acid, naphthalenesulfonic acid, 1-naphthol-4-sulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid, oxalic acid, formic acid, or a combination thereof.

[0097] According to one embodiment, the neutralizing agent may include formic acid, carboxylic acid, propionic acid, butanoic acid, pentanoic acid, or a combination thereof.

[0098] Another aspect of the present invention provides a refractory containing the phenolic resin for refractories.

[0099] For example, the phenolic resin for refractories may be applied to refractories requiring improved strength and heat resistance, without limitation. For example, the refractory may be a firebrick.

[0100] According to one embodiment, when the refractory material is a firebrick, the refractory material may further include alumina clinker, silicon carbide, and graphite. According to another embodiment, the refractory material may further include alumina clinker, silicon carbide, graphite, and pitch. According to another embodiment, the refractory material may further include alumina clinker, silicon carbide, graphite, pitch, borosilicate frit, and metal powder.

[0101] For example, the refractory may include 70 to 85 parts by weight of alumina clinker, 5 to 10 parts by weight of the silicon carbide, 10 to 20 parts by weight of the graphite, and 3 to 4 parts by weight of the phenolic resin for refractories.

[0102] For example, the graphite may include flake graphite, expanded graphite, or a combination thereof.

[0103] For example, the alumina clinker can improve the corrosion resistance of the refractory. For example, the silicon carbide can improve the oxidation resistance of the refractory. For example, the flake graphite can improve the thermal shock resistance and infiltration resistance. For example, the expanded graphite can reduce the elastic modulus of the refractory and improve the structural stability.

[0104] For example, the borosilicate frit may contain silicon oxide (SiO), aluminum oxide (AlO), boron oxide (BO), calcium oxide (CaO), magnesium oxide (MgO), lead monoxide (PbO), and sodium oxide (NaO). For example, the borosilicate frit may contain 60 wt% silicon oxide (SiO), 10 wt% aluminum oxide (AlO), 15 wt% boron oxide (BO), 5 wt% calcium oxide (CaO), 1 wt% magnesium oxide (MgO), 4 wt% lead monoxide (PbO), and 5 wt% sodium oxide (NaO).

[0105] For example, the refractory material may further include 1 to 2 parts by weight of the borosilicate frit.

[0106] For example, the metal silicon powder may be oxidized before carbon or may react with carbon to form silicon carbide, which may then be further oxidized to precipitate carbon, thereby improving the oxidation resistance of the refractory material.

[0107] For example, the refractory material may further include 1 to 2 parts by weight of the metal silicon powder.

[0108] [Term definition] As used herein, C1-C 60 The alkyl group means a monovalent linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, and the like.

[0109] As used herein, C1-C 60 The alkoxy group is -OA. 101 (where A 101 is the C1-C 20 Specific examples of the alkoxy group include methoxy, ethoxy, and isopropyloxy groups.

[0110] As used herein, C6-C 60The aryl group refers to a monovalent group having a carbocyclic aromatic ring system having 6 to 60 carbon atoms, and includes phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, perylenyl, pentaphenyl, heptalenyl, naphthacenyl, picenyl, hexacenyl, pentacenyl, rubicenyl, coronenyl, ovalenyl, and the like. 60 When an aryl group contains two or more rings, the two or more rings may be linked to each other.

[0111] The present invention will be described in more detail below through examples. It will be obvious to those skilled in the art that these examples are provided merely to more specifically explain the present invention, and that the scope of the present invention is not limited by these examples.

[0112] <Example 1. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 1,305 g (17.38 mol) of 40% formaldehyde, (3) 6 g (0.03 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (polydispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 85 °C, reacted for 2 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0113] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 91 g (1.47 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 3 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 523, the weight-average molecular weight was 1,608 g / mol, the PDI (polydispersity index) was 3.12, the viscosity was 1,645 cps, and the residual carbon ratio was 36%.

[0114] <Example 2. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 741 g (9.87 mol) of 40% formaldehyde, (3) 60 g (0.34 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (polydispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 85 °C, reacted for 3 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0115] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 118 g (1.90 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 3 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 423, the weight-average molecular weight was 1,406 g / mol, the PDI (polydispersity index) was 3.32, the viscosity was 1,450 cps, and the residual carbon ratio was 38%.

[0116] <Example 3. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 741 g (9.87 mol) of 40% formaldehyde, (3) 170 g (0.95 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (poly dispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 80 ° C, reacted for 4 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0117] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 118 g (1.90 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 2.5 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 442, the weight-average molecular weight was 1,413 g / mol, the PDI (polydispersity index) was 3.55, the viscosity was 1,520 cps, and the residual carbon content was 38%.

[0118] <Example 4. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 655 g (8.72 mol) of 40% formaldehyde, (3) 239 g (1.34 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (polydispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 80 °C, reacted for 5 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0119] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 118 g (1.90 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 3 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 478, the weight-average molecular weight was 1,632 g / mol, the PDI (polydispersity index) was 3.55, the viscosity was 1,538 cps, and the residual carbon ratio was 39%.

[0120] <Comparative Example 1. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 655 g (8.72 mol) of 40% formaldehyde, (3) 327.6 g (1.83 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (polydispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 80 °C, reacted for 5 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0121] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 118 g (1.90 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 3 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 512, the weight-average molecular weight was 1,701 g / mol, the PDI (polydispersity index) was 3.84, the viscosity was 1,692 cps, and the residual carbon ratio was 39%.

[0122] <Comparative Example 2. Production of phenolic resin for refractories> A four-neck flask equipped with a stirrer, condenser, and thermometer was charged with (1) 546 g (5.80 mol) of phenol, (2) 960 g (12.79 mol) of 40% formaldehyde, (3) 436.8 g (2.44 mol) of lignin, having a number average molecular weight (Mn) of 10,000 ± 2,000 g / mol, a weight average molecular weight of 20,000 ± 5,000 g / mol, a PDI (polydispersity index) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of the lignin compound, and (4) 12 g of 50% NaOH. The mixture was then heated to 80 °C, reacted for 5 hours, and then cooled to obtain a composition containing a phenolic resin for refractories.

[0123] Then, 7 g (0.15 mol) of formic acid, a carboxylic acid neutralizer, and 118 g (1.90 mol) of ethylene glycol, a glycol thickener, were added to the composition at 40°C, and the mixture was degassed for 2 hours to obtain a phenolic resin for refractories. The number-average molecular weight (Mn) of the produced phenolic resin for refractories was 639, the weight-average molecular weight was 1,832 g / mol, the PDI (polydispersity index) was 3.98, the viscosity was 1,684 cps, and the residual carbon ratio was 39%.

[0124] <Experimental Example 1. Evaluation of the physical properties of lignin> (1) Average molecular weight and PDI (polydispersity index) The lignins used in Examples 1 to 4 and Comparative Examples 1 and 2 were each diluted with DMF to 1 wt % and filtered using a 0.45 μm PTFE syringe filter. The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (PDI) of each lignin were measured using gel permeation chromatography (GPC), and the results are listed in Table 1 below.

[0125] In addition, the phenolic resins of Examples 1 to 4 and Comparative Examples 1 and 2 were diluted to 0.5 wt % in a DMF:THF=4:6 solution, filtered using a 0.45 μm PTFE syringe filter, and then the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (PDI) of each phenolic resin were measured using gel permeation chromatography (GPC).

[0126] <Experimental Example 2. Viscosity evaluation of phenolic resin for refractories> The viscosities at 25° C. of the phenolic resins for refractories according to Examples 1 to 4 and Comparative Examples 1 and 2 were measured using a Brookfield viscometer. The respective measurement results are shown in Table 1 below.

[0127] <Experimental Example 3. Evaluation of residual carbon rate of phenolic resin for refractories> A dried sample was prepared by drying 15 g of the phenolic resin for refractories according to Example 1 at 135° C. for 1 hour. 7.5 g of the dried sample was heated at 1,200° C. for 1 hour to carbonize it.

[0128] The weight of the dried sample was measured before and after carbonization, and the residual carbon percentage (%) was calculated using the following formula 1, and the results are shown in Table 1 below.

[0129] [Formula 1] JPEG0007729990000004.jpg24153

[0130] For the phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 and 2, the residual carbon ratios were calculated in the same manner as for the phenolic resin for refractories according to Example 1, and the results are shown in Table 1 below.

[0131] <Experimental Example 4. Heat resistance evaluation> A sample was prepared containing 15 g of the phenolic resin for refractories according to Example 1. The sample was heated at gradually increasing temperatures, and the temperature was measured when the weight of the sample became 50% of the weight before heating.

[0132] The temperatures of the phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 and 2 were measured in the same manner as the lignin-modified phenolic resin according to Example 1, and the results are shown in Table 1 below.

[0133] <Experimental Example 5. Evaluation of refractory properties> 3.5 g of the phenolic resin for refractories according to Example 1 was mixed with 80 g of MgO, 8 g of SiC, and 15 g of C as a support, and then subjected to a pressure of 1,000 kg / cm 2 The specimen was prepared by molding the molded product into a size of 240mm x 240mm x 150mm at a pressure of 1000kJ / cm.

[0134] (1) Wettability and fluidity: The wettability and fluidity of the samples were evaluated relative to Example 1 as the standard (0).

[0135] The case where the wettability and fluidity were superior to those of Example 1 was indicated by ⊚, and the case where the wettability and fluidity were relatively inferior to those of Example 1 was indicated by Δ.

[0136] (2) Usable life: The time until the wettability and fluidity of the sample disappeared was measured and shown in Table 1 below.

[0137] (3) Porosity, volumetric density, and strength: The porosity of the above samples at room temperature and at high temperature was measured in accordance with KS L3304. The volumetric density at room temperature and at high temperature was also measured in accordance with KS L3304. The strength at room temperature and at high temperature was measured in accordance with KS L3315-1. The measurement results are shown in Table 1 below.

[0138] The strengths of the phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 and 2 were measured at room temperature and 1,400°C in the same manner as for the phenolic resin for refractories according to Example 1, and the results are shown in Table 1 below.

[0139] [Table 1]

[0140] As shown in Table 1 above, the phenolic resins for refractories according to the examples have the following characteristics when compared with the phenolic resins for refractories according to the comparative examples: In the examples in which the ratio (mol %) of the number of moles of lignin-based compounds to the number of moles of phenol-based compounds used in the production of the phenolic resin for refractories was in the range of 1 to 23 mol %, the viscosity and residual carbon content could be more easily adjusted to specific ranges than in the comparative examples in which the ratio did not satisfy the range, and therefore refractories with improved heat resistance, processability, and strength could be easily produced.

[0141] Therefore, the phenolic resin for refractories according to the present invention can be used to produce refractories having improved strength, processability, and heat resistance, and can be used to produce refractories (e.g., firebricks) that require improved processability, heat resistance, and strength.

[0142] The above examples and comparative examples are merely illustrative of the present invention, and are not intended to limit the scope of the present invention. A person skilled in the art can implement the present invention by making various modifications thereto, and the technical scope of the present invention should be defined by the appended claims.

Claims

1. a repeating unit (a) derived from a phenol compound; a repeating unit (b) derived from an aldehyde compound; and a repeating unit (c) derived from a lignin compound, In the phenolic resin, the ratio (mol %) of the number of moles of the repeating unit (c) derived from the lignin compound to the number of moles of the repeating unit (a) derived from the phenolic compound is 1 to 23 mol %, The weight of sulfur (S) contained in the lignin-based compound is 1 to 3.0 parts by weight based on 100 parts by weight of the lignin-based compound; In the phenolic resin for refractories, a ratio of the total number of moles of the repeating units (b) derived from the aldehyde compound to the total number of moles of the repeating units (a) derived from the phenol compound is 1.5 to 7.

2. 2. The phenolic resin for refractories according to claim 1, wherein the lignin-based compound has a number average molecular weight (Mn) of 2,200 to 15,000 g / mol, a weight average molecular weight (Mw) of 5,000 to 32,000 g / mol, and a polydispersity index (PDI) of 1 to 6.

3. The phenolic resin for refractories according to claim 1 , wherein the lignin compound comprises kraft lignin, alkaline lignin, or a combination thereof.

4. The phenolic resin for refractories according to claim 1, wherein the phenolic compound is a compound represented by the following chemical formula 1: [Chemical formula 1] In the above Chemical Formula 1, R １ is hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, or a nitro group; Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C ６ -C ６０ aryl groups, or any combination thereof, substituted or unsubstituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, t tert-decyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, tert-pentoxy group, neopentoxy group, isopentoxy group, sec-pentoxy group, 3-pentoxy group, sec-isopentoxy group, n-hexoxy group, isohexoxy group a soxy group, a sec-hexoxy group, a tert-hexoxy group, an n-heptoxy group, an isoheptoxy group, a sec-heptoxy group, a tert-heptoxy group, an n-octoxy group, an isooctoxy group, a sec-octoxy group, a tert-octoxy group, an n-nonoxy group, an isonoxy group, a sec-nonoxy group, a tert-nonoxy group, an n-decoxy (decyloxy) group, an isodecoxy group, a sec-decoxy group, or a tert-decoxy group; Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C １ -C ２０ Alkyl group, C １ -C ２０ Alkoxy group, C ６ -C ６０ phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, perylenyl, pentaphenyl, heptalenyl, naphthacenyl, picenyl, hexacenyl, pentacenyl, rubicenyl, coronenyl, or ovalenyl groups, substituted or unsubstituted with aryl groups, or any combination thereof; or -Si(Q １ ) (Q ２ ) (Q ３ ), -N(Q １ ) (Q ２ ), -C(=O)(Q １ ) or -S(=O) ２ (Q １ ) and Q １ Or Q ３ are each independently hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, C １ -C ２０ Alkyl group, C １ -C ２０ Alkoxy group or C ６ -C ６０ is an aryl group, a1 is an integer from 0 to 5.

5. The phenolic resin for refractories according to claim 1, wherein the aldehyde compound is a compound represented by the following chemical formula 2: [Chemical formula 2] In the above Chemical Formula 2, R ２ is hydrogen, deuterium or -C(=O)(Q １４ ); Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C ６ -C ６０ Aryl groups, or any combination thereof, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, t tert-decyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, tert-pentoxy group, neopentoxy group, isopentoxy group, sec-pentoxy group, 3-pentoxy group, sec-isopentoxy group, n-hexoxy group, isohexoxy group a soxy group, a sec-hexoxy group, a tert-hexoxy group, an n-heptoxy group, an isoheptoxy group, a sec-heptoxy group, a tert-heptoxy group, an n-octoxy group, an isooctoxy group, a sec-octoxy group, a tert-octoxy group, an n-nonoxy group, an isonoxy group, a sec-nonoxy group, a tert-nonoxy group, an n-decoxy (decyloxy) group, an isodecoxy group, a sec-decoxy group, or a tert-decoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C １ -C ２０ Alkyl group, C １ -C ２０ Alkoxy group, C ６ -C ６０ phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, perylenyl, pentaphenyl, heptalenyl, naphthacenyl, picenyl, hexacenyl, pentacenyl, rubicenyl, coronenyl, or ovalenyl groups, each of which may be substituted or unsubstituted with an aryl group or any combination thereof; Q １４ represents hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C １ -C ２０ Alkyl group, C １ -C ２０ Alkoxy group or C ６ -C ６０ It is an aryl group.

6. 2. The phenolic resin for refractories according to claim 1, wherein in the phenolic resin for refractories, a ratio (mol %) of the number of moles of the repeating unit (c) derived from the lignin-based compound is 0.5 to 20 mol % with respect to the number of moles of all repeating units contained in the phenolic resin for refractories.

7. 2. The phenolic resin for refractories according to claim 1, wherein the residual carbon ratio of the phenolic resin for refractories is 20% to 50%.

8. 2. The phenolic resin for refractories according to claim 1, wherein the number average molecular weight (Mn) of the phenolic resin for refractories is 300 g / mol to 800 g / mol, the weight average molecular weight (Mw) of the phenolic resin for refractories is 500 g / mol to 2,000 g / mol, and the polydispersity index (PDI) of the phenolic resin for refractories is 2 to 5.

9. 2. The phenolic resin for refractories according to claim 1, wherein the viscosity of the phenolic resin for refractories at 25°C is 400 cps to 3,000 cps.

10. (a) A method for producing a phenolic resin, the method comprising the step of reacting a phenolic compound, an aldehyde compound, and a lignin compound in the presence of a catalyst to obtain a phenolic resin composition, In the step (a) of obtaining the phenolic resin composition, a ratio (mol %) of the number of moles of the lignin-based compound to the number of moles of the phenol-based compound is 1 to 23 mol %, The weight of sulfur (S) contained in the lignin-based compound is 1 to 3.0 parts by weight based on 100 parts by weight of the lignin-based compound; wherein in the phenolic resin for refractories, a ratio of the total number of moles of the repeating units (b) derived from the aldehyde compound to the total number of moles of the repeating units (a) derived from the phenolic compound is 1.5 to 7.

11. 11. The method for producing a phenolic resin for a refractory material according to claim 10, wherein in step (a) of obtaining the phenolic resin composition, a ratio (wt%) of the weight of the catalyst to the weight of the phenolic compound is 0.5 to 5 wt%.

12. The method for producing a phenolic resin for use in a refractory material according to claim 10, wherein the catalyst includes a basic catalyst or an acidic catalyst.

13. 11. The method for producing a phenolic resin for a refractory material according to claim 10, further comprising the step of (b) adding a thickener and a neutralizer to the phenolic resin composition after the step (a) of obtaining the phenolic resin composition.

14. The method for producing a phenolic resin for use in a refractory material according to claim 13, wherein the thickener comprises a glycol thickener, and the neutralizer comprises a carboxylic acid neutralizer.

15. 14. The method for producing a phenolic resin for a refractory material according to claim 13, wherein in step (b) of adding the thickener and the neutralizing agent, a ratio of the number of moles of the thickener to the number of moles of the neutralizing agent added is 1 to 15.

16. A refractory material comprising the phenolic resin for refractories according to any one of claims 1 to 9.

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