CN114644743B - Preparation process of low-temperature fast curing phenolic resin - Google Patents
Preparation process of low-temperature fast curing phenolic resin Download PDFInfo
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- CN114644743B CN114644743B CN202210474749.4A CN202210474749A CN114644743B CN 114644743 B CN114644743 B CN 114644743B CN 202210474749 A CN202210474749 A CN 202210474749A CN 114644743 B CN114644743 B CN 114644743B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The invention discloses a preparation process of low-temperature fast curing phenolic resin, which comprises the steps of mixing a modifier with a cross-linking agent to enable hydroxyl groups of side chains of the modifier to react with isocyanate groups on the cross-linking agent to prepare a treatment liquid, reacting phenol with formaldehyde to prepare a phenolic solution, reacting the phenolic solution with the treatment liquid to enable partial phenolic hydroxyl groups on the side chains in the phenolic solution to react with chlorine atom sites on the side chains in the treatment liquid to form a grid shape, then carrying out esterification reaction with 1,12-dodecanediol to enable carboxyl groups of side chains of adjacent grid molecules to react with hydroxyl groups on 1,12-dodecanediol to further form a three-dimensional grid structure, and then carrying out resin liquid curing by barium hydroxide and diethylenetriamine to enable the curing temperature and the curing time of the phenolic resin to be greatly reduced, and meanwhile, the toughness of the three-dimensional grid structure is improved.
Description
Technical Field
The invention relates to the technical field of high polymer material preparation, in particular to a preparation process of low-temperature fast curing phenolic resin.
Background
The phenolic resin has excellent heat resistance, ablation resistance, flame retardant property and the like, and is widely used as a general matrix resin of a heat-proof ablation-resistant material. At present, the rapid development of the advanced technology of aerospace and national defense puts higher requirements on the heat resistance and flexibility of a resin matrix: the ablation resistant material should have some flexibility. However, the conventional phenolic resin is difficult to meet the requirements in the aspects of properties such as interlaminar shear strength, elongation at break and the like.
The prior method for realizing low-temperature rapid curing of phenolic resin mainly comprises low-temperature curing modification in the preparation process of the resin and addition of a rapid curing agent in the use process. The modified low-temperature cured phenolic resin is mainly modified by chemical modification and blending modification. The chemical modification is to introduce other ions or groups to participate in the synthesis system of the resin together by adding a catalyst or a modifier, so as to improve the degree of polycondensation reaction, thereby improving the average molecular weight of the polymer or increasing the ortho-para activity of phenol, so as to improve the reaction activity in the curing process.
Disclosure of Invention
The invention aims to provide a preparation process of low-temperature fast curing phenolic resin, which solves the problems of long curing time, high curing temperature and high brittleness of the phenolic resin at the present stage.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of low-temperature fast curing phenolic resin specifically comprises the following steps:
step S1: mixing a modifier and a cross-linking agent, and reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 50-60 ℃ to prepare a treatment fluid;
step S2: uniformly mixing phenol, sodium hydroxide and deionized water, stirring and dropwise adding formaldehyde under the conditions that the rotating speed is 150-200r/min and the temperature is 20-25 ℃, reacting for 2-3h, heating to 80-90 ℃, adding xylenol, and continuously reacting for 0.5-1h to prepare a phenolic solution;
and step S3: uniformly mixing the phenolic solution and the treatment solution, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 150-200r/min and the temperature is 60-70 ℃, reacting for 2-3h, adjusting the pH value of the reaction to be acidic, adding excessive 1,12-dodecanediol and p-toluenesulfonic acid, reacting for 1-2h under the temperature of 90-100 ℃ to prepare phenolic resin solution, uniformly mixing the phenolic resin solution, barium hydroxide and diethylenetriamine, and curing and reacting for 50-70min under the temperature of 20-25 ℃ to prepare the phenolic resin.
Further, the molar ratio of the hydroxyl group in the modifier and the isocyanate group in the crosslinking agent in step S1 is 1:1.
Furthermore, the mass ratio of the phenol, the sodium hydroxide, the deionized water and the formaldehyde in the step S2 is 10.
Furthermore, the phenolic hydroxyl group content of the phenolic solution in the step S3 is 3-5 times of the chlorine atom content in the treatment solution, and the dosage ratio of the phenolic resin solution, the barium hydroxide and the diethylenetriamine is 20mL.
Further, the modifier is prepared by the following steps:
step A1: mixing phenol, potassium carbonate, potassium hydroxide and dimethyl sulfoxide, reacting for 20-30min at the rotation speed of 150-200r/min and the temperature of 25-30 ℃, adding 4,4' -diaminodiphenyl sulfone, heating to the temperature of 170-180 ℃, continuing to react for 8-10h, decoloring by using activated carbon, and recrystallizing a substrate by using N, N-dimethylformamide to prepare an intermediate 1;
the reaction process is as follows:
step A2: uniformly mixing the intermediate 1, anhydrous aluminum chloride and p-hydroxybenzoyl chloride, reacting at the rotation speed of 120-150r/min and the temperature of 50-60 ℃ until no hydrogen chloride gas is generated, adding the reaction solution into ice water, and filtering to remove filtrate to obtain an intermediate 2;
the reaction process is as follows:
step A3: mixing the low intermediate 2 and epoxy chloropropane, stirring for 1.5-3h at the conditions of the rotation speed of 150-200r/min and the temperature of 110-120 ℃, dropwise adding a sodium hydroxide solution for 1.5-2h, reacting for 3-5h at the rotation speed of 600-800r/min after dropwise adding is finished, adding ferric trichloride until the color of the reaction solution is not changed, stopping the reaction and cooling to room temperature, adding dichloromethane, standing for layering, removing a water phase, washing the organic phase with deionized water, drying with anhydrous magnesium sulfate, filtering, removing filter residues, distilling the filtrate at the temperature of 120-125 ℃ to remove low-boiling-point substances, and preparing the modifier.
The reaction process is as follows:
further, the phenol and 4,4' -diaminodiphenyl sulfone used in step A1 are used in a molar ratio of 2:1.
Further, the molar ratio of the intermediate 1 and the p-hydroxybenzoyl chloride in the step A2 is 1:2.
Further, the dosage ratio of the intermediate 2, the epichlorohydrin and the sodium hydroxide solution in the step A3 is 0.1g.
The cross-linking agent is prepared by the following steps:
step B1: dissolving 2-chloro-5-nitrotoluene in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions that the rotating speed is 120-150r/min and the temperature is 25-30 ℃, reacting for 40-50min, adjusting the pH value of a reaction solution to 8, and distilling and crystallizing to obtain an intermediate 3;
the reaction process is as follows:
and step B2: adding ethyl acetate into a reaction kettle, stirring and introducing phosgene at the rotation speed of 150-200r/min and the temperature of 30-40 ℃, dropwise adding an ethyl acetate solution of the intermediate 3, reacting for 6-8h to obtain an intermediate 4, uniformly mixing the intermediate 4 and deionized water, stirring and adding a potassium permanganate aqueous solution at the rotation speed of 200-300r/min and the temperature of 80-85 ℃, reacting for 20-30min, filtering while hot, removing filter residues, distilling the filtrate to obtain the cross-linking agent
The reaction process is as follows:
furthermore, the use amount of the 2-chloro-5-nitrotoluene, the concentrated hydrochloric acid and the tin powder in the step B1 is larger than 4g, and the mass fraction of the concentrated hydrochloric acid is 36 percent.
Further, the molar ratio of the intermediate 3 to phosgene in the step B2 is 1.3.
The invention has the beneficial effects that: the invention provides a low-temperature fast curing phenolic resin, which is prepared by mixing a modifier and a crosslinking agent, enabling hydroxyl groups of side chains of the modifier to react with isocyanate groups on the crosslinking agent to prepare a treatment liquid, enabling phenol to react with formaldehyde to prepare a phenolic solution, enabling the phenolic solution to react with the treatment liquid, enabling partial phenolic hydroxyl groups on the side chains in the phenolic solution to react with chlorine atom sites on the side chains in the treatment liquid to form a grid shape, then carrying out an esterification reaction with 1,12-dodecanediol to enable carboxyl groups of side chains of adjacent grid molecules to react with hydroxyl groups on 1,12-dodecanediol to further form a three-dimensional grid structure, then carrying out resin liquid curing by barium hydroxide and diethylenetriamine to enable the curing temperature and the curing time of the phenolic resin to be greatly reduced, meanwhile, the toughness of the three-dimensional grid structure is improved, the modifier takes phenol as a raw material to react with dimethyl sulfoxide to prepare an intermediate 1, then carrying out a friedel-crafts acylation reaction on the intermediate 1 and p-hydroxybenzoyl chloride to prepare an intermediate 2, and finally carrying out a condensation polymerization reaction with epoxy chloropropane to prepare the modifier, wherein the modifier which contains a large amount of ether bonds and the phenolic resin can increase the toughness of molecules.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation process of low-temperature fast curing phenolic resin specifically comprises the following steps:
step S1: mixing a modifier and a cross-linking agent, and reacting for 3 hours at the rotation speed of 200r/min and the temperature of 50 ℃ to prepare a treatment solution;
step S2: uniformly mixing phenol, sodium hydroxide and deionized water, stirring and dropwise adding formaldehyde under the conditions that the rotating speed is 150r/min and the temperature is 20 ℃, reacting for 2 hours, heating to 80 ℃, adding xylenol, and continuously reacting for 0.5 hour to obtain a phenolic solution;
and step S3: uniformly mixing the phenolic resin solution and the treatment solution, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 150r/min and the temperature is 60 ℃, reacting for 2 hours, adjusting the pH value of the reaction to be acidic, adding excessive 1,12-dodecanediol and p-toluenesulfonic acid, reacting for 1 hour under the condition that the temperature is 90 ℃ to prepare phenolic resin solution, uniformly mixing the phenolic resin solution, barium hydroxide and diethylenetriamine, and curing and reacting for 50 minutes under the condition that the temperature is 20 ℃ to prepare the phenolic resin.
The molar ratio of hydroxyl groups in the modifier and isocyanate groups in the crosslinking agent in step S1 is 1:1.
The mass ratio of the phenol, the sodium hydroxide, the deionized water and the formaldehyde in the step S2 is 10.
And (3) the phenolic hydroxyl content of the phenolic solution in the step (S3) is 3 times of the chlorine atom content in the treatment solution, and the dosage ratio of the phenolic resin solution, the barium hydroxide and the diethylenetriamine is 20mL.
The modifier is prepared by the following steps:
step A1: mixing phenol, potassium carbonate, potassium hydroxide and dimethyl sulfoxide, reacting for 20min at the rotation speed of 150r/min and the temperature of 25 ℃, adding 4,4' -diaminodiphenyl sulfone, heating to the temperature of 170 ℃, continuing to react for 8h, decoloring by using activated carbon, and recrystallizing a substrate by using N, N-dimethylformamide to prepare an intermediate 1;
step A2: uniformly mixing the intermediate 1, anhydrous aluminum chloride and p-hydroxybenzoyl chloride, reacting at the rotation speed of 120r/min and the temperature of 50 ℃ until no hydrogen chloride gas is generated, adding the reaction liquid into ice water, and filtering to remove filtrate to obtain an intermediate 2;
step A3: mixing the intermediate 2 and epoxy chloropropane, stirring for 1.5h at the rotation speed of 150r/min and the temperature of 110 ℃, dropwise adding a sodium hydroxide solution for 1.5h, reacting for 3h at the rotation speed of 600r/min after dropwise adding is finished, adding ferric trichloride until the color of the reaction liquid does not change, stopping the reaction, cooling to room temperature, adding dichloromethane, standing for layering, removing a water phase, washing an organic phase with deionized water, drying with anhydrous magnesium sulfate, filtering, removing filter residues, distilling the filtrate at the temperature of 120 ℃ to remove low-boiling-point substances, and thus obtaining the modifier.
The molar ratio of the phenol used in step A1 to the 4,4' -diaminodiphenyl sulfone used is 2:1.
The dosage molar ratio of the intermediate 1 and the p-hydroxybenzoyl chloride in the step A2 is 1:2.
The dosage ratio of the intermediate 2, the epichlorohydrin and the sodium hydroxide solution in the step A3 is 0.1g.
The cross-linking agent is prepared by the following steps:
step B1: dissolving 2-chloro-5-nitrotoluene in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions that the rotating speed is 120r/min and the temperature is 25 ℃, reacting for 40min, adjusting the pH value of a reaction solution to be 8, and carrying out distillation crystallization to prepare an intermediate 3;
and step B2: adding ethyl acetate into a reaction kettle, stirring and introducing phosgene at the rotation speed of 150r/min and the temperature of 30 ℃, dropwise adding an ethyl acetate solution of the intermediate 3, reacting for 6 hours to obtain an intermediate 4, uniformly mixing the intermediate 4 and deionized water, stirring and adding a potassium permanganate aqueous solution at the rotation speed of 200r/min and the temperature of 80 ℃, reacting for 20 minutes, filtering while hot, removing filter residues, and distilling the filtrate to obtain the cross-linking agent.
The dosage of the 2-chloro-5-nitrotoluene, the concentrated hydrochloric acid and the tin powder in the step B1 is 4 g.
The molar ratio of the intermediate 3 to the phosgene in the step B2 is 1.3, and the mass ratio of the intermediate 4 to the potassium permanganate is 3.5.
Example 2
A preparation process of low-temperature fast curing phenolic resin specifically comprises the following steps:
step S1: mixing a modifier and a cross-linking agent, and reacting for 4 hours at the rotating speed of 200r/min and the temperature of 55 ℃ to prepare a treatment solution;
step S2: uniformly mixing phenol, sodium hydroxide and deionized water, stirring and dropwise adding formaldehyde under the conditions that the rotating speed is 180r/min and the temperature is 23 ℃, reacting for 2.5 hours, heating to 85 ℃, adding xylenol, and continuously reacting for 0.8 hour to obtain a phenolic solution;
and step S3: uniformly mixing the phenolic resin solution and the treatment solution, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 180r/min and the temperature is 65 ℃, reacting for 2.5 hours, adjusting the pH value of the reaction to be acidic, adding excessive 1,12-dodecanediol and p-toluenesulfonic acid, reacting for 1.5 hours under the condition that the temperature is 95 ℃ to prepare phenolic resin solution, uniformly mixing the phenolic resin solution, barium hydroxide and diethylenetriamine, and curing and reacting for 60 minutes under the condition that the temperature is 23 ℃ to prepare the phenolic resin.
The molar ratio of hydroxyl groups in the modifier and isocyanate groups in the crosslinking agent in step S1 is 1:1.
The mass ratio of the phenol, the sodium hydroxide, the deionized water and the formaldehyde in the step S2 is 10.
And (3) the phenolic hydroxyl content of the phenolic solution in the step (S3) is 4 times of the chlorine atom content in the treatment solution, and the dosage ratio of the phenolic resin solution, the barium hydroxide and the diethylenetriamine is 20mL.
The modifier is prepared by the following steps:
step A1: mixing phenol, potassium carbonate, potassium hydroxide and dimethyl sulfoxide, reacting for 25min at the rotation speed of 180r/min and the temperature of 28 ℃, adding 4,4' -diaminodiphenyl sulfone, heating to 175 ℃, continuing to react for 9h, decoloring by using activated carbon, and recrystallizing a substrate by using N, N-dimethylformamide to prepare an intermediate 1;
step A2: uniformly mixing the intermediate 1, anhydrous aluminum chloride and p-hydroxybenzoyl chloride, reacting at the rotation speed of 120r/min and the temperature of 55 ℃ until no hydrogen chloride gas is generated, adding the reaction liquid into ice water, and filtering to remove filtrate to obtain an intermediate 2;
step A3: mixing the intermediate 2 and epoxy chloropropane, stirring for 2 hours at the rotation speed of 180r/min and the temperature of 115 ℃, dropwise adding a sodium hydroxide solution for 1.8 hours, reacting for 4 hours at the rotation speed of 600r/min after dropwise adding, adding ferric trichloride until the reaction solution has no color change, stopping the reaction, cooling to room temperature, adding dichloromethane, standing for layering, removing a water phase, washing an organic phase with deionized water, drying with anhydrous magnesium sulfate, filtering, removing filter residues, distilling the filtrate at the temperature of 123 ℃ to remove low-boiling-point substances, and preparing the modifier.
The molar ratio of the phenol used in step A1 to the 4,4' -diaminodiphenyl sulfone used is 2:1.
The dosage molar ratio of the intermediate 1 and the p-hydroxybenzoyl chloride in the step A2 is 1:2.
The dosage ratio of the intermediate 2, the epichlorohydrin and the sodium hydroxide solution in the step A3 is 0.1g.
The cross-linking agent is prepared by the following steps:
step B1: dissolving 2-chloro-5-nitrotoluene in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions that the rotating speed is 120r/min and the temperature is 28 ℃, reacting for 45min, adjusting the pH value of a reaction solution to be 8, and carrying out distillation crystallization to prepare an intermediate 3;
and step B2: adding ethyl acetate into a reaction kettle, stirring and introducing phosgene at the rotation speed of 180r/min and the temperature of 35 ℃, dropwise adding an ethyl acetate solution of the intermediate 3, reacting for 7 hours to obtain an intermediate 4, uniformly mixing the intermediate 4 and deionized water, stirring and adding a potassium permanganate aqueous solution at the rotation speed of 200-300r/min and the temperature of 83 ℃, reacting for 25 minutes, filtering while hot, removing filter residues, and distilling the filtrate to obtain the cross-linking agent.
The dosage of the 2-chloro-5-nitrotoluene, the concentrated hydrochloric acid and the tin powder in the step B1 is 4 g.
The molar ratio of the intermediate 3 to the phosgene in the step B2 is 1.3, and the mass ratio of the intermediate 4 to the potassium permanganate is 3.5.
Example 3
A preparation process of low-temperature fast curing phenolic resin specifically comprises the following steps:
step S1: mixing a modifier and a cross-linking agent, and reacting for 5 hours at the rotating speed of 300r/min and the temperature of 60 ℃ to prepare a treatment solution;
step S2: uniformly mixing phenol, sodium hydroxide and deionized water, stirring and dripping formaldehyde under the conditions that the rotating speed is 200r/min and the temperature is 25 ℃, reacting for 3 hours, heating to the temperature of 90 ℃, adding xylenol, and continuously reacting for 1 hour to prepare a phenolic solution;
and step S3: uniformly mixing the phenolic resin solution and the treatment solution, stirring and adding a sodium hydroxide solution under the conditions of a rotating speed of 200r/min and a temperature of 70 ℃, reacting for 3 hours, adjusting the pH value of the reaction to be acidic, adding excessive 1,12-dodecanediol and p-toluenesulfonic acid, reacting for 2 hours under the condition of a temperature of 100 ℃ to prepare phenolic resin solution, uniformly mixing the phenolic resin solution, barium hydroxide and diethylenetriamine, and curing and reacting for 70 minutes under the condition of a temperature of 25 ℃ to prepare the phenolic resin.
The molar ratio of hydroxyl groups in the modifier and isocyanate groups in the crosslinking agent in step S1 is 1:1.
The mass ratio of the phenol, the sodium hydroxide, the deionized water and the formaldehyde in the step S2 is 10.
And (3) the phenolic hydroxyl content of the phenolic solution in the step (S3) is 5 times of the chlorine atom content in the treatment solution, and the dosage ratio of the phenolic resin solution, the barium hydroxide and the diethylenetriamine is 20mL.
The modifier is prepared by the following steps:
step A1: mixing phenol, potassium carbonate, potassium hydroxide and dimethyl sulfoxide, reacting for 30min at the rotation speed of 200r/min and the temperature of 30 ℃, adding 4,4' -diaminodiphenyl sulfone, heating to 180 ℃, continuing to react for 10h, decoloring by using activated carbon, and recrystallizing a substrate by using N, N-dimethylformamide to obtain an intermediate 1;
step A2: uniformly mixing the intermediate 1, anhydrous aluminum chloride and p-hydroxybenzoyl chloride, reacting at the rotation speed of 150r/min and the temperature of 60 ℃ until no hydrogen chloride gas is generated, adding the reaction liquid into ice water, and filtering to remove filtrate to obtain an intermediate 2;
step A3: mixing the intermediate 2 and epoxy chloropropane, stirring for 3h at the rotation speed of 200r/min and the temperature of 120 ℃, dropwise adding a sodium hydroxide solution for 2h, reacting for 5h at the rotation speed of 800r/min after dropwise adding, adding ferric trichloride until the reaction solution has no color change, stopping the reaction, cooling to room temperature, adding dichloromethane, standing for layering, removing a water phase, washing an organic phase with deionized water, drying with anhydrous magnesium sulfate, filtering, removing filter residues, distilling the filtrate at the temperature of 125 ℃ to remove low-boiling-point substances, and thus obtaining the modifier.
The molar ratio of the phenol used in step A1 to the 4,4' -diaminodiphenyl sulfone used is 2:1.
The dosage molar ratio of the intermediate 1 and the p-hydroxybenzoyl chloride in the step A2 is 1:2.
The dosage ratio of the intermediate 2, the epichlorohydrin and the sodium hydroxide solution in the step A3 is 0.1g.
The cross-linking agent is prepared by the following steps:
step B1: dissolving 2-chloro-5-nitrotoluene in toluene, adding concentrated hydrochloric acid, stirring and adding tin powder under the conditions that the rotating speed is 150r/min and the temperature is 30 ℃, reacting for 50min, adjusting the pH value of a reaction solution to be 8, and carrying out distillation crystallization to prepare an intermediate 3;
and step B2: adding ethyl acetate into a reaction kettle, stirring and introducing phosgene under the conditions of a rotating speed of 200r/min and a temperature of 40 ℃, dropwise adding an ethyl acetate solution of the intermediate 3, reacting for 8 hours to obtain an intermediate 4, uniformly mixing the intermediate 4 and deionized water, stirring and adding a potassium permanganate aqueous solution under the conditions of a rotating speed of 300r/min and a temperature of 85 ℃, reacting for 30 minutes, filtering while hot, removing filter residues, and distilling the filtrate to obtain the cross-linking agent.
The dosage of the 2-chloro-5-nitrotoluene, the concentrated hydrochloric acid and the tin powder in the step B1 is 4 g.
The molar ratio of the intermediate 3 to the phosgene in the step B2 is 1.3, and the mass ratio of the intermediate 4 to the potassium permanganate is 3.5.
Comparative example 1
Compared with example 1, the comparative example uses no modifier and cross-linking agent, and directly carries out high-temperature curing by using phenolic aldehyde solution.
Comparative example 2
The comparative example is the phenolic resin disclosed in Chinese patent CN 111410814A.
Comparative example 3
The comparative example is the phenolic resin disclosed in Chinese patent CN 112851894A.
The phenolic resins obtained in examples 1 to 3 and comparative examples 1 to 3 were tested for tensile strength, flexural strength and impact strength in accordance with the GB/T2567-2008 standard, and the results are shown in the following tables;
as can be seen from the above table, the phenolic resins obtained in examples 1-3 have tensile strengths of 17.5-17.9MPa, bending strengths of 120.3-121.1MPa, and impact strengths of 9.5-9.8KJ/m 2 The curing time of the phenolic resin is 3.8-5h, and the curing temperature is not more than 100 ℃.
The foregoing is illustrative and explanatory only of the present invention, and it is intended that the present invention cover modifications, additions, or substitutions by those skilled in the art, without departing from the spirit of the invention or exceeding the scope of the claims.
Claims (6)
1. The preparation process of the low-temperature fast curing phenolic resin is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: mixing and reacting a modifier and a cross-linking agent to prepare a treatment solution;
step S2: mixing and stirring phenol, sodium hydroxide and deionized water, dripping formaldehyde, reacting, heating, adding xylenol, and continuing to react to obtain a phenolic solution;
and step S3: mixing and stirring the phenolic resin solution and the treatment solution, adding a sodium hydroxide solution, reacting, adjusting the pH value of the reaction to be acidic, adding excessive 1,12-dodecane diol and p-toluenesulfonic acid, reacting to obtain a phenolic resin solution, uniformly mixing the phenolic resin solution, barium hydroxide and diethylenetriamine, and carrying out a curing reaction to obtain a phenolic resin;
the modifier is prepared by the following steps:
step A1: mixing phenol, potassium carbonate, potassium hydroxide and dimethyl sulfoxide for reaction, adding 4,4' -diaminodiphenyl sulfone, heating for continuous reaction, decoloring by using activated carbon, and recrystallizing a substrate by using N, N-dimethylformamide to prepare an intermediate 1;
step A2: mixing the intermediate 1, anhydrous aluminum chloride and p-hydroxybenzoyl chloride for reaction until no hydrogen chloride gas is generated, adding the reaction solution into ice water, and filtering to remove filtrate to obtain an intermediate 2;
step A3: mixing and stirring the intermediate 2 and epoxy chloropropane, dropwise adding a sodium hydroxide solution, reacting, adding ferric trichloride until the color of the reaction solution is not changed, stopping the reaction, cooling to room temperature, adding dichloromethane, standing for layering, removing a water phase, washing an organic phase with deionized water, drying with anhydrous magnesium sulfate, filtering, removing filter residues, distilling the filtrate to remove low-boiling-point substances, and preparing a modifier;
the cross-linking agent is prepared by the following steps:
step B1: dissolving 2-chloro-5-nitrotoluene in toluene, adding concentrated hydrochloric acid, stirring, adding tin powder, reacting, adjusting the pH value of a reaction solution, and carrying out distillation crystallization to obtain an intermediate 3;
and step B2: adding ethyl acetate into a reaction kettle, stirring, introducing phosgene, dropwise adding an ethyl acetate solution of the intermediate 3, reacting to obtain an intermediate 4, uniformly mixing the intermediate 4 and deionized water, stirring, adding a potassium permanganate aqueous solution, reacting, filtering while hot, removing filter residues, and distilling the filtrate to obtain the cross-linking agent.
2. The process for preparing the low-temperature fast curing phenolic resin according to claim 1, which is characterized in that: the method specifically comprises the following steps: the molar ratio of the phenol used in step A1 to the 4,4' -diaminodiphenyl sulfone used is 2:1.
3. The process for preparing the low-temperature fast curing phenolic resin according to claim 1, which is characterized in that: the method specifically comprises the following steps: the dosage molar ratio of the intermediate 1 and the p-hydroxybenzoyl chloride in the step A2 is 1:2.
4. The process for preparing the low-temperature fast curing phenolic resin according to claim 1, which is characterized in that: the method specifically comprises the following steps: the use ratio of the intermediate 2, the epichlorohydrin and the sodium hydroxide solution in the step A3 is 0.1g.
5. The process for preparing the low-temperature fast curing phenolic resin according to claim 1, which is characterized in that: the method specifically comprises the following steps: the dosage of the 2-chloro-5-nitrotoluene, the concentrated hydrochloric acid and the tin powder in the step B1 is 4 g.
6. The process for preparing the low-temperature fast curing phenolic resin according to claim 1, which is characterized in that: the method specifically comprises the following steps: the molar ratio of the intermediate 3 to the phosgene in the step B2 is 1.3, and the mass ratio of the intermediate 4 to the potassium permanganate is 3.5.
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| CN112851894A (en) * | 2021-03-10 | 2021-05-28 | 北京化工大学 | Modified phenolic resin and preparation method thereof |
| CN114130212A (en) * | 2021-11-30 | 2022-03-04 | 天津工业大学 | Method for preparing separation membrane by using small molecule monomer |
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| CN111410814A (en) * | 2020-05-11 | 2020-07-14 | 武汉理工大学 | Low-temperature cured phenolic resin and preparation method thereof |
| CN112851894A (en) * | 2021-03-10 | 2021-05-28 | 北京化工大学 | Modified phenolic resin and preparation method thereof |
| CN114130212A (en) * | 2021-11-30 | 2022-03-04 | 天津工业大学 | Method for preparing separation membrane by using small molecule monomer |
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Denomination of invention: Preparation process of low-temperature rapid curing phenolic resin Effective date of registration: 20230825 Granted publication date: 20221202 Pledgee: China Construction Bank Corporation Qingyuan Sub branch Pledgor: ZHEJIANG ANYI NEW MATERIAL CO.,LTD. Registration number: Y2023330001849 |
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