Modified naphthol resin and preparation method thereof

Abstract

The invention provides a preparation method of modified naphthol resin, which comprises the following steps: sequentially carrying out nitration reaction and hydrogenation reaction on naphthol resin to form the modified naphthol resin with amido in the structure. A solvent used in the hydrogenation reaction comprises tetrahydrofuran, toluene, isopropanol, an amide solvent or the cosolvent.

Description

Technical Field

[0001] The invention relates to a resin and a preparation method thereof, in particular to a modified naphthol resin and a preparation method thereof. Background Art

[0002] In the field of electronic products or their manufacturing, there is often a demand for resin materials such as insulating materials, adhesives, and film raw materials. Currently, epoxy resin or polyphenylene ether (PPE) resin is more widely used. However, epoxy resin or polyphenylene ether may not have good dielectric properties or heat resistance, which may cause corresponding limitations in the application of electronic products. Summary of the invention

[0003] The present invention is directed to a modified naphthol resin and a preparation method thereof. The preparation method of the modified naphthol resin of the present invention has a higher hydrogenation rate.

[0004] According to an embodiment of the present invention, the preparation method of the modified naphthol resin comprises the following steps: the naphthol resin is subjected to a nitration reaction and a hydrogenation reaction in sequence to form a modified naphthol resin having an amino group in its structure. The solvent used in the hydrogenation reaction comprises tetrahydrofuran, toluene, isopropanol, an amide solvent or the above-mentioned co-solvent.

[0005] The modified naphthol resin of the present invention includes the modified naphthol resin prepared by the above-mentioned modified naphthol resin preparation method. The modified naphthol resin has a structure represented by [Formula 4] described below.

[0006] Based on the above, since the solvent used in the hydrogenation reaction includes tetrahydrofuran, toluene, isopropanol, amide solvents or the above co-solvents, the preparation method of the modified naphthol resin can have a higher hydrogenation rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 The present invention is a schematic flow chart of a method for preparing a modified naphthol resin according to an embodiment of the present invention.

[0008] Description of Reference Numerals

[0009] S10, S20, S30: steps. DETAILED DESCRIPTION

[0010] In the following detailed description, for the purpose of illustration and not limitation, exemplary embodiments that disclose specific details are set forth to provide a thorough understanding of the various principles of the present invention. However, it will be apparent to one of ordinary skill in the art that, with the benefit of this disclosure, the present invention may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, descriptions of well-known devices, methods, and materials may be omitted to avoid obscuring the description of the various principles of the present invention.

[0011] Ranges may be expressed herein as from "about" one particular value to "about" another particular value, which may also be expressed directly as one particular value and / or to another particular value. When expressing the range, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when a value is expressed as an approximation by using the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each range may be expressly related to or independent of the other endpoint.

[0012] In this document, non-limiting terms (such as: may, can, for example or other similar terms) mean that implementation, inclusion, addition or existence are optional or necessary.

[0013] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. It will also be understood that terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning consistent with their meaning in the relevant technical context and should not be interpreted in an idealized or overly formal sense unless explicitly defined as such herein.

[0014] Please refer to Figure 1 The preparation method of the modified naphthol resin may include the following steps: Step S10: providing an unmodified naphthol resin. Step S20: subjecting the unmodified naphthol resin to a nitration reaction. Step S30: subjecting the product of the nitration reaction to a hydrogenation reaction in a specific solvent to generate a modified naphthol resin.

[0015] [Unmodified Naphthol Resin]

[0016] In one embodiment, the unmodified naphthol resin may be The above naphthol group may include 1-naphthol group or 2-naphthol

[0017] In one embodiment, the unmodified naphthol resin may not have any nitro, nitroso or amine groups on the corresponding naphthol groups. In one embodiment, the unmodified naphthol resin does not have any nitro, nitroso or amine groups.

[0018] In one embodiment, the chemical formula of the unmodified naphthol resin may be as shown in the following [Formula 1].

[0019] [Formula 1]

[0020]

[0021] In [Formula 1], n can be a positive integer between 2 and 40.

[0022] In one embodiment, the chemical formula of the unmodified naphthol resin may be similar to [Formula 1]. For example, the hydrogen atom attached to the carbon atom may be substituted by an alkyl group having one to five carbon atoms (which can be calculated as: C1-C5). For another example, the hydroxyl group in the naphthol group may be located at other substitution positions.

[0023] In one embodiment, the number-average molecular weight (Mn) or weight-average molecular weight (Mw) of the polymer can be measured by gel permeation chromatography (GPC).

[0024] In one embodiment, the average value of n (the average value is not necessarily an integer) may be between 4 and 31, based on the number average molecular weight or the weight average molecular weight.

[0025] In one embodiment, the unmodified naphthol resin may be a commercially available product (e.g., trade name 4000, manufactured by Shanghai Hengfeng New Material Technology Co., Ltd.).

[0026] <Nitrification reaction>

[0027] Unmodified naphthol resin can be nitrated by a nitrating agent.

[0028] In one embodiment, the nitrification reaction can be performed in a common nitrification reaction tank.

[0029] In one embodiment, the nitrating agent used in the nitration reaction is halonitrobenzene.

[0030] In one embodiment, considering the corresponding reactivity and / or steric effects of chemical reaction, the halonitrobenzene in the nitration reaction is 4-halonitrobenzene. For example, the nitration reaction can be performed by adding 4-halonitrobenzene to a solution in which unmodified naphthol resin is dissolved.

[0031] The chemical formula of 4-halonitrobenzene can be shown as the following [Formula 2].

[0032] [Formula 2]

[0033]

[0034] In [Formula 1], X may be a fluoro group, a chloro group, a bromo group or an iodo group.

[0035] In one embodiment, considering the reactivity of the reactants, preferably, X is fluorine (ie, 4-fluoronitrobenzene).

[0036] In one embodiment, the ratio of the total molar number of hydroxyl groups in the unmodified naphthol resin to the molar number of 4-halonitrobenzene may be 1:1 to 1:2.5; preferably, 1:1.01 to 1:1.05.

[0037] In one embodiment, the total molar number of hydroxyl groups in the unmodified naphthol resin can be estimated by the molar number of the reactants used to generate the unmodified naphthol resin.

[0038] In one embodiment, the total molar number of hydroxyl groups in the unmodified naphthol resin can be calibrated or estimated by commonly used standards (such as, but not limited to, ISO 4629-2:2016, ASTM E222-10, GB / T 12008.3, and CNS 6681).

[0039] In one embodiment, considering the corresponding reactivity, the nitration reaction is preferably performed in an alkaline environment.

[0040] In one embodiment, considering the corresponding reactivity and the corresponding solubility of the unmodified naphthol resin, the solvent used in the nitration reaction can be a co-solvent including an amide solvent; or, an amide solvent. The aforementioned amide solvent can include but is not limited to: N-methylpyrrolidone (Methylpyrrolidone, NMP), dimethylacetamide (dimethylacetamide, DMAC), dimethylformamide (dimethylformamide, DMF) or tetramethylurea (Tetramethylurea, TMU).

[0041] In one embodiment, the corresponding pH value can be adjusted by adding an alkali agent (such as sodium carbonate, potassium carbonate or other similar substances).

[0042] In one embodiment, the molar number of the corresponding hydroxyl ions in the alkali agent is about 1 to 2 times the total molar number of hydroxyl groups in the unmodified naphthol resin.

[0043] In one embodiment, the solvent for the nitration reaction may be, for example, 5 mol to 7 mol of potassium carbonate dissolved in 6 mol of dimethylacetamide; or a dimethylacetamide solution with the same amount of base.

[0044] The unmodified naphthol resin of the above-mentioned [Formula 1] and the halonitrobenzene of the above-mentioned [Formula 2] are subjected to a nitration reaction to generate a naphthol resin having a nitro structure as shown in the following [Formula 3].

[0045] [Formula 3]

[0046]

[0047] The definition of n in [Formula 3] is substantially the same as the definition of n in its corresponding [Formula 1]. The reason for the aforementioned or hereinafter described "n being substantially the same" is that in a chemical reaction, there may be unintentional, but unexpected and / or unavoidable side reactions.

[0048] <Hydrogenation reaction>

[0049] The modified naphthol resin shown in the following [Formula 4] can be produced by hydrogenating the naphthalene ring resin having a nitro structure of the above-mentioned [Formula 3].

[0050] [Formula 4]

[0051]

[0052] The definition of n in [Formula 4] is basically the same as the definition of n in the corresponding [Formula 1] and / or [Formula 3].

[0053] In one embodiment, the hydrogenation reaction can be carried out in a common hydrogenation reaction tank. For example, a gas guide agitator is provided in the hydrogenation reaction tank. Furthermore, after the reaction liquid is placed in the hydrogenation reaction tank, hydrogen gas can be introduced into the hydrogenation reaction tank to carry out the hydrogenation reaction. The amount of hydrogen gas introduced and / or the flow rate of hydrogen gas introduced can be adjusted according to the set gas pressure (about 5 bar to about 100 bar).

[0054] In one embodiment, the temperature of the hydrogenation reaction does not substantially exceed the boiling point or azeotropic point of the solvent used.

[0055] In one embodiment, the hydrogenation reaction is carried out in a solvent at a temperature of about 50°C to 120°C; preferably, about 80°C to 110°C.

[0056] In one embodiment, the hydrogenation reaction can be carried out in tetrahydrofuran (THF), toluene, isopropanol (IPA), an amide solvent (e.g., dimethylacetamide (DMAC)), or the above-mentioned co-solvent. The solvent used in the hydrogenation reaction may have a direct effect on the hydrogenation rate and / or side reaction.

[0057] In one embodiment, the solvent for the hydrogenation reaction may be a co-solvent of toluene and isopropanol, wherein the volume ratio of toluene to isopropanol may be about 80:20 to 100:0; preferably, about 80:20 to 75:25.

[0058] In one embodiment, the solvent for the hydrogenation reaction may be a co-solvent formed by dimethylacetamide and toluene or dimethylacetamide, wherein the volume ratio of dimethylacetamide to toluene may be about 75:25 to 100:0; preferably, about 90:10 to 100:0.

[0059] In one embodiment, considering the previously performed nitration reaction, the solvent used in the hydrogenation reaction can be similar to the solvent used in the previously performed nitration reaction. In one embodiment, the solvent used in the hydrogenation reaction can be a co-solvent including an amide solvent; or, an amide solvent.

[0060] In one embodiment, the solvent used in the hydrogenation reaction is only an amide solvent, and other non-amide solvents are not included. In one embodiment, if the solvent used in the hydrogenation reaction is only an amide solvent, a higher hydrogenation rate may be achieved.

[0061] In one embodiment, the pressure of the reaction gas (eg, hydrogen) in the hydrogenation reaction may be about 5 bar to about 100 bar; preferably, the pressure may be about 15 bar to about 30 bar.

[0062] In one embodiment, the reaction time of the hydrogenation reaction is about 4 hours to 12 hours; preferably, about 8 hours to 12 hours.

[0063] In one embodiment, the hydrogenation reaction can be carried out at a pressure of about 5 bar to 100 bar for about 4 hours to 12 hours; preferably, it can be carried out at a pressure of about 15 bar to 30 bar; preferably, it can be carried out at a pressure of about 8 hours to 12 hours; more preferably, the hydrogenation reaction can be carried out at a pressure of about 5 bar to 30 bar for about 8 hours to 12 hours.

[0064] In one embodiment, the hydrogenation reaction may be performed under appropriate heating under a corresponding pressure atmosphere.

[0065] In one embodiment, the hydrogenation reaction may include using a suitable catalyst. For example, the reaction liquid and the hydrogenation catalyst may be placed in a hydrogenation reaction tank and mixed. Furthermore, after the reaction liquid is placed in the hydrogenation reaction tank, hydrogen gas may be introduced into the hydrogenation reaction tank to perform the hydrogenation reaction. After the hydrogenation reaction, the hydrogenation catalyst may be removed by filtering.

[0066] In one embodiment, a hydrogenation catalyst can be used to promote the hydrogenation reaction of the terminal nitro group. The hydrogenation catalyst can be a ruthenium (Ru) catalyst, a palladium (Pd) catalyst, a rhodium (Rh) catalyst, a platinum (Pt) catalyst, a nickel (Ni) catalyst, or a combination thereof.

[0067] In one embodiment, the hydrogenation catalyst is, for example, a metal, a metal alloy or a solid heterogeneous catalyst containing a metal having a porous structure. For example, it may include, but is not limited to, ruthenium-metal oxide (such as ruthenium-magnesium oxide (Ru-MgO) or ruthenium-titanium dioxide (Ru-TiO2)), palladium carbon or similar palladium carbon catalyst (Palladium on carbon, Pd / C), platinum black, Raney Nickel or a porous alumina (such as γ-Al2O3) carrier including platinum, rhodium and / or palladium.

[0068] In one embodiment, based on 100 parts by weight of the total amount of reactants used, the amount of hydrogenation catalyst used is about 0.5 to 2 parts by weight; preferably, about 1.0 to 1.4 parts by weight; and more preferably, about 1.2 parts by weight (i.e., 1.2±10%wt%).

[0069] In one embodiment, by the aforementioned method, the hydrogenation rate of the hydrogenation reaction can be about 90% or more; preferably, it can be about 94% or more; and even more preferably, it can be about 98% or more.

[0070] In one embodiment, the hydrogenation rate can be estimated by a characteristic spectrum comparison method. For example, the hydrogenation rate can be estimated by the decrease and / or increase of the corresponding infrared characteristic spectrum of the terminal nitro group and / or the terminal amine group.

[0071] In one embodiment, the hydrogenation reaction may include the following reaction conditions: the solvent is a co-solvent of toluene and isopropanol, wherein the volume ratio of toluene to isopropanol is about 80:20 to 75:25; based on the total amount of reactants used being 100 parts by weight, the amount of hydrogenation catalyst used is 1.2 parts by weight (i.e., 1.2±10%wt%, 1.08wt% to 1.32wt%); the reaction pressure is about 5 bar (i.e., 5±10% bar, 4.5 bar to 5.5 bar); the reaction temperature is about 110°C (i.e., 110±10°C, 100°C to 120°C); and the reaction time is about 5 hours (i.e., 5±0.5 hours, 4.5 hours to 5.5 hours). Moreover, the hydrogenation rate corresponding to the above reaction conditions may be about 94%. Moreover, the polymer dispersity index (PDI) corresponding to the above reaction conditions is about 3.03.

[0072] In one embodiment, the hydrogenation reaction may include the following reaction conditions: the solvent is an amide solvent and other non-amide solvents (such as dimethylacetamide and toluene); based on the total amount of the reactants used being 100 parts by weight, the amount of the hydrogenation catalyst used is about 1.2 parts by weight (i.e., 1.2±10%wt%, 1.08wt%~1.32wt%); the reaction pressure is about 20 bar (i.e., 20±10% bar, 18 bar~22 bar); the reaction temperature is about 90°C (i.e., 90±10°C, 80°C~100°C); and the reaction time is about 10 hours (i.e., 5±0.5 hours, 4.5 hours~5.5 hours). Moreover, the hydrogenation rate corresponding to the above reaction conditions can be about 98% or more. Moreover, the polymer dispersibility index corresponding to the above reaction conditions is about 1.63, which may be due to the use of amide solvents, thereby reducing the possibility of side reactions.

[0073] In one embodiment, the hydrogenation reaction may include the following reaction conditions: the solvent is only an amide solvent (such as dimethylacetamide); based on the total amount of reactants used being 100 parts by weight, the amount of hydrogenation catalyst used is about 1.2 parts by weight (i.e., 1.2±10%wt%, 1.08wt%~1.32wt%); the reaction pressure is about 20 bar (i.e., 20±10%bar, 18bar~22bar); the reaction temperature is about 90°C (i.e., 90±10°C, 80°C~100°C); and the reaction time is about 10 hours (i.e., 5±0.5 hours, 4.5 hours~5.5 hours). Moreover, the hydrogenation rate corresponding to the above reaction conditions can be about 99% or more. Moreover, the polymer dispersibility index corresponding to the above reaction conditions is about 1.53, which may be due to the use of only amide solvents, which greatly reduces the possibility of side reactions.

[0074] <Application of modified naphthol resin>

[0075] Since the modified naphthol resin shown in [Formula 4] can have better quality (eg, more uniform in functional groups, morphology, and / or structure), it can be suitable for application in electronic products.

[0076] For example, the modified naphthol resin shown in [Formula 4] can be used for the synthesis of maleimide resin, benzoxazine resin and / or polyimide resin (PI resin). The corresponding maleimide resin, benzoxazine resin and / or polyimide resin can be used for the production of electronic products (such as copper clad laminate (CCL) used to manufacture circuit boards).

[0077] In one embodiment, the modified naphthol resin shown in [Formula 4] is used in electronic products. Since the modified naphthol resin used has good quality, the electronic products can also have good quality or good yield.

[0078] <Preparation Example of Modified Naphthol Resin>

[0079] A commercially available unmodified naphthol resin (trade name 4000, manufactured by Shanghai Hengfeng New Materials Technology Co., Ltd., and represented by Suiye Industrial; including the unmodified naphthol resin shown in [Formula 1]) added to about 6 mol of dimethylacetamide (DMAC) to dissolve it. Then, about 1.25 mol of potassium carbonate and about 1.25 mol of 4-fluoronitrobenzene are added, reacted at a temperature of about 120°C for about 5 hours, and then cooled to room temperature. Then, filter to remove solids, and then precipitate with a mixed solution of methanol and water to obtain a precipitate of nitrated naphthol resin (such as [Formula 3]). Then, the above precipitate is added to a mixed solvent formed by toluene and isopropanol (volume ratio is about 80:20), and about 1.2 parts by weight of palladium carbon catalyst (based on the weight of the above precipitate as 100 parts by weight) is added, and reacted at a temperature of about 110°C and a pressure of about 5 bar for about 8 hours to carry out a hydrogenation reaction and obtain the modified naphthol resin of Example 1 (such as [Formula 4]). The obtained modified naphthol resin was evaluated by the following evaluation methods, and the results are shown in [Table 1].

[0080] The modified naphthol resins of Examples 2 to 3 were prepared by the same or similar steps as those of Example 1, and the difference was that the solvent, reaction time, reaction temperature and / or reaction pressure used in the hydrogenation reaction were changed (as shown in [Table 1]). The obtained modified naphthol resins were evaluated by the following evaluation methods, and the results are shown in [Table 1].

[0081] [Table 1]

[0082]

[0083] <Evaluation method>

[0084] Number average molecular weight (Mn): The prepared modified naphthol resin was dissolved in tetrahydrofuran (THF) to prepare a test solution with a concentration of 1 wt %. Then, the test solution was measured for number average molecular weight by gel permeation chromatography (GPC).

[0085] Weight average molecular weight (Mw): The prepared modified naphthol resin was dissolved in tetrahydrofuran (THF) to prepare a test solution with a concentration of 1 wt %. Then, the test solution was measured for weight average molecular weight by gel permeation chromatography (GPC).

[0086] Polydispersity index (PDI): The measured weight average molecular weight is divided by the number average molecular weight (i.e., Mw / Mn) to obtain the polydispersity index (PDI). The smaller the PDI, the more concentrated the distribution of molecular weight is. Under the same or similar conditions of the initial reactants, catalysts, and their corresponding amounts, the smaller the PDI, the smaller the possibility of the corresponding side reaction, and the more concentrated the distribution of molecular weight is. Therefore, if the distribution of molecular weight is more moderate (i.e., the smaller the PDI), it can be expressed as more uniform in functional groups, morphology, and / or structure, and can be called a more uniform reaction / synthesis. In addition, if the distribution of molecular weight is more moderate (i.e., the smaller the PDI), the proportion of side reaction products (such as: larger polymer molecules formed by repolymerization) may be relatively small, so in terms of product application, it can also be more stable for subsequent processing or application, so that the subsequent processed products can have better quality or better yield.

[0087] Solubility in toluene: Place 1 gram of the prepared modified naphthol resin in a container, and add toluene to make a solution weighing 2 grams. Shake the solution at room temperature and let it stand for about 30 minutes. When it becomes a clear solution, measure its solubility.

[0088] Solubility in butanone: Place 1 gram of the prepared modified naphthol resin in a container, and add butanone to make a solution weighing 2 grams. Shake the solution at room temperature and let it stand for about 30 minutes. When it becomes a clear solution, measure its solubility.

[0089] Dielectric constant (Dk): The prepared modified naphthol resin was coated on a substrate, baked at 120°C for 2 minutes, and then hot-pressed at 210°C for 3 hours to form a film with a thickness of 100 μm. Then, the dielectric constant (Dk) at a frequency of 10 GHz was measured by a dielectric analyzer (model E4991A, manufactured by Agilent Technologies, Inc.). The smaller the dielectric constant, the better the dielectric properties of the modified naphthol resin.

[0090] Dielectric loss (dissipation factor, Df): The prepared modified naphthol resin was coated on a substrate, baked at 120°C for 2 minutes, and then hot-pressed at 210°C for 3 hours to form a film with a thickness of 100 μm. Then, the dielectric loss (Df) at a frequency of 10 GHz was measured by a dielectric analyzer (model E4991A, manufactured by Agilent Technologies). The smaller the dielectric loss, the better the dielectric properties of the modified naphthol resin.

[0091] Glass transition temperature (Tg): The glass transition temperature (Tg) of the prepared modified naphthol resin is measured by a dynamic mechanical analyzer (DMA). The higher the Tg, the better the ability of the modified naphthol resin to resist phase change, that is, the better the heat resistance. The heating rate during measurement: 10℃ / min. The temperature range during measurement: 30℃~300℃ (heating, cooling, heating).

[0092] Peel strength: The prepared modified naphthol resin was coated on a substrate and baked at 120°C for 2 minutes to form a resin film. Then, copper foil was stacked on the upper and lower surfaces of the resin film and hot pressed at 210°C for 3 hours to form a film with a thickness of 200 microns. Then, the peel strength was measured by a universal tensile machine. The greater the peel strength, the better the ability of the modified naphthol resin to resist peeling from the substrate, that is, good peel resistance.

[0093] <Evaluation Results>

[0094] As shown in Table 1, the preparation method of the modified naphthol resin includes sequentially subjecting the unmodified naphthol resin to a nitration reaction and a hydrogenation reaction to form a modified naphthol resin having an aminophenyl group in its structure. Furthermore, the hydrogenation reaction is at least carried out in a specific solvent, so that a better hydrogenation rate can be obtained. In addition, the obtained modified naphthol resin can also have a better molecular weight distribution.

[0095] In addition, compared to the modified naphthol resin (Example 1) obtained by using a mixed solvent formed by toluene and isopropanol as a solvent for the hydrogenation reaction, the modified naphthol resin (Example 2 or Example 3) obtained by using dimethylacetamide as a solvent for the hydrogenation reaction has a higher hydrogenation rate and a smaller polydispersity index (i.e., a more uniform molecular weight distribution).

[0096] In addition, compared to the modified naphthol resin obtained by using a mixed solvent as the solvent for the hydrogenation reaction (Example 1 or Example 2), the modified naphthol resin obtained by using only an amide solvent (such as dimethylacetamide) as the solvent for the hydrogenation reaction (Example 3) has a higher hydrogenation rate and a smaller polydispersity index (i.e., the molecular weight distribution is more uniform).

[0097] In addition, compared to the modified naphthol resin obtained by hydrogenation reaction at a temperature greater than 90°C and a pressure less than 15 bar (Example 1), the modified naphthol resin obtained by hydrogenation reaction at a temperature of 50°C to 90°C and a pressure of 15 bar to 50 bar (Example 2 or Example 3) has a higher hydrogenation rate and a smaller polydispersity index (i.e., a more uniform molecular weight distribution).

[0098] In summary, the preparation method of the modified naphthol resin of the present invention can have a higher hydrogenation rate. In addition, the modified naphthol resin can have good molecular weight distribution uniformity, and is suitable for being used as a hardener or for forming naphthol resins with other reactive groups, and has good applicability.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a modified naphthol resin, characterized in that: include: The naphthol resin is subjected to nitration reaction and hydrogenation reaction in sequence to form a modified naphthol resin having an amino group in its structure. The solvent used in the hydrogenation reaction includes tetrahydrofuran, toluene, isopropanol, amide solvents or the above co-solvents.

2. The preparation method of modified naphthol resin according to claim 1, wherein The solvent used in the hydrogenation reaction at least includes an amide solvent.

3. The preparation method of modified naphthol resin according to claim 1, characterized in that, The amide solvent includes N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea or the above co-solvents.

4. The preparation method of modified naphthol resin according to claim 3, characterized in that, The amide solvent at least includes dimethylacetamide.

5. The preparation method of modified naphthol resin according to claim 1, characterized in that, The hydrogenation reaction is carried out in the following environment: Reaction gas pressure of 5 bar to 100 bar; 4 to 12 hours reaction time; and Reaction temperature of 50°C to 120°C.

6. The preparation method of modified naphthol resin according to claim 1, characterized in that, The hydrogenation reaction further comprises: using a hydrogenation catalyst, wherein the amount of the hydrogenation catalyst used is 0.5 to 2 parts by weight based on 100 parts by weight of the total amount of the reactants used.

7. The preparation method of modified naphthol resin according to claim 1, characterized in that, The nitration reaction is carried out in an alkaline environment.

8. The preparation method of modified naphthol resin according to claim 1, characterized in that, The nitrating agent used in the nitration reaction is halonitrobenzene.

9. The method for preparing modified naphthol resin according to claim 1, wherein The naphthol resin has a structure represented by the following [Formula 1]: In [Formula 1], n represents a positive integer of 2 to 40.

10. A modified naphthol resin, characterized in that: The modified naphthol resin is prepared by the method for preparing the modified naphthol resin according to claim 1, and the modified naphthol resin has a structure represented by the following [Formula 4]: In [Formula 4], n represents a positive integer of 2 to 40.

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