Preparation method of phenolic resin with high curing speed

Abstract

The invention discloses a preparation method of phenolic resin with high curing speed, and relates to the technical field of phenolic resin, the preparation method comprises the following steps: S1, putting a phenolic organic compound and an acidic solution into a reaction kettle; s2, pouring an aldehyde organic compound, and heating the interior of the reaction kettle to 200-300 DEG C; s3, adding a metal oxide, heating to 300-400 DEG C, and stirring; s4, reducing the temperature in the reaction kettle to 150 DEG C; s5, high-temperature acid gas is introduced into the reaction kettle from the bottom of the reaction kettle, moisture in the reaction kettle can be rapidly evaporated through the high-temperature acid gas, the high-temperature acid gas can be fully mixed with the phenolic organic compound and the aldehyde organic compound, the reaction efficiency is improved, the curing efficiency of the phenolic resin is improved, and the service life of the phenolic resin is prolonged. The high-temperature acid gas is injected in a pulse impact mode, the high-temperature acid gas can be fully mixed with the phenolic organic compound and the aldehyde organic compound, the effect of vibrating the separated phenolic resin is achieved, and the curing efficiency of the phenolic resin is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of phenolic resins, and specifically relates to a preparation method of a phenolic resin with a fast curing speed. Background Art

[0002] Phenolic resin (also known as bakelite, bakelite powder) is a colorless or yellowish-brown transparent substance, resistant to weak acids and weak bases, decomposes when exposed to strong acids, corrodes when exposed to strong bases, insoluble in water, and soluble in organic solvents such as acetone and alcohol. It is divided into two categories: thermosetting and thermoplastic. Phenolic resin is obtained by the polycondensation of phenol aldehyde or its derivatives. The phenolic resin sold in the market often contains colorants and shows colors such as red, yellow, black, green, brown, and blue, and is available in granular and powdery forms.

[0003] The existing preparation process of phenolic resin is relatively conventional. According to the patent number: CN113646349B, patent name: Preparation method of alkoxylated soluble phenolic resin type phenolic resin, which records "a method for preparing alkoxylated soluble phenolic resin type phenolic resin, the method includes: (a) reacting a phenolic compound which is a mixture of phenol and p-alkylphenol with an aldehyde compound in the presence of a basic compound to obtain a soluble phenolic resin type phenolic resin; and (b) reacting the soluble phenolic resin type phenolic resin with an alcohol compound to prepare an alkoxylated soluble phenolic resin type phenolic resin". Those skilled in the art can know that the preparation of phenolic resin is obtained by reacting a phenolic compound with an aldehyde compound in a catalyst. However, the preparation efficiency has not been improved well. Moreover, during the preparation process of phenolic resin, the phenolic resin needs to be cured, and at this time, the phenolic resin needs to be dried or evaporated to treat the moisture in the phenolic resin to improve the curing speed, which increases the process and reduces the production efficiency at the same time.

[0004] In summary, a preparation method of a phenolic resin with a fast curing speed is designed. Summary of the Invention

[0005] In order to overcome the above deficiencies, the present invention provides a preparation method of a phenolic resin with a fast curing speed.

[0006] The present invention achieves the above object through the following technical solutions: A preparation method of a phenolic resin with a fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle; S2: Pour in aldehyde organic compounds, and heat the temperature inside the reaction kettle to 200 - 300 °C; S3: Add metal oxides, and heat to 300 - 400 °C for stirring; S4: Lower the temperature in the reaction kettle to 150 °C; S5: Introduce high-temperature acidic gas into the reactor from the bottom of the reactor until the water in the reactor evaporates completely, leaving phenolic resin. Among them, in step S5, the high-temperature acidic gas is injected into the acidic solution in the reactor in the form of pulsed impact.

[0007] Preferably, in steps S1 and S2, the molar ratio of phenolic organic compound to aldehyde organic compound is 1:0.97 or 1:1. Improper ratio of phenol to aldehyde in phenolic resin will affect the curing speed. Adjusting the ratio appropriately to enhance the cross-linking effect can promote curing. After experiments, when the molar ratio of phenolic organic compound to aldehyde organic compound is 1:0.97 or 1:1, the curing speed of phenolic resin is the best.

[0008] Preferably, in step S1, the acidic solution is sulfuric acid or phosphoric acid, and in step S2, the heating time in the reactor is 8 - 16 h.

[0009] Preferably, in step S3, the metal oxide is magnesium oxide, molybdenum or tungsten oxide. Molybdic acid or tungstic acid reacts with phenol and formaldehyde to embed metal elements into the resin main chain in the form of chemical bonds. The bond energy of molybdenum-oxygen bond (Mo - O) is higher than that of ordinary C - C bond, which significantly improves the heat resistance and ablation resistance. Magnesium oxide, etc. are dispersed into the resin matrix by ball milling or in-situ reaction. The molar ratio of the metal oxide to the mixture of phenolic organic compound and aldehyde organic compound is 0.1 - 0.3.

[0010] Preferably, in step S4, after the temperature in the reactor drops to 150 °C, phenolic resin begins to precipitate in the reactor. At this time, an organic solution is appropriately added. The organic solution is an alcohol or ketone solvent, which can reduce the energy required for the curing reaction and accelerate the reaction speed.

[0011] Preferably, in step S5, the temperature of the high-temperature acidic gas is 800 - 1000 °C, and the high-temperature acidic gas is sulfuric acid or phosphoric acid.

[0012] Preferably, the phenolic organic compound is at least one of p-cresol, p-tert-butylphenol, p-ethylphenol and p-tert-octylphenol, and the aldehyde organic compound is at least one of paraformaldehyde, formaldehyde and glyoxal.

[0013] Preferably, in step S5, the pulse impact frequency of the high-temperature acidic gas is 100 Hz - 1000 Hz. The higher the pulse impact frequency, the more obvious the mechanical vibration effect on the precipitated phenolic resin.

[0014] The beneficial effect of the present invention is: in the preparation method of the phenolic resin with fast curing speed: 1. By means of high-temperature acidic gas, not only can the moisture in the reaction kettle be rapidly evaporated, but also it can be fully mixed with phenolic organic compounds and aldehyde organic compounds, improving the reaction efficiency, thereby enhancing the curing efficiency of phenolic resin. 2. Injecting high-temperature acidic gas in a pulsed impact manner can not only fully mix the high-temperature acidic gas with phenolic organic compounds and aldehyde organic compounds, but also have a vibration effect on the precipitated phenolic resin, accelerating the curing efficiency of phenolic resin. 3. Introducing divalent metal ions, metal oxides or compounds containing metal elements can be introduced into phenolic resin by physical blending or chemical bonding, which can promote resin curing and reduce the molding pressure. Specific embodiments

[0015] Now, the present invention will be further described in detail.

[0016] A preparation method of phenolic resin with fast curing speed includes the following steps: S1: Put phenolic organic compounds and acidic solution into a reaction kettle. S2: Pour in aldehyde organic compounds, heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid or phosphoric acid, the heating time in the reaction kettle is 8 - 16 h, the molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:0.97 or 1:1. The phenolic organic compound is at least one of p-cresol, p-tert-butylphenol, p-ethylphenol, and p-tert-octylphenol, and the aldehyde organic compound is at least one of paraformaldehyde, formaldehyde, and glyoxal. S3: Add metal oxide, heat to 300 - 400 °C and stir. The metal oxide is molybdenum or tungsten oxide, magnesium oxide, and the molar ratio of the metal oxide to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.1 - 0.3. S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, an organic solution can be appropriately added. The organic solution can be an alcohol or ketone solvent. S5: From the bottom of the reaction kettle, introduce high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 800 - 1000 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the moisture in the reaction kettle evaporates completely, leaving phenolic resin. The frequency of pulsed impact of the high-temperature acidic gas is 100 Hz - 1000 Hz, and the high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific example 1:

[0018] A preparation method of phenolic resin with fast curing speed includes the following steps: S1: Put phenolic organic compounds and acidic solution into a reaction kettle.

[0019] S2: Pour in the aldehyde organic compound. The molar ratio of the phenolic organic compound to the aldehyde organic compound is 1:0.97. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h; S3: Add the metal oxide and heat to 300 - 400 °C for stirring. The metal oxide is molybdenum or tungsten oxide, magnesium oxide. The molar ratio of the metal oxide to the mixture of the phenolic organic compound and the aldehyde organic compound is 0.1; S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent; S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 800 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving phenolic resin. The pulsed impact frequency of the high-temperature acidic gas is 100 Hz, and the high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Example 2:

[0021] A preparation method of phenolic resin with fast curing speed, comprising the following steps: S1: Put the phenolic organic compound and the acidic solution into the reaction kettle.

[0022] S2: Pour in the aldehyde organic compound. The molar ratio of the phenolic organic compound to the aldehyde organic compound is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h; S3: Add the metal oxide and heat to 300 - 400 °C for stirring. The metal oxide is molybdenum or tungsten oxide, magnesium oxide. The molar ratio of the metal oxide to the mixture of the phenolic organic compound and the aldehyde organic compound is 0.1; S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent; S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 800 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving phenolic resin. The pulsed impact frequency of the high-temperature acidic gas is 100 Hz, and the high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Example 3:

[0024] A preparation method of phenolic resin with fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle.

[0025] S2: Pour in aldehyde organic compounds. The molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h. S3: Add metal oxides, heat to 300 - 400 °C and stir. The metal oxides are molybdenum or tungsten oxides, magnesium oxide. The molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.1. S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent. S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 800 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving phenolic resin. The pulse impact frequency of the high-temperature acidic gas is 100 Hz. The high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Example 4:

[0027] A preparation method of phenolic resin with a fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle.

[0028] S2: Pour in aldehyde organic compounds. The molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h. S3: Add metal oxides, heat to 300 - 400 °C and stir. The metal oxides are molybdenum or tungsten oxides, magnesium oxide. The molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.2. S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent. S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 900 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving phenolic resin. The pulse impact frequency of the high-temperature acidic gas is 100 Hz. The high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Example 5:

[0030] A preparation method of a phenolic resin with a fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle.

[0031] S2: Pour in aldehyde organic compounds. The molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h; S3: Add metal oxides, heat to 300 - 400 °C and stir. The metal oxides are molybdenum or tungsten oxides, magnesium oxide. The molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.3; S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent; S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 900 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving the phenolic resin. The pulsed impact frequency of the high-temperature acidic gas is 100 Hz. The high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Example 6:

[0033] A preparation method of a phenolic resin with a fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle.

[0034] S2: Pour in aldehyde organic compounds. The molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h; S3: Add metal oxides, heat to 300 - 400 °C and stir. The metal oxides are molybdenum or tungsten oxides, magnesium oxide. The molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.3; S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent; S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 1000 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving the phenolic resin. The pulsed impact frequency of the high-temperature acidic gas is 100 Hz. The high-temperature acidic gas is sulfuric acid or phosphoric acid. Specific Embodiment 7:

[0036] A preparation method of a phenolic resin with a fast curing speed, comprising the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle.

[0037] S2: Pour in aldehyde organic compounds. The molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1. The phenolic organic compound is p-cresol, and the aldehyde organic compound is paraformaldehyde. Heat the internal temperature of the reaction kettle to 200 - 300 °C. The acidic solution is sulfuric acid, and the heating time in the reaction kettle is 8 - 16 h; S3: Add metal oxides and heat to 300 - 400 °C for stirring. The metal oxides are molybdenum or tungsten oxides, magnesium oxide. The molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.3; S4: When the temperature in the reaction kettle drops to 150 °C, phenolic resin begins to precipitate in the reaction kettle. At this time, appropriately add an alcohol solvent; S5: From the bottom of the reaction kettle, introduce a high-temperature acidic gas into the reaction kettle. The temperature of the high-temperature acidic gas is 1000 °C. The high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulsed impact until the water in the reaction kettle evaporates completely, leaving the phenolic resin. The pulsed impact frequency of the high-temperature acidic gas is 1000 Hz. The high-temperature acidic gas is sulfuric acid or phosphoric acid.

[0038] In the three embodiments, from the end of step S4 to the end of step S5, until the water in the reaction kettle evaporates completely, leaving the phenolic resin, the time consumed is Hn, where n is the nth embodiment; In Embodiment 1, H1 = 3 h; in Embodiment 2, H2 = 2.5 h; in Embodiment 3, H3 = 3 h; in Embodiment 4, H4 = 2 h; in Embodiment 5, H5 = 1.8 h; in Embodiment 6, H6 = 1.5 h; in Embodiment 7, H6 = 1.1 h.

[0039] In summary, the molar ratio between phenolic organic compounds and aldehyde organic compounds affects the curing efficiency of phenolic resin. When the molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:1, the curing efficiency of phenolic resin is the highest; In step S3, the higher the molar ratio of the added metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds, the higher the curing efficiency of phenolic resin; In step S5, the higher the temperature of the high-temperature acidic gas, the higher the curing efficiency of phenolic resin; In step S5, the higher the pulsed impact frequency of the high-temperature acidic gas, the higher the curing efficiency of phenolic resin.

[0040] Based on the inspiration of the present invention, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A preparation method of a phenolic resin with a fast curing speed, characterized in that: It includes the following steps: S1: Put phenolic organic compounds and an acidic solution into a reaction kettle; S2: Pour aldehyde organic compounds into it, and heat the internal temperature of the reaction kettle to 200~300°C; S3: Add metal oxides, and heat to 300~400°C for stirring; S4: Let the temperature in the reaction kettle drop to 150°C; S5: From the bottom of the reaction kettle, introduce high-temperature acidic gas into the reaction kettle until the water in the reaction kettle evaporates completely, leaving phenolic resin; Among them, in step S5, the high-temperature acidic gas is injected into the acidic solution in the reaction kettle in the form of pulse impact.

2. The preparation method of a phenolic resin with fast curing speed according to claim 1, characterized in that: In steps S1 and S2, the molar ratio of phenolic organic compounds to aldehyde organic compounds is 1:0.97 or 1:

1.

3. The preparation method of a phenolic resin with fast curing speed according to claim 1, characterized in that: In step S1, the acidic solution is sulfuric acid or phosphoric acid. In step S2, the heating time in the reaction kettle is 8-16h.

4. The preparation method of a phenolic resin with a fast curing rate according to claim 1, characterized in that: In step S3, the metal oxides are magnesium oxide, molybdenum or tungsten oxides, and the molar ratio of the metal oxides to the mixture of phenolic organic compounds and aldehyde organic compounds is 0.1~0.

3.

5. The preparation method of a phenolic resin with fast curing speed according to claim 1, characterized in that: In step S4, after the temperature in the reaction kettle drops to 150°C, phenolic resin begins to precipitate in the reaction kettle. At this time, an organic solution is appropriately added. The organic solution is an alcohol or ketone solvent.

6. The preparation method of a phenolic resin with a fast curing rate according to claim 1, characterized in that: In step S5, the temperature of the high-temperature acidic gas is 800~1000°C, and the high-temperature acidic gas is sulfuric acid or phosphoric acid.

7. The preparation method of a phenolic resin with fast curing speed according to claim 1, characterized in that: The phenolic organic compounds are at least one of p-cresol, p-tert-butylphenol, p-ethylphenol and p-tert-octylphenol, and the aldehyde organic compounds are at least one of paraformaldehyde, formaldehyde and glyoxal.

8. The preparation method of a phenolic resin with fast curing speed according to claim 1, characterized in that: In step S5, the frequency of the pulse impact of the high-temperature acidic gas is 100Hz~1000Hz.