A curing agent for phenol-formaldehyde resins and a method for its production

Abstract

The application relates to the technical field of phenolic resin curing, and discloses a curing agent for phenolic resin and a preparation method thereof. The curing agent for phenolic resin is composed of two parts of component A and component B. Component A comprises the following raw materials: a wear-resistant filler for promoting curing, and polyvinylpyrrolidone. Component B comprises the following raw materials: a toughening anti-aging curing product, and dioctyl phthalate. The component A of the phenolic resin curing agent prepared by the application is pre-cured at 120-130 DEG C, and the component B is post-cured at 140-150 DEG C. Through the synergistic effect of the two, the curing process of the phenolic resin can be effectively promoted, the cured phenolic resin can form a compact three-dimensional network structure, the mechanical strength, toughness and wear resistance of the phenolic resin can be effectively improved, the phenolic resin is endowed with excellent anti-aging capacity, and the service life of the phenolic resin is greatly prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of phenolic resin curing, in particular to a curing agent for phenolic resin and a preparation method thereof. BACKGROUND

[0002] As one of the earliest industrialized application of thermosetting resin, phenolic resin has highly conjugated benzene ring system and cross-linked network structure in its molecular structure, which endows it with excellent thermal stability. As an insulating material, phenolic resin plays an important role in the fields of aerospace, electronics, building decoration, transportation, etc. However, with the evolution of modern industrial technology towards precision, integration and long service life, the traditional phenolic resin system gradually exposes its performance short board.

[0003] The performance limitations of phenolic resin are essentially related to its curing mechanism. As a typical condensation type thermosetting resin, it needs to be converted from linear to three-dimensional network structure through the action of a curing agent. Although ordinary phenolic resin curing agents can achieve the curing of phenolic resin, the cross-linking density is low, which easily forms a mechanically weak area. The cured material often has the problems of poor toughness, poor wear resistance and low mechanical strength. In addition, in long-term engineering applications, phenolic resin is easily affected by heat and oxygen environment, and has a fast aging process and a short service life, which has been difficult to meet the current use requirements.

[0004] The patent with publication number CN107446097B discloses a preparation method of a high-temperature-resistant phenolic resin using organic silicon resin as a curing agent. The organic silicon resin precursor is heated in an oil bath under nitrogen protection, and after stirring and reaction, it is mixed uniformly with phenolic resin under nitrogen protection to obtain a mixed liquid, which is injected into a mold cavity and then cured and demolded to obtain a high-temperature-resistant phenolic resin. The organic silicon resin prepared by the patent as a curing agent has strong instantaneous heat resistance and high mechanical property retention rate at high temperature. However, the anti-aging ability of the phenolic resin in the patent is general, and the service life is not long, which greatly limits its long-term engineering application. SUMMARY

[0005] The present application relates to the technical field of phenolic resin curing, in particular to a curing agent for phenolic resin and a preparation method thereof.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] The application discloses a curing agent for phenolic resin, which is composed of two parts, namely, a first component and a second component; the first component comprises the following raw materials in parts by weight: 6-8 parts of a curing-promoting wear-resistant filler, and 1-2 parts of polyvinylpyrrolidone; the second component comprises the following raw materials in parts by weight: 15-20 parts of a toughening anti-aging curing product, and 2-3 parts of dioctyl phthalate; the curing-promoting wear-resistant filler is prepared by reacting chloropropylized vermiculite powder with aminomethanesulfonic acid; the chloropropylized vermiculite powder is prepared by surface modification of (3-chloropropyl)tris(trimethylsiloxy)silane on vermiculite powder; the toughening anti-aging curing product is prepared by reacting vanillyl alcohol modified polyethylene glycol diglycidyl ether with lysine; and the vanillyl alcohol modified polyethylene glycol diglycidyl ether is prepared by reacting polyethylene glycol diglycidyl ether with vanillyl alcohol.

[0008] Further, the preparation of the curing-promoting wear-resistant filler comprises the following steps:

[0009] S1: vermiculite powder is placed in anhydrous ethanol, ultrasonic dispersion is carried out for 10-12 min, then (3-chloropropyl)tris(trimethylsiloxy)silane is added, an oxalic acid solution is used to adjust the pH to 4-6, the temperature is increased to 55-60 DEG C, and reaction is carried out for 6-8 h; after extraction, washing and drying, chloropropylized vermiculite powder is obtained;

[0010] S2: the chloropropylized vermiculite powder is placed in toluene, ultrasonic dispersion is carried out for 15-18 min, then aminomethanesulfonic acid and an accelerator are added, the temperature is increased to 45-55 DEG C, and reaction is carried out for 3-5 h; after extraction, washing and drying, the curing-promoting wear-resistant filler is obtained.

[0011] Further, in step S1, the mass ratio of the vermiculite powder, the anhydrous ethanol and the (3-chloropropyl)tris(trimethylsiloxy)silane is 2-4:70-90:0.5-1.5.

[0012] Further, in step S2, the mass ratio of the chloropropylized vermiculite powder, toluene, aminomethanesulfonic acid and potassium carbonate is 3.2-4:90-110:3.5-4.2:0.03-0.08.

[0013] In the scheme, the vermiculite powder is surface modified by (3-chloropropyl) tris (trimethylsiloxy) silane to introduce chloropropyl to obtain chloropropylated vermiculite powder, and then under the action of a promoter, substitution reaction occurs between active chlorine in the structure of the chloropropylated vermiculite powder and amino groups in the structure of aminomethyl sulfonic acid to obtain a solidification-promoting wear-resistant filler; the solidification-promoting wear-resistant filler uses vermiculite powder as a base material, and the dispersibility of the vermiculite powder in a resin matrix is enhanced after surface modification, effectively enhancing the wear resistance of the phenolic resin; meanwhile, the sulfonic acid groups are grafted on the surface of the vermiculite powder to protect the vermiculite powder from migration, so that the vermiculite powder can provide high-concentration hydrogen ions in the solidification process of the phenolic resin, effectively reducing the activation energy of the hydroxymethyl condensation reaction, effectively promoting the formation of a hydroxymethyl condensation network in the initial solidification of the phenolic resin, and forming a synergistic effect with the subsequent supplemental solidification to improve the compactness of the solidified phenolic resin and effectively enhance the tensile strength, toughness and wear resistance of the solidified phenolic resin.

[0014] Further, in step S1, the mass fraction of oxalic acid is 30-40%.

[0015] Further, in step S2, the promoter is any one of potassium carbonate and pyridine.

[0016] Further, the preparation of the toughening and anti-aging solidification product comprises the following steps:

[0017] SS1: polyethylene glycol diglycidyl ether and vanillyl alcohol are placed in toluene, fully mixed and stirred, then boron trifluoride ether is added, and the reaction is carried out by heating, and after the solvent is removed by reduced pressure distillation, the product is collected to obtain vanillyl alcohol modified polyethylene glycol diglycidyl ether;

[0018] SS2: vanillyl alcohol modified polyethylene glycol diglycidyl ether and lysine are placed in N,N-dimethylformamide, fully mixed and stirred, then a catalyst is added, and the reaction is carried out by heating to 95-100 DEG C for 3-4 h, and after distillation under reduced pressure, the product is collected to obtain a toughening and anti-aging solidification product.

[0019] Further, in step SS1, the mass ratio of polyethylene glycol diglycidyl ether, vanillyl alcohol, toluene, boron trifluoride ether is 2.5-3.2:2.2-3:50-70:0.2-0.5.

[0020] Further, in step SS2, the mass ratio of vanillyl alcohol modified polyethylene glycol diglycidyl ether, lysine, N,N-dimethylformamide, catalyst is 3-3.4:2-4:80-90:0.3-0.8.

[0021] In the scheme, under the action of boron trifluoride ether, ring opening reaction occurs between the epoxy group in the polyethylene glycol diglycidyl ether structure and the active hydroxyl group in the vanillyl alcohol structure, to obtain vanillyl alcohol modified polyethylene glycol diglycidyl ether, and then under the action of a catalyst, esterification reaction occurs between the hydroxyl group in the vanillyl alcohol modified polyethylene glycol diglycidyl ether and the carboxyl group in the lysine structure, to obtain a toughening anti-aging cured product; the toughening anti-aging cured product has a polyethylene glycol flexible chain segment in the structure, forming a rigid-flexible combined molecular structure, the flexible chain segment can absorb external stress, effectively disperse the stress generated in the curing process, reduce the possibility of brittle fracture of the phenolic resin, and improve the impact resistance thereof; the phenolic hydroxyl group contained in the structure can effectively capture free radicals, inhibit the aging process of the phenolic resin, and effectively prolong the service life of the phenolic resin; meanwhile, the amino group contained in the structure can form a stable imine bond with the methylol group in the phenolic resin in the curing process of the phenolic resin, produce a crosslinking structure, complete the late-stage supplemental curing, and produce a synergistic effect with the early-stage curing to effectively improve the crosslinking density, enhance the compactness of the phenolic resin structure, and further enhance the impact resistance, tensile strength and wear resistance of the phenolic resin, effectively expanding the use field of the phenolic resin.

[0022] Further, in step SS1, the temperature of the temperature rising reaction is 85-90 DEG C, and the time is 5-6h.

[0023] Further, in step SS2, the catalyst is p-toluenesulfonic acid.

[0024] A preparation method of a curing agent for a phenolic resin, comprising the following steps:

[0025] Step one, the curing-resistant filler and polyvinylpyrrolidone are placed in a high-speed mixer, mixed at 50-55 DEG C for 10-15 min, and then transferred to a three-roll mill for grinding, to obtain a curing agent component A;

[0026] Step two, the toughening anti-aging cured product and dioctyl phthalate are mixed, and then homogeneously dispersed at 45-50 DEG C, to obtain a curing agent component B.

[0027] Further, in step one, the roller spacing of the three-roll mill is 40-50 mu m, 20-30 mu m or 10-20 mu m.

[0028] The present application has the following advantages:

[0029] The application can effectively promote the curing process of the phenolic resin by preparing the main components of the A component and the B component of the phenolic resin curing agent, the A component is pre-cured at 120-130 DEG C, the B component is post-cured at 140-150 DEG C, and the synergistic effect of the two can effectively promote the curing process of the phenolic resin, and the cured phenolic resin can form a dense three-dimensional network structure, effectively improve the mechanical strength, toughness and wear resistance of the phenolic resin, and endow it with excellent anti-aging ability, greatly expand its application field, and effectively prolong the service life of the phenolic resin.

[0030] Of course, implementing any product of the present application does not necessarily require all the advantages described above. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0032] Figure 1 The preparation flow chart of the A component and the B component of the phenolic resin curing agent of the present application. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] The preparation method of the curing-promoting wear-resistant filler and the toughening anti-aging curing product in the following embodiments and comparative examples of the present application is as follows:

[0035] I. Preparation of the curing-promoting wear-resistant filler

[0036] S1: 3g of vermiculite powder was placed in 80ml of anhydrous ethanol, ultrasonic dispersion was carried out for 11min, then 1g of (3-chloropropyl)tris(trimethylsiloxy)silane was added, a 35wt% oxalic acid solution was used to adjust the pH to 5, the temperature was raised to 58 DEG C and reacted for 7h, and then the product was extracted, washed and dried to obtain chloropropylated vermiculite powder;

[0037] S2: 3.6 g of chloropropylated vermiculite powder was placed in 100 ml of toluene, ultrasonic dispersion for 16 min, then 3.8 g of aminomethanesulfonic acid and 0.05 g of potassium carbonate were added, and the temperature was raised to 50°C for 4 h. After filtration, washing and drying, the curing-promoting wear-resistant filler was obtained.

[0038] The nitrogen and sulfur contents of the chloropropylated vermiculite powder and the curing-promoting wear-resistant filler were analyzed using an EMA 502 elemental analyzer. The analysis showed that the chloropropylated vermiculite powder did not contain nitrogen and sulfur, while the nitrogen content of the curing-promoting wear-resistant filler was 1.9% and the sulfur content was 4.4%. This was because the active chlorine on the surface of the chloropropylated vermiculite powder reacted with the amino group in the aminomethanesulfonic acid structure, introducing nitrogen and sulfur.

[0039] II. Preparation of toughening and anti-aging curing product

[0040] SS1: 2.8 g of polyethylene glycol diglycidyl ether and 2.6 g of vanillyl alcohol were placed in 60 ml of toluene, mixed and stirred thoroughly, then 0.3 g of boron trifluoride ether was added, the temperature was raised to 88°C for 5.5 h, and the solvent was removed by distillation under reduced pressure. The product was collected to obtain vanillyl alcohol modified polyethylene glycol diglycidyl ether.

[0041] SS2: 3.2 g of vanillyl alcohol modified polyethylene glycol diglycidyl ether and 3 g of lysine were placed in 85 ml of N,N-dimethylformamide, mixed and stirred thoroughly, then 0.6 g of p-toluenesulfonic acid was added, the temperature was raised to 98°C for 3.5 h, and the product was collected after distillation under reduced pressure to obtain the toughening and anti-aging curing product.

[0042] The nitrogen and oxygen contents of the vanillyl alcohol modified polyethylene glycol diglycidyl ether and the toughening and anti-aging curing product were analyzed using an EMA 502 elemental analyzer. The analysis showed that the vanillyl alcohol modified polyethylene glycol diglycidyl ether did not contain nitrogen, and the oxygen content was 30.6%; while the nitrogen content of the toughening and anti-aging curing product was 6.8% and the oxygen content was 25.1%. Through comparison, it was found that the nitrogen element appeared in the toughening and anti-aging curing product while the oxygen content decreased, which was due to the esterification reaction between the hydroxyl group in the structure of the vanillyl alcohol modified polyethylene glycol diglycidyl ether and the carboxyl group in the structure of lysine, introducing nitrogen element while removing water, resulting in the decrease of oxygen element.

[0043] Example 1

[0044] A curing agent for phenolic resin, composed of two parts, component A and component B; component A includes the following raw materials by weight: 6 parts of curing-promoting wear-resistant filler, 1 part of polyvinylpyrrolidone; component B includes the following raw materials by weight: 15 parts of toughening and anti-aging curing product, 2 parts of dioctyl phthalate;

[0045] The preparation method of the phenolic resin curing agent comprises the following steps:

[0046] Step one, the curing-promoting wear-resistant filler and polyvinylpyrrolidone are placed in a high-speed mixer, mixed at 50 DEG C for 10 min, then transferred to a three-roll grinding machine, the roller spacing is set to 40 mu m, 20 mu m, 10 mu m, and the curing agent component A is obtained after grinding;

[0047] Step two, the toughening and anti-aging curing product is mixed with dioctyl phthalate, then homogeneously dispersed at 45 DEG C to obtain the curing agent component B.

[0048] Example 2

[0049] A phenolic resin curing agent is composed of two parts of component A and component B; the component A comprises the following raw materials by weight: 7 parts of curing-promoting wear-resistant filler, 1.5 parts of polyvinylpyrrolidone; the component B comprises the following raw materials by weight: 18 parts of toughening and anti-aging curing product, 2.5 parts of dioctyl phthalate;

[0050] The preparation method of the phenolic resin curing agent comprises the following steps:

[0051] Step one, the curing-promoting wear-resistant filler and polyvinylpyrrolidone are placed in a high-speed mixer, mixed at 52 DEG C for 12 min, then transferred to a three-roll grinding machine, the roller spacing is set to 45 mu m, 25 mu m, 15 mu m, and the curing agent component A is obtained after grinding;

[0052] Step two, the toughening and anti-aging curing product is mixed with dioctyl phthalate, then homogeneously dispersed at 48 DEG C to obtain the curing agent component B.

[0053] Example 3

[0054] A phenolic resin curing agent is composed of two parts of component A and component B; the component A comprises the following raw materials by weight: 7 parts of curing-promoting wear-resistant filler, 1.5 parts of polyvinylpyrrolidone; the component B comprises the following raw materials by weight: 18 parts of toughening and anti-aging curing product, 2.5 parts of dioctyl phthalate;

[0055] The preparation method of the phenolic resin curing agent comprises the following steps:

[0056] Step one, the curing-promoting wear-resistant filler and polyvinylpyrrolidone are placed in a high-speed mixer, mixed at 55 DEG C for 15 min, then transferred to a three-roll grinding machine, the roller spacing is set to 50 mu m, 30 mu m, 20 mu m, and the curing agent component A is obtained after grinding;

[0057] Step two, the toughening and anti-aging curing product is mixed with dioctyl phthalate, then homogeneously dispersed at 50 DEG C to obtain the curing agent component B.

[0058] Comparative Example 1

[0059] A curing agent for phenolic resin, which is composed of two parts of component A and component B; wherein component A comprises the following raw materials in parts by weight: 1.5 parts of polyvinylpyrrolidone; component B comprises the following raw materials in parts by weight: 18 parts of toughening anti-aging curing product, 2.5 parts of dioctyl phthalate;

[0060] The preparation method of the curing agent for phenolic resin comprises the following steps:

[0061] Step one, place the polyvinylpyrrolidone in a high-speed mixer, mix at 52℃ for 12min, then transfer to a three-roll mill, set the roller spacing to 45μm, 25μm, 15μm, grind to obtain component A of the curing agent;

[0062] Step two, mix the toughening anti-aging curing product and dioctyl phthalate, then homogeneously disperse at 48℃ to obtain component B of the curing agent.

[0063] Comparative Example 2

[0064] A curing agent for phenolic resin, which is composed of two parts of component A and component B; wherein component A comprises the following raw materials in parts by weight: 7 parts of curing-promoting wear-resistant filler, 1.5 parts of polyvinylpyrrolidone; component B comprises the following raw materials in parts by weight: 2.5 parts of dioctyl phthalate;

[0065] The preparation method of the curing agent for phenolic resin comprises the following steps:

[0066] Step one, place the curing-promoting wear-resistant filler and polyvinylpyrrolidone in a high-speed mixer, mix at 52℃ for 12min, then transfer to a three-roll mill, set the roller spacing to 45μm, 25μm, 15μm, grind to obtain component A of the curing agent;

[0067] Step two, homogeneously disperse the dioctyl phthalate at 48℃ to obtain component B of the curing agent.

[0068] Comparative Example 3

[0069] A curing agent for phenolic resin, which is composed of two parts of component A and component B; wherein component A comprises the following raw materials in parts by weight: 7 parts of curing-promoting wear-resistant filler, 1.5 parts of polyvinylpyrrolidone; component B comprises the following raw materials in parts by weight: 18 parts of polyethylene glycol diglycidyl ether, 2.5 parts of dioctyl phthalate;

[0070] The preparation method of the curing agent for phenolic resin comprises the following steps:

[0071] Step one, put the curing-promoting wear-resistant filler and polyvinylpyrrolidone into a high-speed mixer, mix at 52℃ for 12min, then transfer to a three-roll mill, set the roller spacing to 45μm, 25μm, 15μm, after grinding, get the curing agent component A;

[0072] Step two, mix the polyethylene glycol diglycidyl ether and dioctyl phthalate, then homogenously disperse at 48℃, get the curing agent component B.

[0073] Comparative example 4

[0074] A curing agent for phenolic resin, composed of two parts, component A and component B; component A includes the following raw materials by weight: 7 parts of curing-promoting wear-resistant filler, 1.5 parts of polyvinylpyrrolidone; component B includes the following raw materials by weight: 18 parts of vanillyl alcohol modified polyethylene glycol diglycidyl ether, 2.5 parts of dioctyl phthalate;

[0075] The preparation method of the curing agent for phenolic resin, including the following steps:

[0076] Step one, put the curing-promoting wear-resistant filler and polyvinylpyrrolidone into a high-speed mixer, mix at 52℃ for 12min, then transfer to a three-roll mill, set the roller spacing to 45μm, 25μm, 15μm, after grinding, get the curing agent component A;

[0077] Step two, mix the vanillyl alcohol modified polyethylene glycol diglycidyl ether and dioctyl phthalate, then homogenously disperse at 48℃, get the curing agent component B.

[0078] Performance detection

[0079] Mix the curing agent component A prepared in example 1 to example 3, comparative example 1 to comparative example 4 with phenolic resin respectively in a mold, the mass ratio of component A to phenolic resin is 0.8:10, pre-cure at 125℃ for 1h, then add the curing agent component B for phenolic resin respectively, the mass ratio of component B to phenolic resin is 1.2:10, continue to cure for 2h, then demold, make samples that meet the specifications; detect the tensile strength of the samples and the samples treated in a 100℃ aging oven for 24h according to the standard GB / T1040.1-2018, judge the anti-aging ability of the samples; test the impact strength of the samples according to the standard GB / T1843-2008, judge the toughness and impact resistance of the samples; test the abrasion of the samples according to the standard GB / T5478-2008, judge the wear resistance of the samples; the specific test results are shown in the table below:

[0080]

[0081] From the above table, it can be seen that the samples prepared in Examples 1-3 have excellent tensile strength, anti-aging ability, impact resistance and wear resistance. In the sample prepared in Comparative Example 1, no curing-promoting wear-resistant filler is added, and in the sample prepared in Comparative Example 2, no toughening anti-aging curing agent is added. Therefore, the sample prepared in Comparative Example 1 has general compactness, but good anti-aging ability and toughness, and poor wear resistance. The sample prepared in Comparative Example 2 has general wear resistance, poor toughness and anti-aging ability. In the sample prepared in Comparative Example 3, polyethylene glycol diglycidyl ether is directly added. Due to the introduction of epoxy groups, the compactness of the sample is enhanced, and therefore the tensile strength, toughness and wear resistance are excellent, but the anti-aging ability is poor. In the sample prepared in Comparative Example 4, vanillyl alcohol modified polyethylene glycol diglycidyl ether is directly added. The anti-aging ability is good, but the compactness of the sample is general, and therefore the tensile strength, toughness and wear resistance are inferior to those of the samples prepared in Examples.

[0082] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the skilled person in the art can combine and combine the different embodiments or examples described in the present specification and the features of the different embodiments or examples, without contradiction.

[0083] The above is only an example and description of the concept of the present application. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the scope defined by the concept of the application, which shall belong to the protection scope of the present application.

Claims

1. A curing agent for phenolic resin, characterized in that, The application relates to a solidifying agent, which is composed of two parts, namely a component A and a component B; the component A comprises the following raw materials in parts by weight: 6-8 parts of a solidifying-promoting wear-resistant filler, 1-2 parts of polyvinylpyrrolidone; the component B comprises the following raw materials in parts by weight: 15-20 parts of a toughening and anti-aging solidifying agent, 2-3 parts of dioctyl phthalate; the solidifying-promoting wear-resistant filler is prepared by reacting chloropropylized vermiculite powder with aminomethanesulfonic acid; the chloropropylized vermiculite powder is prepared by surface modification of (3-chloropropyl)tris(trimethylsiloxy)silane on vermiculite powder; the toughening and anti-aging solidifying agent is prepared by reacting vanillyl alcohol modified polyethylene glycol diglycidyl ether with lysine; and the vanillyl alcohol modified polyethylene glycol diglycidyl ether is prepared by reacting polyethylene glycol diglycidyl ether with vanillyl alcohol.

2. The curing agent for phenol resin according to claim 1, characterized by The preparation method of the solidifying-promoting wear-resistant filler comprises the following steps: S1: vermiculite powder is placed in anhydrous ethanol, ultrasonic dispersion is carried out for 10-12 min, then (3-chloropropyl)tris(trimethylsiloxy)silane is added, an oxalic acid solution is used to adjust the pH to 4-6, the temperature is raised to 55-60 DEG C, and reaction is carried out for 6-8 h; after filtration, washing and drying, chloropropylized vermiculite powder is obtained; S2: the chloropropylized vermiculite powder is placed in toluene, ultrasonic dispersion is carried out for 15-18 min, then aminomethanesulfonic acid and an accelerator are added, the temperature is raised to 45-55 DEG C, and reaction is carried out for 3-5 h; after filtration, washing and drying, the solidifying-promoting wear-resistant filler is obtained.

3. The curing agent for phenol resin according to claim 2, characterized by In step S1, the mass fraction of oxalic acid in the oxalic acid solution is 30-40%.

4. The curing agent for phenol resin according to claim 2, characterized by In step S2, the accelerator is any one of potassium carbonate and pyridine.

5. The curing agent for phenol-formaldehyde resins according to claim 1, characterized in that, The preparation method of the toughening and anti-aging solidifying agent comprises the following steps: SS1: polyethylene glycol diglycidyl ether and vanillyl alcohol are placed in toluene, fully mixed and stirred, then boron trifluoride ether is added, reaction is carried out by raising the temperature, the solvent is removed by distillation under reduced pressure, and the product is collected to obtain vanillyl alcohol modified polyethylene glycol diglycidyl ether; SS2: the vanillyl alcohol modified polyethylene glycol diglycidyl ether and lysine are placed in N,N-dimethylformamide, fully mixed and stirred, then a catalyst is added, the temperature is raised to 95-100 DEG C, and reaction is carried out for 3-4 h; after distillation under reduced pressure, the product is collected to obtain the toughening and anti-aging solidifying agent.

6. The curing agent for phenol-formaldehyde resins according to claim 5, characterized in that, In step SS1, the temperature of the reaction by raising the temperature is 85-90 DEG C, and the time is 5-6 h.

7. The curing agent for phenol resin according to claim 5, characterized by comprising: In step SS2, the catalyst is p-toluenesulfonic acid.

8. A method for producing the curing agent for phenol formaldehyde resins according to claim 1, characterized by, The application further relates to a preparation method of the solidifying agent, which comprises the following steps: Step one: the solidifying-promoting wear-resistant filler and polyvinylpyrrolidone are placed in a high-speed mixer, mixed at 50-55 DEG C for 10-15 min, then transferred to a three-roll mill for grinding to obtain the component A of the solidifying agent; Step two: the toughening and anti-aging solidifying agent and dioctyl phthalate are mixed, then uniformly dispersed at 45-50 DEG C to obtain the component B of the solidifying agent.

9. The method for preparing a curing agent for phenolic resin according to claim 8, characterized in that, In step one, the roll spacing of the three-roll mill is 40-50 mu m, 20-30 mu m and 10-20 mu m.

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