KR20230064374A - A phenolic resin for refractory, process of preparing the phenolic resin for refractory and refractory including the same - Google Patents

Abstract

The present invention relates to a phenolic resin for refractories and a method for manufacturing the phenolic resin for refractories, wherein the phenolic resin can be more suitably used for refractories requiring improved heat resistance, processability, and strength. The phenolic resin contains 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-like compound.

Description

Phenolic resin for refractory materials, manufacturing method of phenolic resin for refractory materials and refractories containing the same

The present invention relates to a phenolic resin for refractories, a method for preparing a phenolic resin for refractories, and a refractory containing the same.

Woody waste materials (biomass) such as bark, thinning materials, and construction waste materials have been disposed of until now. However, recently, as the environmental pollution issue has become an important task, the reuse and recycling methods of the biomass have begun to be reviewed.

The main components of the biomass include cellulose, hemicellulose and lignin. Among these, lignin contained in an amount of about 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 studied.

In this regard, chemical products such as resins were using fossil resources such as petroleum as raw materials. However, as the concept of carbon neutrality has recently been introduced, the demand for using the biomass as a raw material has been increasing. Accordingly, there is an active movement to substitute plant-derived resins (bioplastics) for plastic products such as packaging materials, members of home appliances, and members for automobiles.

In particular, trees form an interpenetrating polymer network (IPN) structure of hydrophilic linear polymeric polysaccharides (cellulose and hemicellulose) and hydrophobic cross-linked lignin. Among these, lignin is attracting attention as a raw material for plant-derived heat-resistant resin materials among biomass. Lignin is a polymer with a cross-linked structure having a basic backbone of hydroxyphenyl propane units. Lignin accounts for about 25% by mass of trees and has a chemical structure of polyphenols, and has been expected as a substitute material for petroleum-derived phenolic resins.

However, resins made from raw materials of general plant-derived heat-resistant resin materials have problems in that they cannot simultaneously satisfy sufficient heat resistance, processability, and strength. In particular, although lignin is expected to have excellent heat resistance compared to other bioplastics represented by polylactic acid, since it has an alcoholic hydroxyl group and a phenolic hydroxyl group, it has a higher softening temperature and melting point than general phenolic resins, resulting in reduced processability. did For this reason, there were limitations in application to automobile parts, OA-related parts, refractories, and casting products.

US Patent Publication No. 2015/0210904

Accordingly, a technical problem to be solved by the present invention is to provide a phenolic resin for refractories and a method for manufacturing the refractories capable of obtaining refractories having improved heat resistance, workability and strength. It is also to provide a refractory material containing the phenolic resin for the refractory material.

One aspect of the present invention is a repeating unit (a) derived from a phenolic compound; repeating units (b) derived from aldehyde-type compounds; and a repeating unit (c) derived from a lignin-type compound, wherein the repeating unit (c) derived from the lignin-type compound relative to the number of moles of the repeating unit (a) derived from the phenol-type compound in the phenol resin ) The ratio (mol%) of the number of moles is 1 to 23 mol%, and relates to a phenolic resin for refractories.

Another aspect of the present invention is (a) reacting a phenolic compound, an aldehyde compound and a lignin compound in the presence of a catalyst to obtain a phenolic resin composition; A phenolic resin for refractories comprising a ratio (%) of the number of moles of the lignin-type compound to the number of moles of the phenolic compound in step (a) of obtaining the phenolic resin composition is 1 mol% to 23 mol%. It's about manufacturing methods.

Another aspect of the present invention relates to a refractory material comprising the phenolic resin for the refractory material.

The phenolic resin for refractories according to the present invention may have improved heat resistance and processability. In addition, the method for manufacturing a phenolic resin for refractories according to the present invention can easily manufacture a phenolic resin for refractories with improved heat resistance and workability. Thus, the refractory containing the phenolic resin for refractories may have improved workability, heat resistance and strength.

In the following, various aspects and various embodiments of the present invention are described in more detail.

Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as 'comprise' or 'having' are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Specifically, one aspect of the present invention is a repeating unit (a) derived from a phenolic compound; repeating units (b) derived from aldehyde-type compounds; and a repeating unit (c) derived from a lignin-type compound, wherein the repeating unit (c) derived from the lignin-type compound relative to the number of moles of the repeating unit (a) derived from the phenol-type compound in the phenol resin ) is about 1 to 23 mol%, relative to the phenolic resin for refractories.

For example, the ratio (mol%) of the number of moles of the repeating unit (c) derived from the ligrin compound to the number of moles of the repeating unit (a) derived from the phenolic compound in the phenolic resin is 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 from about 5 to 17 mole %.

For example, when the ratio (%) of the total number of moles of the repeating unit (a) derived from the phenolic compound to the total number of moles of the repeating unit (c) derived from the lignin compound in the phenolic resin satisfies the above range, The viscosity of the composition containing the phenolic resin may be reduced. Accordingly, the processability of the phenolic resin is improved, the porosity of the refractory manufactured therefrom may be reduced, and the strength of the refractory may be improved.

For example, the lignin compounds refer to polymeric phenolic compounds composed of basic skeletons such as gaiacil lignin (G-type), syringyr lignin (S-type), and P-hydroxyphenyl lignin (H-type). can

For example, the lignin compounds refer to polymeric phenolic compounds composed of basic skeletons such as gaiacil lignin (G-type), syringyr lignin (S-type), and P-hydroxyphenyl lignin (H-type). can

The lignin compound is a compound included in all plants, and may refer to a compound derived from any one of hardwoods, conifers, and herbaceous woods. For example, lignin derived from hardwood family wood may include G-type lignin and S-type lignin. For example, lignin derived from woods of the invasion tree family may include G-type lignin. For example, lignin derived from woods of the herbaceous family may include H-forms, G-forms and S-forms.

The lignin-like compound may be obtained by extracting natural lignin contained in wood. For example, the lignin-type compound may be a compound included in a solution discharged in the process of transforming the wood into pulp using an industrial method. For example, the lignin compounds refer to alkali lignin, soda lignin, sulfite lignin, kraft lignin, etc. contained in the waste liquid discharged in the process of making pulp using the soda method, sulfurous acid method, kraft method, etc. for the wood. can do.

For example, the lignin-like compound may include kraft lignin, alkaline lignin, or a combination thereof.

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

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

For example, the weight of sulfur (S) contained in the lignin-like compound may be about 1 to 3.0 parts by weight based on 100 parts by weight of the lignin-like compound. For example, the weight of sulfur (S) included in the lignin compound may be 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 compound.

For example, the content of sulfur (S) contained in lignin compounds can be measured through organic elemental analysis (OEA). For example, the content of sulfur (S) contained in lignin compounds can be measured using Flash EA 1112 Elemental Analyzer (Thermo Fisher Co.).

When the sulfur (S) content contained in the lignin-type compound satisfies the above range, the viscosity and residual carbon ratio of the phenolic resin containing the repeating unit (C) derived from the lignin-type compound are easily adjusted to a specific range, , the heat resistance and strength of the refractories prepared therefrom can be simultaneously improved.

According to one embodiment, the number average molecular weight (Mn) of the lignin-type compound may be about 2,200 to 15,000 g/mol. For example, the number average molecular weight (Mn) of the lignin-type compound is 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.

For example, the weight average molecular weight (Mw) of the lignin-type compound may be about 5,000 to 33,000 g/mol. For example, the weight average molecular weight (Mw) of the lignin compound is 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.

For example, the lignin compound may have a polymer density index (PDI) of about 1 to about 6. For example, the PDI of the lignin 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.

For example, when the average molecular weight and PDI of the lignin-type compound satisfy the above ranges, the viscosity and residual carbon ratio of the phenolic resin containing the repeating unit (C) derived from the lignin-type compound can be easily controlled within a specific range. can Accordingly, the strength and heat resistance of the refractory including the same may be further improved.

The phenolic compound may be a compound represented by Formula 1 below.

<Formula 1>

In Formula 1,

R ₁ is hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or

Deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₆ -C ₆₀ aryl group, or a methyl group unsubstituted or substituted with any combination thereof, an ethyl group, an n -propyl group, iso propyl group, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isoox ethyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, 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, sec -hexoxy group, tert -hexoxy group, n -heptoxy group, isoheptoxy group, sec - Heptoxy group, tert -heptoxy group, n -octoxy group, isooctoxy group, sec -octoxy group, tert -octoxy group, n -nonoxy group, isononoxy group, sec -nonoxy group, tert -nonoxy group, n -decoxy group , isodexoxy, sec -decoxy or tert -decoxy; or

Substituted with heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₆₀ aryl group, or any combination thereof substituted or unsubstituted phenyl group, pentalenyl group, naphthyl group, azulenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrene Nyl group, chrysenyl group, perylenyl group, pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group or an ovalenyl group; or

-Si(Q ₁ )(Q ₂ )(Q ₃ ), -N(Q ₁ )(Q ₂ ), -C(=0)(Q ₁ ) or -S(=0) ₂ (Q ₁ );

Q ₁ to Q ₃ are each independently selected from hydrogen, heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, or a C ₆ -C ₆₀ It may be an aryl group.

a1 may be an integer from 0 to 5. For example, a1 may be 0 or 1.

For example, a1 means the number of R ₁ s , and when a1 is 2 or more, 2 or more R _1s may be the same as or different from each other.

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

For example, bisphenol compounds 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 combinations thereof.

The aldehyde compound may be a compound represented by Formula 2 below.

<Formula 2>

In Formula 2,

R ₂ is hydrogen, deuterium or -C(=0)(Q ₁₄ ); or

Deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₆ -C ₆₀ aryl group, or a methyl group unsubstituted or substituted with any combination thereof, an ethyl group, an n -propyl group, iso propyl group, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isoox ethyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, 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, sec -hexoxy group, tert -hexoxy group, n -heptoxy group, isoheptoxy group, sec - Heptoxy group, tert -heptoxy group, n -octoxy group, isooctoxy group, sec -octoxy group, tert -octoxy group, n -nonoxy group, isononoxy group, sec -nonoxy group, tert -nonoxy group, n -decoxy group , isodexoxy, sec -decoxy or tert -decoxy; or

Substituted with heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₆₀ aryl group, or any combination thereof substituted or unsubstituted phenyl group, pentalenyl group, naphthyl group, azulenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrene Nyl group, chrysenyl group, perylenyl group, pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group or an ovalenyl group; ego,

Q ₁₄ may be hydrogen, heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group or a C ₆ -C ₆₀ aryl group. .

For example, R ₂ is hydrogen, deuterium, methyl group, ethyl group, propyl group, methylethyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, phenyl group, or - C(=0)(Q ₁₄ ); or a C ₁ -C ₂₀ alkyl group substituted with a deuterium, methyl, ethyl, propyl, methylethyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl or phenyl group; It may be a phenyl group, a biphenyl group, a naphthyl group, or a furan group.

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

According to one embodiment, the ratio (mol%) of the number of moles of the repeating unit (c) derived from the lignin compound in the phenolic resin is about 0.5% to 20% by mole based on the total number of moles of the repeating units included in the phenolic resin. can be

For example, the number of moles of the repeating unit (c) derived from the lignin-like compound is the molecular weight of the total repeating unit (c) derived from the total lignin-like compound, the molecular weight of gyacyl lignin (type G), and the syringyr lignin ( It may mean a value divided by the average value (179 g/mol) of the molecular weight of S type) and the molecular weight of P-hydroxyphenyl lignin (H type). For example, the molecular weight of gaiacil lignin (type G) is 179 g/mol, the molecular weight of syringyr lignin (type S) is 209/mol, and the molecular weight of P-hydroxyphenyl lignin (type H) is 149 g/mol. may be mol.

For example, the ratio (mol%) of the number of moles of the repeating unit (c) derived from the lignin compound in the phenolic resin is about 0.5% to 20% by mole, based on the total number of moles of the repeating unit included in the phenolic resin. 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%, about 2 mol% to 11 mol%. .

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 the composition including the phenolic resin for refractories is reduced, thereby improving its processability. It can be. In addition, the strength of the refractory containing the phenolic resin for the refractory may be improved.

According to one embodiment, the ratio of the number of moles of the repeating unit (b) derived from the aldehyde compound to the number of moles of the repeating unit (a) derived from the phenolic compound in the phenolic resin may be about 1 to 7. For example, the ratio of the number of moles of the repeating unit (b) derived from the aldehyde compound to the number of moles of the repeating unit (a) derived from the phenolic compound in the phenol resin is 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.

According to one embodiment, the molar ratio (mol%) of the repeating unit (a) derived from the phenolic compound in the phenolic resin is about 10 mol% to 70 mol% based on the total number of moles of repeating units included in the phenolic resin. there is.

For example, the mole ratio (%) of the repeating unit (a) derived from a phenolic compound in the phenol resin is about 20 to 60 mol%, about 20 to 50 mol%, based on the total number of moles of the repeating units included in the phenol resin. , 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 mole %, about 28 to 38 mole %, about 33 to 38 mole %, or about 33 to 37 mole %.

For example, when the molar ratio of the repeating units included in the phenolic resin for refractory material satisfies the above range, the viscosity of the composition including the phenolic resin for refractory material may be reduced. Accordingly, the processability of the phenolic resin for refractories is improved, and the strength of the refractories may be improved by reducing the porosity of the refractories manufactured therefrom.

According to one embodiment, the residual carbon ratio of the phenol resin may be about 20% to 50%.

For example, the residual carbon ratio may refer to a weight ratio of the phenol resin after carbonization to the weight of the phenol resin before carbonization when the phenol resin is carbonized by heating at 1200° C. for 1 hour.

For example, the carbon retention rate may be calculated through Equation 1 below.

<Equation 1>

For example, the residual carbon ratio represents the weight of the phenolic resin remaining after carbonization, and the greater the residual carbon ratio, the greater the weight of the remaining phenolic resin. Accordingly, as the residual carbon ratio increases, the weight of the remaining phenolic resin increases, and thus the heat resistance of the phenolic resin may be improved. However, when the residual carbon ratio is less than the above range, it is difficult to expect sufficient strength and heat resistance improvement effect, and when the residual carbon ratio exceeds the above range, the viscosity of the phenolic resin for refractories is excessively increased and the workability of the phenolic resin for refractories is lowered, The porosity of the refractory including the same may be increased, and thus the strength of the refractory may decrease. Accordingly, the phenolic resin for refractories according to the present application satisfies a specific carbon ratio, so that heat resistance and strength of refractories including the phenolic resin may be further improved.

According to another embodiment, the residual carbon ratio of the phenolic resin for refractories is 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%.

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

According to one embodiment, the polymer density index (PDI) of the phenolic resin for refractories may be about 2 to 5. For example, the PDI 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.

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 is 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.

For example, when the average molecular weight and PDI of the phenolic resin for refractory materials satisfy the above ranges, heat resistance and strength of the refractory material including the phenolic resin for refractory material may be simultaneously improved.

According to one embodiment, the viscosity of the phenolic resin for refractories may be about 400cps to about 3,000cps. For example, the viscosity of the phenolic resin for refractories is about 800cps to 3,000cps, about 120cps to 3,000cps, about 400 to 2,000cps, about 400 to 1,700cps, about 400 to 1650cps, about 1,200 to 1,650cps, about 1,400 to It may be 1,650 cps, 1,200 to 1,600 cps or 1,200 to 1,535 cps.

Another aspect of the present invention includes (a) reacting a phenol-type compound, an aldehyde-type compound, and a lignin-type compound in the presence of a catalyst to obtain a phenolic resin composition; The weight ratio (%) of the lignin-type compound to the weight of the phenol-type compound may be 1% by weight to 45% by weight.

For example, the types and properties of the phenolic compound, the aldehyde compound, and the lignin compound, and the physical properties of the phenolic resin for refractories are referred to the above description.

According to one embodiment, the weight ratio (wt%) of the lignin-type compound to the weight of the phenol-type compound during the step of obtaining the phenolic resin may be about 1% to 45% by weight. For example, in the step of obtaining the phenol resin, the weight ratio (%) of the lignin-type compound to the weight of the phenol-type compound is about 1 wt% to 43 wt%, about 1 wt% to 32 wt%, about 2 % to 45%, about 7% to 45%, about 10% to 45%, about 10% to 43% or about 10% to 32%.

Another aspect of the present invention includes (a) reacting a phenol-type compound, an aldehyde-type compound and a lignin-type compound in the presence of a catalyst to obtain a phenolic resin composition; in the step (a) of obtaining the phenolic resin composition The ratio (mol%) of the number of moles of the repeating unit (c) derived from the ligrin compound to the weight of the phenolic compound is about 1 to 23 mol%. .

For example, in the step of obtaining the phenolic resin composition, the ratio (mol%) of the number of moles of the ligrin compound to the number of moles of the phenolic compound is about 1 to 23 mol%, about 3 to 23 mol%, about 5 to 23 mole %, about 1 to 21 mole %, about 1 to 17 mole %, about 3 to 17 mole % or about 5 to 17 mole %.

For example, the number of moles of the lignin-like compound is determined by the total weight of the repeating unit (c) derived from the total lignin-like compound, the molecular weight of greecyr lignin (G-type), the molecular weight of syringyr lignin (S-type), and the P- It may mean a value divided by the average value (179 g/mol) of molecular weight of hydroxyphenyl lignin (H-type).

For example, when the weight ratio (wt% or mol%) of the lignin-type compound to the weight of the phenol-type compound satisfies the above range, the viscosity and residual carbon ratio of the phenol resin for refractories to be produced can be easily adjusted within a specific range. there is. Accordingly, the prepared phenolic resin for refractories has excellent heat resistance and processability, so that heat resistance and strength of refractories including the phenolic resin may be further improved.

For example, in step (a) of obtaining a phenol resin composition, a phenol resin composition including a phenol resin may be prepared by reacting a phenol compound, an aldehyde compound, and a lignin compound in the presence of a catalyst.

For example, step (a) of obtaining the phenolic resin composition may be performed at a temperature range of about 70 to 100° C. for about 1 to 5 hours.

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

According to one embodiment, in step (a) of obtaining the phenolic resin composition, the ratio of the number of moles of the aldehyde-type compound to the number of moles of the phenol-type compound may be about 1 to 7. More preferably, the ratio of the number of moles of the aldehyde-type compound to the number of moles of the phenol-type compound in the step of obtaining the phenolic resin composition is 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.

According to one embodiment, the weight ratio (wt%) of the phenolic compound in step (a) of obtaining the phenolic resin composition is the weight of the phenolic compound, the weight of the aldehyde compound and the weight of the phenolic compound included in the phenolic resin composition. about 10 to 70% by weight relative to the total weight of the lignin-like compounds.

For example, in step (a) of obtaining the phenolic resin composition, the weight ratio (wt%) of the phenolic compound is the weight of the phenolic compound, the weight of the aldehyde compound, and the lignin contained in the phenolic resin composition. 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%, based on the total weight of the compounds About 35 to 70 mole%, about 20 to 50 mole%, about 20 to 41 mole%, about 20 to 38 mole%, about 32 to 38 mole%, about 33 to 38 mole%, or about 33 to 37 mole% can

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 weight of the phenolic compound is about 1 to 5 wt%, about 1.5 to 5 wt%, about 3 to 5 % by weight, about 0.5 to 4%, about 0.5 to 3% or about 1 to 3%.

For example, the catalyst may include a basic catalyst or an acidic 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 acidic catalyst, the phenolic resin for the refractory material may be a novolac resin.

According to one embodiment, the basic catalyst is NaOH, Ba(OH) ₂ , Ca(OH) ₂ , Mg(OH) ₂ , KOH, NH ₄ OH, N(CH ₂ CH ₂ OH) _3, N(CH ₂ CH ₃ ) ₃ , hexamine, tetraethylamine, tetraamine, tetraethylenepentamine, or combinations thereof.

According to another embodiment, the acidic catalyst is hydrochloric acid, nitric acid, sulfuric acid, ethane sulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, chlorobenzenesulfonic acid, 3,4-dichlorobenzenesulfonic acid, cresol sulfonic acid, phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, octylphenol sulfonic acid, naphthalene sulfonic acid, 1-naphthol-4-sulfonic acid, dodecyl sulfonic acid, dodecyl benzenesulfonic acid, phosphoric acid, oxalic acid, formic acid, or combinations thereof. there is.

According to one embodiment, the method for preparing the phenolic resin for refractories may further include (b) adding a thickener and a neutralizer to the phenolic resin composition.

For example, in the step of adding a thickener and a neutralizer to the phenolic resin composition, a phenolic resin for refractories may be obtained by performing a degassing process on the phenolic resin composition with the thickener and the neutralizer.

For example, the step of adding a thickener and a neutralizer to the phenolic resin composition may improve strength and heat resistance of a refractory material including the phenolic resin for refractory material by adjusting physical properties of the phenolic resin composition. For example, the step of adding a thickener and a neutralizer to the phenolic resin composition adjusts the viscosity, residual carbon ratio, number average molecular weight (Mn), weight average molecular weight (Mw), and PDI of the phenolic resin composition, The strength and heat resistance of a refractory containing a resin can be improved.

For example, the ratio of the number of moles of the thickener to the number of moles of the neutralizing agent added may range from about 1 to about 15. For example, the ratio of the number of moles of the thickener to the number of moles of the neutralizing agent is 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.

When the ratio of the number of moles of the thickener to the number of moles of the neutralizer satisfies the above range, the residual carbon ratio of the phenolic resin for refractories may be easily adjusted within a specific range. Accordingly, the strength and heat resistance of the refractory material including the phenolic resin for refractory material may be further improved.

According to one embodiment, the thickener may include a natural polysaccharide, carboxymethylcellulose, methylcellulose, an ester-based thickener, or a glycol-based thickener. For example, thickeners may include glycol-based thickeners.

According to one embodiment, the thickener may include a compound containing an -O- group and having a boiling point of 150 to 300°C. For example, the thickener may include a glycol compound including an -O- group and having a boiling point of 150 to 300°C.

For example, the thickening agent may include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol or combinations thereof.

According to one embodiment, the neutralizer is NaOH, Ba(OH) ₂ , Ca(OH) ₂ , Mg(OH) ₂ , KOH, NH ₄ OH, N(CH ₂ CH ₂ OH) _3, N(CH ₂ CH ₃ ) ₃ , hexamine, tetraethylamine, tetraamine, tetraethylenepentamine, hydrochloric acid, nitric acid, sulfuric acid, ethanesulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, chlorobenzenesulfonic acid, 3,4-dichlorobenzenesulfonic acid, Cresol sulfonic acid, phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, octyl phenol sulfonic acid, naphthalene sulfonic acid, 1-naphthol-4-sulfonic acid, dodecyl sulfonic acid, dodecyl benzenesulfonic acid, phosphoric acid, oxalic acid, formic acid or combinations thereof.

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

Another aspect of the present invention provides a refractory containing the phenolic resin for the refractory.

For example, the phenolic resin for refractories can be applied without limitation to refractories requiring improved strength and heat resistance. For example, the refractory material may be a refractory brick or the like.

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

For example, the refractory may include 70 to 85 parts by weight of the 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 the refractory.

For example, the graphite may include impression graphite, expanded graphite, or a combination thereof.

For example, the alumina clinker may improve corrosion resistance of the refractory. For example, the silicon carbide may improve oxidation resistance of the refractory material. For example, the impression graphite may improve thermal shock resistance and permeation resistance. For example, the expanded graphite may improve structural stability by lowering the modulus of elasticity of the refractory.

For example, the borosilicate frits include silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), boron oxide (B ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), and lead monoxide (PbO). , sodium oxide (Na ₂ O) may be included. For example, borosilicate frit contains 60% by weight of silicon oxide (SiO ₂ ), 10% by weight of aluminum oxide (Al ₂ O ₃ ), 15% by weight of boron oxide (B ₂ O ₃ ), 5% by weight of calcium oxide (CaO), It may include 1% by weight of magnesium oxide (MgO), 4% by weight of lead monoxide (PbO), and 5% by weight of sodium oxide (Na ₂ O).

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

For example, the metal silicon powder is oxidized before carbon or reacts with carbon to form silicon carbide and then oxidized again to precipitate carbon, thereby improving the oxidation resistance of the refractory.

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

[Definition of Terms]

In the present specification, C ₁ -C ₆₀ alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent 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, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -iso Pentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, tert -decyl group, etc. .

In the present specification, the C ₁ -C ₆₀ alkoxy group refers to a monovalent group having a chemical formula of -OA ₁₀₁ (where A ₁₀₁ is the C ₁ -C ₂₀ alkyl group), and specific examples thereof include a methoxy group and an ethoxy group , isopropyloxy groups, and the like.

In the present specification, a C ₆ -C ₆₀ aryl group refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and includes a phenyl group, a pentalenyl group, a naphthyl group, an azulenyl group, an indacenyl group, and an acetyl group. Naphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, perylenyl group, pentaphenyl group, Heptalenyl group, naphthacenyl group, picenyl group, hexacenyl group, pentacenyl group, rubicenyl group, coronenyl group, ovalenyl group and the like are included. When the C ₆ -C ₆₀ aryl group includes two or more rings, the two or more rings may be linked to each other.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for explaining the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

Example 1. Preparation of phenolic resin for refractories

In a four-necked flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenolic compound, 1305 g (17.38 mol) of 40% formaldehyde as an aldehyde compound, and a lignin-like compound with a number average molecular weight of 10,000 ± 2,000 g / mol, 6 g (0.03 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 85°C and reacting for 2 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid, a neutralizing agent for carboxylic acids, and 91 g (1.47 mol) ethylene glycol, a glycol thickener, were added to the composition at 40 ° C., followed by degassing for 3 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 523, the weight average molecular weight was 1,608 g/mol, the PDI was 3.12, the viscosity was 1645cps, and the residual carbon ratio was 36%.

Example 2. Preparation of phenolic resin for refractories

In a four-necked flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenol compound, 741 g (9.87 mol) of 40% formaldehyde as an aldehyde compound, and a lignin compound with a number average molecular weight of 10,000 ± 2,000 g / mol, 60 g (0.34 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 85°C and reacting for 3 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid as a neutralizing agent for carboxylic acids and 118 g (1.90 mol) of ethylene glycol as a glycol thickener were added to the composition at 40 ° C., followed by degassing for 3 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 423, the weight average molecular weight was 1,406 g/mol, the PDI was 3.32, the viscosity was 1450 cps, and the residual carbon ratio was 38%.

Example 3. Preparation of phenolic resin for refractories

In a four-necked flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenol compound, 741 g (9.87 mol) of 40% formaldehyde as an aldehyde compound, and a lignin compound with a number average molecular weight of 10,000 ± 2,000 g / mol, 170 g (0.95 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 80°C and reacting for 4 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid, a neutralizing agent for carboxylic acids, and 118 g (1.90 mol) ethylene glycol, a glycol thickener, were added to the composition at 40° C., followed by degassing for 2.5 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 442, the weight average molecular weight was 1,413 g/mol, the PDI was 3.55, the viscosity was 1520cps, and the residual carbon ratio was 38%.

Example 4. Preparation of phenolic resin for refractories

In a four-necked flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenol compound, 655 g (8.72 mol) of 40% formaldehyde as an aldehyde compound, and a lignin compound having a number average molecular weight of 10,000 ± 2,000 g / mol, 239 g (1.34 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 80°C and reacting for 5 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid as a neutralizing agent for carboxylic acids and 118 g (1.90 mol) of ethylene glycol as a glycol thickener were added to the composition at 40 ° C., followed by degassing for 3 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 478, the weight average molecular weight was 1,632 g/mol, the PDI was 3.55, the viscosity was 1538cps, and the residual carbon ratio was 39%.

Comparative Example 1. Preparation of phenolic resin for refractories

In a four-neck flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenol compound, 655 g (8.72 mol) of 40% formaldehyde as an aldehyde compound, and a lignin compound having a number average molecular weight of 10,000 ± 2,000 g / mol, 327.6 g (1.83 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 80°C and reacting for 5 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid as a neutralizing agent for carboxylic acids and 118 g (1.90 mol) of ethylene glycol as a glycol thickener were added to the composition at 40 ° C., followed by degassing for 3 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 512, the weight average molecular weight was 1,701 g/mol, the PDI was 3.84, the viscosity was 1692cps, and the residual carbon ratio was 39%.

Comparative Example 2. Preparation of phenolic resin for refractories

In a four-necked flask equipped with a stirrer, condenser, and thermometer, 546 g (5.80 mol) of phenol as a phenolic compound, 960 g (12.79 mol) of 40% formaldehyde as an aldehyde compound, and lignin-like compound having a number average molecular weight of 10,000 ± 2,000 g / mol, 436.8 g (2.44 mol) of lignin having a weight average molecular weight of 20,000 ± 5,000 g / mol, a poly dispersity index (PDI) of 2 ± 0.5, and a sulfur content of 3.0 parts by weight or less based on 100 parts by weight of lignin compounds, and 12 g of 50% NaOH was added. Thereafter, after raising the temperature to 80°C and reacting for 5 hours, it was cooled to obtain a composition containing a phenolic resin for refractories.

Thereafter, 7 g (0.15 mol) of formic acid, a neutralizing agent for carboxylic acids, and 118 g (1.90 mol) ethylene glycol, a glycol thickener, were added to the composition at 40 ° C., followed by degassing for 2 hours to obtain a phenolic resin for refractories. . The number average molecular weight of the prepared phenolic resin for refractories was 639, the weight average molecular weight was 1,832 g/mol, the PDI was 3.98, the viscosity was 1684cps, and the residual carbon ratio was 39%.

Experimental Example 1. Evaluation of physical properties of lignin

(1) Average molecular weight and polymer density index (PDI)

After diluting the lignin used in Examples 1 to 4 and Comparative Examples 1 to 2 in DMF at 1% by weight, filtering using a 0.45 μm PTFE syringe filter, using gel permeation chromatography (GPC), The number average molecular weight (Mn), weight average molecular weight (Mw) and polymer density index (PDI) of each lignin were measured and listed in Table 1 below.

In addition, after diluting the phenolic resins of Examples 1 to 4 and Comparative Examples 1 to 2 at 0.5% by weight in a DMF:THF = 4:6 solution, filtering using a 0.45 μm PTFE syringe filter, gel permeation chromatography (GPC) was used to measure the number average molecular weight (Mn), weight average molecular weight (Mw), and polymer density index (PDI) of each phenolic resin.

Experimental Example 2. Viscosity evaluation of phenolic resin for refractories

For the phenolic resins for refractories according to Examples 1 to 4 and Comparative Examples 1 to 2, the viscosity at 25°C was measured using a Brookfield viscometer. Each measurement result is shown in Table 1 below.

Experimental Example 3. Evaluation of residual carbon ratio of phenolic resin for refractories

A dry sample was prepared by drying 15 g of the phenolic resin for refractories according to Example 1 at 135° C. for 1 hour. Carbonization was performed by heating 7.5 g of the dried sample at 1,200° C. for 1 hour.

The weight of the dry sample before and after carbonization was measured, and the remaining carbon percentage (%) was calculated according to Equation 1 below, which is shown in Table 1 below.

<Equation 1>

For the phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 to 2, residual carbon ratios were calculated in the same manner as for the phenolic resins for refractories according to Example 1, and the residual carbon ratios were respectively listed in Table 1 below.

Experimental Example 4. Evaluation of heat resistance

A sample containing 15 g of phenolic resin for refractories according to Example 1 was prepared. The sample was gradually heated to a high temperature, and the temperature when the weight of the sample became 50% of the weight before heating was measured.

For the phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 to 2, the temperatures were measured in the same manner as the lignin-modified phenolic resins according to Example 1, and the temperatures are listed in Table 1 below, respectively.

Experimental Example 5. Evaluation of physical properties of refractories

After mixing 3.5 g of phenolic resin for refractories according to Example 1, 80 g of MgO, 8 g of SiC, and 15 g of C as a support, a sample was prepared by molding to 240 mm X 240 mm X 150 mm at a pressure of 1,000 kg/cm ² .

(1) Wettability and fluidity: relative wettability and fluidity of the sample were evaluated based on Example 1 (O).

A case in which wettability and fluidity were superior to Example 1 was indicated by ◎, and a case in which wettability and flowability were relatively deteriorated compared to Example 1 was indicated by △.

(2) Pot life: The time at which wettability and fluidity disappear for the sample was measured and listed in Table 1 below.

(3) Porosity, volumetric specific gravity and strength: room temperature and high temperature porosity of the above samples were measured according to KS L3304. Room temperature and high temperature volumetric specific gravity was also measured according to KS L3304. Room temperature and high temperature strength were measured according to KS L 3315-1. The measurement results are shown in Table 1 below.

The phenolic resins for refractories according to Examples 2 to 4 and Comparative Examples 1 to 2 were measured in the same manner as the phenolic resins for refractories according to Example 1 at room temperature and 1,400 ° C.

Example
One Example
2 Example
3 Example
4 comparative example
One comparative example
2 moles of lignin/moles of phenol (mol%) One 6 16 23 32 42 Weight of lignin/weight of phenol (wt%) One 11 31 44 60 80 moles of formaldehyde/moles of phenol 3 1.7 1.7 1.5 1.5 2.2 Phenolic resin physical properties Mn 523 423 442 478 512 639 Mw 1608 1406 1413 1632 1701 1832 PDI 3.12 3.32 3.55 3.55 3.84 3.98 viscosity 1645 1450 1520 1538 1692 1684 residual carbon rate 36 38 38 39 39 39 wettability, fluidity ○ ◎ ◎ ○ △ △ Pot life (h) 9 12 10 8 6 4 porosity
(%) Normal temperature (25℃) 2.4 2.4 2.5 2.5 2.4 2.5 High temperature (1,400℃) 9.6 8.5 9.1 9.3 10.5 11.3 bulk density
(g/cm ² ) Normal temperature (25℃) 3.04 3.03 3.03 3.05 3.08 3.13 High temperature (1,400℃) 2.98 2.96 2.95 2.95 2.97 2.98 robbery
(Kgf/cm ² ) Normal temperature (25℃) 605 645 629 610 594 573 High temperature (1,400℃) 509 562 540 527 498 465

As shown in Table 1, the phenolic resins for refractories according to Examples are compared with the phenolic resins for refractories according to Comparative Examples,

Preparation of phenolic resin for refractories Examples in which the ratio (mol%) of the number of moles of the ligrin-type compound to the number of moles of the phenol-type compound used are in the range of 1 to 23% by mole have a higher viscosity than the comparative examples that do not satisfy the above range. And the residual carbon ratio could be easily adjusted to a specific range. Accordingly, it was possible to easily manufacture a refractory material having improved heat resistance, workability and strength.

Therefore, the phenolic resin for refractories according to the present invention can produce refractories with improved strength, processability and heat resistance, and can be suitably used for refractories (eg, refractory bricks) requiring improved processability, heat resistance and strength.

The above-described examples and comparative examples are examples for explaining the present invention, but the present invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.

Claims (20)

repeating units (a) derived from phenolic compounds;
repeating units (b) derived from aldehyde-type compounds; and
A phenolic resin comprising a repeating unit (c) derived from a lignin-like compound,
The ratio (mol%) of the number of moles of the repeating unit (c) derived from the ligrin compound to the number of moles of the repeating unit (a) derived from the phenolic compound in the phenolic resin is 1 to 23% by mole. for phenolic resins.
According to claim 1,
The lignin 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 polymer density index (PDI) of 1 to 6. profit.
According to claim 1,
The lignin-type compound is a phenolic resin for refractories including kraft lignin, alkali lignin, or a combination thereof.
According to claim 1,
The weight of sulfur (S) contained in the lignin-type compound is 3.0 parts by weight or less based on 100 parts by weight of the lignin-type compound.
According to claim 1,
The phenolic compound is a compound represented by the following formula (1), a phenolic resin for refractories:
<Formula 1>

In Formula 1,
R ₁ is hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or
Deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₆ -C ₆₀ aryl group, or unsubstituted or substituted with any combination thereof, a methyl group, an ethyl group, an n -propyl group, Isopropyl group, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group , sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, 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, sec -hexoxy group, tert -hexoxy group, n -heptoxy group, isoheptoxy group, sec -heptoxy group, tert -heptoxy group, n -octoxy group, isooctoxy group, sec -octoxy group, tert -octoxy group, n -nonoxy group, isononoxy group, sec -nonoxy group, tert -nonoxy group, n -decox time, isodesoxi, sec -desox, or tert -desox; or
Substituted with heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₆₀ aryl group, or any combination thereof substituted or unsubstituted, phenyl group, pentalenyl group, naphthyl group, azulenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pi Renyl group, chrysenyl group, perylenyl group, pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group or an ovalenyl group; or
-Si(Q ₁ )(Q ₂ )(Q ₃ ), -N(Q ₁ )(Q ₂ ), -C(=0)(Q ₁ ) or -S(=0) ₂ (Q ₁ );
Q ₁ to Q ₃ are each independently selected from hydrogen, heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, or a C ₆ -C ₆₀ An aryl group,
a1 is an integer from 0 to 5; According to claim 1,
The aldehyde compound is a compound represented by the following formula (2), a phenolic resin for refractories:
<Formula 2>

In Formula 2,
R ₂ is hydrogen, deuterium or -C(=0)(Q ₁₄ ); or
Deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₆ -C ₆₀ aryl group, or a methyl group unsubstituted or substituted with any combination thereof, an ethyl group, an n -propyl group, iso propyl group, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isoox ethyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, 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, sec -hexoxy group, tert -hexoxy group, n -heptoxy group, isoheptoxy group, sec - Heptoxy group, tert -heptoxy group, n -octoxy group, isooctoxy group, sec -octoxy group, tert -octoxy group, n -nonoxy group, isononoxy group, sec -nonoxy group, tert -nonoxy group, n -decoxy group , isodexoxy, sec -decoxy or tert -decoxy; or
Substituted with heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₆₀ aryl group, or any combination thereof substituted or unsubstituted phenyl group, pentalenyl group, naphthyl group, azulenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrene Nyl group, chrysenyl group, perylenyl group, pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group or an ovalenyl group; ego,
Q ₁₄ is hydrogen, heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, or a C ₆ -C ₆₀ aryl group. According to claim 1,
The mole ratio (mol%) of the repeating unit (c) derived from the lignin-type compound in the phenolic resin for refractories is 0.5 to 20% by mole with respect to the total number of moles of repeating units included in the phenolic resin for refractories. profit. According to claim 1,
In the phenolic resin for refractories, the ratio of the total number of moles of repeating units (b) derived from the aldehyde compound to the total number of moles of repeating units (a) derived from the phenolic compound is 1 to 7. According to claim 1,
The residual carbon ratio of the phenolic resin for refractories is 20% to 50%, a phenolic resin for refractories. According to claim 1,
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) is 500 g / mol to 2,000 g / mol, and the PDI is 2 to 5, a refractory for phenolic resins. According to claim 1,
The viscosity at 25 ° C. of the phenolic resin for refractory is 400cps to 3,000cps, phenolic resin for refractory. (a) reacting a phenol-type compound, an aldehyde-type compound, and a lignin-type compound in the presence of a catalyst to obtain a phenolic resin composition; In the method for producing a phenolic resin comprising a,
The ratio (mol%) of the number of moles of the lignin-type compound to the weight of the phenol-type compound in step (a) of obtaining the phenolic resin is about 1 to 23 mole%. According to claim 12,
In step (a) of obtaining the phenolic resin composition, the ratio of the number of moles of the aldehyde-type compound to the number of moles of the phenol-type compound is 1 to 7. According to claim 12,
The weight ratio (weight%) of the catalyst to the weight of the phenolic compound in step (a) of obtaining the phenolic resin is 0.5 to 5% by weight. According to claim 12,
The weight of sulfur (S) contained in the lignin-like compound is 3.0 parts by weight or less based on 100 parts by weight of the lignin-like compound. According to claim 12,
The catalyst is a method for producing a phenolic resin for refractories comprising a basic catalyst or an acidic catalyst. According to claim 12,
After step (a) of obtaining the phenol resin composition, (b) adding a thickener and a neutralizer to the phenol resin composition; Further comprising a method for producing a phenolic resin for refractories. According to claim 17,
The thickener includes a glycol thickener, and the neutralizer includes a carboxylic acid type neutralizer, a method for producing a phenolic resin for refractories. According to claim 17,
In the step (b) of adding the thickener and the neutralizer, the ratio of the number of moles of the thickener to the number of moles of the neutralizer added is 1 to 15, a method for producing a phenolic resin for refractories. A refractory material comprising the phenolic resin for a refractory material according to any one of claims 1 to 11.