CN111825832A - Epoxy resin curing agent and preparation method thereof - Google Patents
Epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN111825832A CN111825832A CN202010772202.3A CN202010772202A CN111825832A CN 111825832 A CN111825832 A CN 111825832A CN 202010772202 A CN202010772202 A CN 202010772202A CN 111825832 A CN111825832 A CN 111825832A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/54—Amino amides>
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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Abstract
The invention discloses an epoxy resin curing agent and a preparation method thereof, wherein the epoxy resin curing agent comprises the following raw materials in parts by weight: 3-5 parts of component A, 3-5 parts of component B and 30-50 parts of carbon nano tube; the component A has good volatility resistance, and can not volatilize in the using process, so that the user can be protected from being forced to suck to cause human body injury; the component B is prepared by taking methyl methacrylate and butyl acrylate as raw materials to prepare acrylic acid microsphere emulsion, the acrylic resin has good water resistance, and further ethyl orthosilicate is used for connecting nano silicon on the surface of acrylic acid, so that gamma-aminopropyl triethoxysilane is hydrolyzed to generate silanol which reacts with active groups on the surface of the acrylic acid/nano silicon composite microsphere to generate silicon-oxygen bonds to improve the water resistance effect, so that the component A and the component B are further embedded into the curing agent prepared from the carbon nano tubes, and the acrylic acid microsphere emulsion has good water resistance and is not easy to volatilize, and can increase the strength of epoxy resin.
Description
Technical Field
The invention belongs to the technical field of curing agent preparation, and particularly relates to an epoxy resin curing agent and a preparation method thereof.
Background
Epoxy resins are prepolymers of thermoplastic polymers, which have excellent mechanical and thermal properties and are widely used in various fields. The epoxy resin is thermoplastic linear structure, and after being heated, the solid resin can be softened and melted to be changed into viscous state or liquid state, and the viscosity of the liquid resin is reduced after being heated. The epoxy resin must react with the curing agent to convert the epoxy resin into a high polymer with a three-dimensional reticular cubic structure, and then the epoxy resin shows a series of excellent performances, so that the structure and the quality of the curing agent directly influence the application effect of the epoxy resin.
The existing epoxy resin curing agent has high volatility, so that a user can be forced to suck the curing agent when the curing agent is used, the human body is injured, the curing agent is subjected to water soaking after the epoxy resin is immobilized, and the curing agent is precipitated due to poor water resistance of the curing agent, so that the use performance of the epoxy resin is reduced.
Disclosure of Invention
The invention aims to provide an epoxy resin curing agent and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the existing epoxy resin curing agent has high volatility, so that a user can be forced to suck the curing agent when the curing agent is used, the human body is injured, the curing agent is subjected to water soaking after the epoxy resin is immobilized, and the curing agent is precipitated due to poor water resistance of the curing agent, so that the use performance of the epoxy resin is reduced.
The purpose of the invention can be realized by the following technical scheme:
an epoxy resin curing agent comprises the following raw materials in parts by weight: 3-5 parts of component A, 3-5 parts of component B and 30-50 parts of carbon nano tube;
the epoxy resin curing agent is prepared by the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1-1.5h under the conditions that the temperature is 60-65 ℃ and the frequency is 30-50kHz, then heating to 90-100 ℃, carrying out heat preservation for 3-5h, adding deionized water until the pH value is 6-7, centrifuging the filtrate for 5-10min under the condition that the rotation speed is 10000-12000r/min to remove supernatant, washing precipitates with deionized water until the pH value of a cleaning solution is 7, and drying to obtain modified carbon nano tubes;
step S2: adding the modified carbon nano tube prepared in the step S1 into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30-40min under the condition that the rotating speed is 300-500r/min, carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 1-3MHz, filtering to remove filtrate, and drying the filter cake for 5-10h under the condition that the temperature is 70-80 ℃ to prepare the epoxy resin curing agent.
Further, the mixed acid is prepared by mixing a sulfuric acid solution and a nitric acid solution in a volume ratio of 3:1, wherein the mass fraction of the sulfuric acid solution is 70-75%, and the mass fraction of the nitric acid solution is 60-70%.
Further, the component A is prepared by the following steps:
step A1: introducing chlorine gas into an isopropyl benzene reaction kettle under the illumination condition of the rotation speed of 100-;
the reaction process is as follows:
step A2: adding monoethyl phthalate into tetrahydrofuran, stirring at the rotation speed of 150-200r/min until the monoethyl phthalate is completely dissolved, adding benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 prepared in the step A1, continuously stirring for 2-3h at the temperature of 25-30 ℃, removing tetrahydrofuran under the vacuum condition, adding reactants into dichloromethane at the temperature of 85-90 ℃ until the reactants are completely dissolved, washing with a saturated sodium carbonate solution, standing for layering, drying with sodium sulfate, and distilling at the temperature of 85-90 ℃ to prepare an intermediate 2;
the reaction process is as follows:
step A3: adding the intermediate 2 prepared in the step A2 and tetrahydrofuran into a reaction kettle, continuously stirring until the intermediate 2 is completely dissolved, adding a nitric acid solution into the reaction kettle, reacting at the rotation speed of 100-120r/min and the temperature of 60-65 ℃ to prepare an intermediate 3, adding the intermediate 3, iron powder and a hydrochloric acid solution into the reaction kettle, and reacting at the temperature of 30-40 ℃ for 1-1.5h to prepare an intermediate 4;
the reaction process is as follows:
step A4: adding tetrabutyl titanate and ethanol into a reaction kettle, stirring until the tetrabutyl titanate and the ethanol are uniformly mixed, adding kaolin powder, carrying out ultrasonic treatment for 30-40min under the condition of the frequency of 30-50kHz, stirring for 30-40min under the conditions of the rotation speed of 300-80 ℃ and the temperature of 78-83 ℃, filtering to remove filtrate, adding a filter cake into deionized water, dispersing until the filtrate is uniformly dispersed, adding 4-dimethylaminopyridine and the intermediate 4 prepared in the step A3, stirring for 8-10h under the conditions of the rotation speed of 100-150r/min and the temperature of 40-50 ℃, filtering to remove the filtrate to obtain carrier amine, adding hydrazine hydrate and the ethanol into the reaction kettle, stirring until the hydrazine hydrate and the ethanol are uniformly mixed, adding the carrier amine, refluxing for 5-8h under the condition of the temperature of 80-85 ℃, the filtrate was removed by filtration to give component A.
Further, the dosage of cumene and chlorine in the step A1 is 1:1, the dosage ratio of the monoethyl phthalate, tetrahydrofuran, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 in the step A2 is 2-2.3g:10mL:3g:1.3-1.5mL, the dosage ratio of the intermediate 2 and nitric acid solution in the step A3 is 1:1-1.2, the mass fraction of the nitric acid solution is 30-40%, the dosage of the intermediate 3 and hydrochloric acid solution is 2-3g:5mL, the mass fraction of the hydrochloric acid solution is 10-15%, the dosage of iron powder is 3-5% of the mass of the intermediate 3, the dosage of tetrabutyl titanate in the step A4 is 3-3.5% of the mass of kaolin powder, the dosage of the filter cake and the intermediate 4 is 1-1.5g:3mL, the dosage of the 4-dimethylamino pyridine is 5-10% of the mass of the intermediate 4.
Further, the component B is prepared by the following steps:
step B1: adding methyl methacrylate, butyl acrylate and potassium persulfate into a reaction kettle, mixing to prepare a mixed solution, adding xylene into the reaction kettle, stirring and dropwise adding the mixed solution at the conditions of the rotation speed of 150-;
step B2: regulating the pH value of the acrylic acid microsphere emulsion prepared in the step B1 to 4-5, adding tetraethoxysilane into the acrylic acid microsphere emulsion, carrying out heat preservation for 15-20h at the temperature of 50-60 ℃, centrifuging for 5-8min at the rotation speed of 4000-5000r/min, removing supernatant, washing the precipitate with deionized water for 2-3 times, and washing for 30-50s each time to prepare acrylic acid/nano silicon composite microspheres;
step B3: and D, adding the acrylic acid/nano-silicon composite microspheres prepared in the step B2 into tetrahydrofuran, dispersing until the acrylic acid/nano-silicon composite microspheres are uniformly dispersed, adding gamma-aminopropyl triethoxysilane, ethanol and sodium dodecyl benzene sulfonate, stirring for 30-40min at the rotation speed of 200-300r/min and the temperature of 40-50 ℃, heating to 60-65 ℃, adding ammonium persulfate, continuously stirring for 3-6h, and distilling to remove ethanol and tetrahydrofuran at the temperature of 80-90 ℃ to obtain the component B.
Further, the mass ratio of the methyl methacrylate, the butyl acrylate and the potassium persulfate in the step B1 is 4:3:0.4-0.6, the mass ratio of the xylene to the mixed solution is 1:1, the mass of the toluene solution is 14-16% of that of the xylene, the toluene solution is toluene containing 0.5-0.8% of potassium persulfate, the mass ratio of the ethyl orthosilicate in the step B2 is 10-15% of that of the acrylic microsphere emulsion, the mass ratio of the gamma-aminopropyltriethoxysilane, the ethanol and the sodium dodecylbenzene sulfonate in the step B3 is 5mL:10mL:0.1-0.3g, and the mass ratio of the gamma-aminopropyltriethoxysilane is 3-5% of that of the acrylic acid/nano silicon composite microspheres.
A preparation method of an epoxy resin curing agent specifically comprises the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1-1.5h under the conditions that the temperature is 60-65 ℃ and the frequency is 30-50kHz, then heating to 90-100 ℃, carrying out heat preservation for 3-5h, adding deionized water until the pH value is 6-7, centrifuging the filtrate for 5-10min under the condition that the rotation speed is 10000-12000r/min to remove supernatant, washing precipitates with deionized water until the pH value of a cleaning solution is 7, and drying to obtain modified carbon nano tubes;
step S2: adding the modified carbon nano tube prepared in the step S1 into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30-40min under the condition that the rotating speed is 300-500r/min, carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 1-3MHz, filtering to remove filtrate, and drying the filter cake for 5-10h under the condition that the temperature is 70-80 ℃ to prepare the epoxy resin curing agent.
The invention has the beneficial effects that: the invention prepares a component A in the process of preparing an epoxy resin curing agent, isopropyl benzene is taken as a raw material, substitution reaction is carried out on isopropyl benzene and chlorine under the illumination condition to convert two hydrogen on isopropyl into chlorine, then the isopropyl benzene and liquid ammonia react to convert chlorine into amino to prepare an intermediate 1, further phthalic acid monoethyl ester is used to protect two amino groups on the intermediate to prepare an intermediate 2, the intermediate 2 is inserted into nitro group at para position of benzene ring under the action of nitric acid solution to prepare an intermediate 3, further iron powder is used to reduce nitro group into amino group to prepare an intermediate 4, kaolin powder is modified by tetrabutyl titanate to convert hydroxyl on the surface of the kaolin powder into carboxyl, and then amidation reaction is carried out on the intermediate 4 under the action of 4-dimethylamino pyridine to fix molecules of the intermediate 4 on the surface of the kaolin powder, and then hydrazine hydrate is used for deprotection, so that the protected amino group is deprotected, compared with the traditional amine curing agent, the component A has good volatility resistance, and can not volatilize in the use process, thereby protecting a user from being forced to absorb to cause human body damage; and a component B is prepared, the component B takes methyl methacrylate and butyl acrylate as raw materials to prepare acrylic acid microsphere emulsion, the acrylic resin has good water resistance, the acrylic acid surface is further connected with nano silicon by using ethyl orthosilicate, and then the gamma-aminopropyl triethoxysilane is hydrolyzed to generate silanol which reacts with active groups on the surface of the acrylic acid/nano silicon composite microsphere to generate silicon-oxygen bonds to improve the water resistance effect, so that the component A and the component B are further embedded into the carbon nano tube to prepare the curing agent, and the curing agent has good water resistance and is difficult to volatilize, and can increase the strength of the epoxy resin.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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
An epoxy resin curing agent comprises the following raw materials in parts by weight: 3 parts of component A, 3 parts of component B and 30 parts of carbon nano tubes;
the epoxy resin curing agent is prepared by the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1h at the temperature of 60 ℃ and the frequency of 30kHz, then heating to 90 ℃, carrying out heat preservation for 3h, adding deionized water until the pH value is 6, centrifuging the filtrate for 5min at the rotation speed of 10000r/min to remove supernatant, washing the precipitate with deionized water until the pH value of the washing solution is 7, and drying to obtain modified carbon nano tubes;
step S2: and (3) adding the modified carbon nano tube prepared in the step (S1) into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30min under the condition that the rotating speed is 300r/min, carrying out ultrasonic treatment for 1h under the condition that the frequency is 1MHz, filtering to remove filtrate, and drying the filter cake for 5h under the condition that the temperature is 70 ℃ to prepare the epoxy resin curing agent.
The component A is prepared by the following steps:
step A1: introducing chlorine gas into an isopropyl benzene reaction kettle under the illumination condition that the rotating speed is 100r/min, reacting for 30min, adding liquid ammonia, and reacting for 3h under the conditions that the temperature is 95 ℃ and the pressure is 4.5MPa to obtain an intermediate 1;
step A2: adding monoethyl phthalate into tetrahydrofuran, stirring at the rotation speed of 150r/min until the monoethyl phthalate is completely dissolved, adding benzotriazole-1-yl-oxy-tripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 prepared in the step A1, continuously stirring for 2 hours at the temperature of 25 ℃, removing tetrahydrofuran under the vacuum condition, adding reactants into dichloromethane at the temperature of 85 ℃ until the reactants are completely dissolved, washing with a saturated sodium carbonate solution, standing for layering, drying with sodium sulfate, and distilling at the temperature of 85 ℃ to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and tetrahydrofuran into a reaction kettle, continuously stirring until the intermediate 2 is completely dissolved, adding a nitric acid solution into the reaction kettle, reacting at the rotation speed of 100r/min and the temperature of 60 ℃ to prepare an intermediate 4, adding the intermediate 4, iron powder and a hydrochloric acid solution into the reaction kettle, and reacting at the temperature of 30 ℃ for 1 hour to prepare an intermediate 5;
step A4: adding tetrabutyl titanate and ethanol into a reaction kettle, stirring until the tetrabutyl titanate and the ethanol are uniformly mixed, adding kaolin powder, carrying out ultrasonic treatment for 30min under the condition of the frequency of 30kHz, stirring for 30min under the conditions of the rotating speed of 300r/min and the temperature of 78 ℃, filtering to remove filtrate, adding a filter cake into deionized water, dispersing until the filtrate is uniformly dispersed, adding 4-dimethylaminopyridine and the intermediate 4 prepared in the step A3, stirring for 8h under the conditions of the rotating speed of 100r/min and the temperature of 40 ℃, filtering to remove the filtrate to obtain carrier amine, adding hydrazine hydrate and the ethanol into the reaction kettle, stirring until the hydrazine hydrate and the ethanol are uniformly mixed, adding the carrier amine, refluxing for 5h under the temperature of 80 ℃, filtering to remove the filtrate to obtain the component A.
The component B is prepared by the following steps:
step B1: adding methyl methacrylate, butyl acrylate and potassium persulfate into a reaction kettle, mixing to obtain a mixed solution, adding xylene into the reaction kettle, stirring and dropwise adding the mixed solution at the rotation speed of 150r/min and the temperature of 100 ℃, wherein the dropwise adding time is 1h, after the dropwise adding is finished, heating at the temperature of 110 ℃, adding a toluene solution, keeping the temperature for 40min, adding sodium dodecyl benzene sulfonate, stirring at the rotation speed of 120r/min and the temperature of 70 ℃ for 20min, and thus obtaining an acrylic acid microsphere emulsion;
step B2: adjusting the pH value of the acrylic acid microsphere emulsion prepared in the step B1 to 4, adding ethyl orthosilicate into the acrylic acid microsphere emulsion, keeping the temperature at 50 ℃ for 15 hours, centrifuging for 5 minutes at the rotation speed of 4000r/min, removing supernatant, washing the precipitate with deionized water for 2 times, and washing for 30s each time to prepare acrylic acid/nano-silicon composite microspheres;
step B3: and D, adding the acrylic acid/nano-silicon composite microspheres prepared in the step B2 into tetrahydrofuran, dispersing until the acrylic acid/nano-silicon composite microspheres are uniformly dispersed, adding gamma-aminopropyl triethoxysilane, ethanol and sodium dodecyl benzene sulfonate, stirring for 30min at the rotation speed of 200r/min and the temperature of 40 ℃, heating to 60 ℃, adding ammonium persulfate, continuously stirring for 3h, and distilling to remove ethanol and tetrahydrofuran at the temperature of 80 ℃ to obtain the component B.
Example 2
An epoxy resin curing agent comprises the following raw materials in parts by weight: 4 parts of component A, 4 parts of component B and 40 parts of carbon nano tubes;
the epoxy resin curing agent is prepared by the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1h at the temperature of 60 ℃ and the frequency of 30kHz, then heating to 90 ℃, carrying out heat preservation for 3h, adding deionized water until the pH value is 6, centrifuging the filtrate for 5min at the rotation speed of 10000r/min to remove supernatant, washing the precipitate with deionized water until the pH value of the washing solution is 7, and drying to obtain modified carbon nano tubes;
step S2: and (3) adding the modified carbon nano tube prepared in the step (S1) into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30min under the condition that the rotating speed is 300r/min, carrying out ultrasonic treatment for 1h under the condition that the frequency is 1MHz, filtering to remove filtrate, and drying the filter cake for 5h under the condition that the temperature is 70 ℃ to prepare the epoxy resin curing agent.
The component A is prepared by the following steps:
step A1: introducing chlorine gas into an isopropyl benzene reaction kettle under the illumination condition that the rotating speed is 100r/min, reacting for 30min, adding liquid ammonia, and reacting for 3h under the conditions that the temperature is 95 ℃ and the pressure is 4.5MPa to obtain an intermediate 1;
step A2: adding monoethyl phthalate into tetrahydrofuran, stirring at the rotation speed of 150r/min until the monoethyl phthalate is completely dissolved, adding benzotriazole-1-yl-oxy-tripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 prepared in the step A1, continuously stirring for 2 hours at the temperature of 25 ℃, removing tetrahydrofuran under the vacuum condition, adding reactants into dichloromethane at the temperature of 85 ℃ until the reactants are completely dissolved, washing with a saturated sodium carbonate solution, standing for layering, drying with sodium sulfate, and distilling at the temperature of 85 ℃ to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and tetrahydrofuran into a reaction kettle, continuously stirring until the intermediate 2 is completely dissolved, adding a nitric acid solution into the reaction kettle, reacting at the rotation speed of 100r/min and the temperature of 60 ℃ to prepare an intermediate 4, adding the intermediate 4, iron powder and a hydrochloric acid solution into the reaction kettle, and reacting at the temperature of 30 ℃ for 1 hour to prepare an intermediate 5;
step A4: adding tetrabutyl titanate and ethanol into a reaction kettle, stirring until the tetrabutyl titanate and the ethanol are uniformly mixed, adding kaolin powder, carrying out ultrasonic treatment for 30min under the condition of the frequency of 30kHz, stirring for 30min under the conditions of the rotating speed of 300r/min and the temperature of 78 ℃, filtering to remove filtrate, adding a filter cake into deionized water, dispersing until the filtrate is uniformly dispersed, adding 4-dimethylaminopyridine and the intermediate 4 prepared in the step A3, stirring for 8h under the conditions of the rotating speed of 100r/min and the temperature of 40 ℃, filtering to remove the filtrate to obtain carrier amine, adding hydrazine hydrate and the ethanol into the reaction kettle, stirring until the hydrazine hydrate and the ethanol are uniformly mixed, adding the carrier amine, refluxing for 5h under the temperature of 80 ℃, filtering to remove the filtrate to obtain the component A.
The component B is prepared by the following steps:
step B1: adding methyl methacrylate, butyl acrylate and potassium persulfate into a reaction kettle, mixing to prepare a mixed solution, adding xylene into the reaction kettle, stirring and dropwise adding the mixed solution at the rotation speed of 180r/min and the temperature of 105 ℃, wherein the dropwise adding time is 1.3h, heating after the dropwise adding is finished, adding a toluene solution at the temperature of 115 ℃, keeping the temperature for 45min, adding sodium dodecyl benzene sulfonate, stirring at the rotation speed of 120r/min and the temperature of 75 ℃ for 25min, and preparing an acrylic acid microsphere emulsion;
step B2: adjusting the pH value of the acrylic acid microsphere emulsion prepared in the step B1 to 4, adding ethyl orthosilicate into the acrylic acid microsphere emulsion, keeping the temperature at 55 ℃ for 18 hours, centrifuging for 6 minutes at the rotation speed of 4000r/min, removing supernatant, washing the precipitate with deionized water for 2 times, and washing for 40s each time to prepare acrylic acid/nano-silicon composite microspheres;
step B3: and D, adding the acrylic acid/nano-silicon composite microspheres prepared in the step B2 into tetrahydrofuran, dispersing until the acrylic acid/nano-silicon composite microspheres are uniformly dispersed, adding gamma-aminopropyl triethoxysilane, ethanol and sodium dodecyl benzene sulfonate, stirring at the rotation speed of 200r/min and the temperature of 45 ℃ for 35min, heating to the temperature of 65 ℃, adding ammonium persulfate, continuously stirring for 5h, and distilling at the temperature of 85 ℃ to remove ethanol and tetrahydrofuran to obtain a component B.
Example 3
An epoxy resin curing agent comprises the following raw materials in parts by weight: 5 parts of component A, 5 parts of component B and 50 parts of carbon nano tubes;
the epoxy resin curing agent is prepared by the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1.5h under the conditions that the temperature is 65 ℃ and the frequency is 50kHz, then heating to 100 ℃, carrying out heat preservation for 5h, adding deionized water to the pH value of 7, centrifuging the filtrate for 10min at the rotation speed of 12000r/min to remove supernatant, washing precipitates with the deionized water until the pH value of washing liquid is 7, and drying to obtain modified carbon nano tubes;
step S2: and (3) adding the modified carbon nano tube prepared in the step (S1) into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 40min at the rotation speed of 500r/min, carrying out ultrasonic treatment for 1.5h at the frequency of 3MHz, filtering to remove filtrate, and drying the filter cake for 10h at the temperature of 80 ℃ to obtain the epoxy resin curing agent.
The component A is prepared by the following steps:
step A1: introducing chlorine gas into an isopropyl benzene reaction kettle under the illumination condition that the rotating speed is 150r/min, reacting for 40min, adding liquid ammonia, and reacting for 4h under the conditions that the temperature is 100 ℃ and the pressure is 5.0MPa to obtain an intermediate 1;
step A2: adding monoethyl phthalate into tetrahydrofuran, stirring at the rotation speed of 200r/min until the monoethyl phthalate is completely dissolved, adding benzotriazole-1-yl-oxy-tripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 prepared in the step A1, continuously stirring for 3 hours at the temperature of 30 ℃, removing tetrahydrofuran under the vacuum condition, adding reactants into dichloromethane at the temperature of 90 ℃ until the reactants are completely dissolved, washing with a saturated sodium carbonate solution, standing for layering, drying with sodium sulfate, and distilling at the temperature of 90 ℃ to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and tetrahydrofuran into a reaction kettle, continuously stirring until the intermediate 2 is completely dissolved, adding a nitric acid solution into the reaction kettle, reacting at the rotation speed of 120r/min and the temperature of 65 ℃ to prepare an intermediate 4, adding the intermediate 4, iron powder and a hydrochloric acid solution into the reaction kettle, and reacting at the temperature of 40 ℃ for 1.5 hours to prepare an intermediate 5;
step A4: adding tetrabutyl titanate and ethanol into a reaction kettle, stirring until the tetrabutyl titanate and the ethanol are uniformly mixed, adding kaolin powder, carrying out ultrasonic treatment for 40min under the condition that the frequency is 50kHz, stirring for 40min under the conditions that the rotating speed is 500r/min and the temperature is 83 ℃, filtering to remove filtrate, adding a filter cake into deionized water, dispersing until the filtrate is uniformly dispersed, adding 4-dimethylaminopyridine and the intermediate 4 prepared in the step A3, stirring for 10h under the conditions that the rotating speed is 150r/min and the temperature is 50 ℃, filtering to remove the filtrate to obtain carrier amine, adding hydrazine hydrate and the ethanol into the reaction kettle, stirring until the hydrazine hydrate and the ethanol are uniformly mixed, adding the carrier amine, refluxing for 8h under the temperature of 85 ℃, filtering to remove the filtrate to obtain the component A.
The component B is prepared by the following steps:
step B1: adding methyl methacrylate, butyl acrylate and potassium persulfate into a reaction kettle, mixing to prepare a mixed solution, adding xylene into the reaction kettle, stirring and dropwise adding the mixed solution at the rotation speed of 200r/min and the temperature of 110 ℃, wherein the dropwise adding time is 1.5h, heating after the dropwise adding is finished, adding a toluene solution at the temperature of 120 ℃, continuously keeping the temperature for 50min, adding sodium dodecyl benzene sulfonate, stirring at the rotation speed of 150r/min and the temperature of 80 ℃ for 30min, and preparing an acrylic acid microsphere emulsion;
step B2: adjusting the pH value of the acrylic acid microsphere emulsion prepared in the step B1 to 5, adding ethyl orthosilicate into the acrylic acid microsphere emulsion, keeping the temperature at 60 ℃ for 20 hours, centrifuging for 8 minutes at the rotating speed of 5000r/min, removing supernatant, washing the precipitate with deionized water for 3 times, and washing for 50s each time to prepare acrylic acid/nano-silicon composite microspheres;
step B3: and D, adding the acrylic acid/nano-silicon composite microspheres prepared in the step B2 into tetrahydrofuran, dispersing until the acrylic acid/nano-silicon composite microspheres are uniformly dispersed, adding gamma-aminopropyl triethoxysilane, ethanol and sodium dodecyl benzene sulfonate, stirring for 40min at the rotation speed of 300r/min and the temperature of 50 ℃, heating to the temperature of 65 ℃, adding ammonium persulfate, continuously stirring for 6h, and distilling to remove ethanol and tetrahydrofuran at the temperature of 90 ℃ to obtain the component B.
Comparative example
The comparative example is a common epoxy resin curing agent in the market.
The epoxy resin curing agents prepared in the above examples 1 to 3 and comparative example were subjected to a performance test, the test results of which are shown in the following table 1;
the volatilization rate is as follows: adding the epoxy resin curing agent prepared in the examples 1-3 and the comparative example into epoxy resin, uniformly mixing, coating on an iron plate, placing the iron plate in water for soaking after the coating is completely dried, and observing the surface of the coating;
TABLE 1
As can be seen from Table 1 above, the epoxy resin curing agents obtained in examples 1 to 3 did not foam even after 120 hours of immersion in water, while the epoxy resin curing agents obtained in comparative examples foamed even after 96 hours of immersion, and the present invention showed good water resistance and did not volatilize as a solid curing agent.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. An epoxy resin curing agent, which is characterized in that: the feed comprises the following raw materials in parts by weight: 3-5 parts of component A, 3-5 parts of component B and 30-50 parts of carbon nano tube;
the epoxy resin curing agent is prepared by the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1-1.5h under the conditions that the temperature is 60-65 ℃ and the frequency is 30-50kHz, then heating to 90-100 ℃, carrying out heat preservation for 3-5h, adding deionized water until the pH value is 6-7, centrifuging the filtrate for 5-10min under the condition that the rotation speed is 10000-12000r/min to remove supernatant, washing precipitates with deionized water until the pH value of a cleaning solution is 7, and drying to obtain modified carbon nano tubes;
step S2: adding the modified carbon nano tube prepared in the step S1 into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30-40min under the condition that the rotating speed is 300-500r/min, carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 1-3MHz, filtering to remove filtrate, and drying the filter cake for 5-10h under the condition that the temperature is 70-80 ℃ to prepare the epoxy resin curing agent.
2. The epoxy resin curing agent according to claim 1, wherein: the mixed acid is prepared by mixing a sulfuric acid solution and a nitric acid solution in a volume ratio of 3:1, wherein the mass fraction of the sulfuric acid solution is 70-75%, and the mass fraction of the nitric acid solution is 60-70%.
3. The epoxy resin curing agent according to claim 1, wherein: the component A is prepared by the following steps:
step A1: introducing chlorine gas into an isopropyl benzene reaction kettle under the illumination condition of the rotation speed of 100-;
step A2: adding monoethyl phthalate into tetrahydrofuran, stirring at the rotation speed of 150-200r/min until the monoethyl phthalate is completely dissolved, adding benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 prepared in the step A1, continuously stirring for 2-3h at the temperature of 25-30 ℃, removing tetrahydrofuran under the vacuum condition, adding reactants into dichloromethane at the temperature of 85-90 ℃ until the reactants are completely dissolved, washing with a saturated sodium carbonate solution, standing for layering, drying with sodium sulfate, and distilling at the temperature of 85-90 ℃ to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and tetrahydrofuran into a reaction kettle, continuously stirring until the intermediate 2 is completely dissolved, adding a nitric acid solution into the reaction kettle, reacting at the rotation speed of 100-120r/min and the temperature of 60-65 ℃ to prepare an intermediate 3, adding the intermediate 3, iron powder and a hydrochloric acid solution into the reaction kettle, and reacting at the temperature of 30-40 ℃ for 1-1.5h to prepare an intermediate 4;
step A4: adding tetrabutyl titanate and ethanol into a reaction kettle, stirring until the tetrabutyl titanate and the ethanol are uniformly mixed, adding kaolin powder, carrying out ultrasonic treatment for 30-40min under the condition of the frequency of 30-50kHz, stirring for 30-40min under the conditions of the rotation speed of 300-80 ℃ and the temperature of 78-83 ℃, filtering to remove filtrate, adding a filter cake into deionized water, dispersing until the filtrate is uniformly dispersed, adding 4-dimethylaminopyridine and the intermediate 4 prepared in the step A3, stirring for 8-10h under the conditions of the rotation speed of 100-150r/min and the temperature of 40-50 ℃, filtering to remove the filtrate to obtain carrier amine, adding hydrazine hydrate and the ethanol into the reaction kettle, stirring until the hydrazine hydrate and the ethanol are uniformly mixed, adding the carrier amine, refluxing for 5-8h under the condition of the temperature of 80-85 ℃, the filtrate was removed by filtration to give component A.
4. The epoxy resin curing agent according to claim 3, wherein: the dosage of cumene and chlorine in the step A1 is 1:1, the dosage ratio of monoethyl phthalate, tetrahydrofuran, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and the intermediate 1 in the step A2 is 2-2.3g:10mL:3g:1.3-1.5mL, the dosage ratio of the intermediate 2 and nitric acid solution in the step A3 is 1:1-1.2, the mass fraction of the nitric acid solution is 30-40%, the dosage of the intermediate 3 and hydrochloric acid solution is 2-3g:5mL, the mass fraction of the hydrochloric acid solution is 10-15%, the dosage of iron powder is 3-5% of the mass of the intermediate 3, the dosage of tetrabutyl titanate in the step A4 is 3-3.5% of the mass of kaolin powder, the dosage of the filter cake and the intermediate 4 is 1-1.5g:3mL, the dosage of the 4-dimethylamino pyridine is 5-10% of the mass of the intermediate 4.
5. The epoxy resin curing agent according to claim 1, wherein: the component B is prepared by the following steps:
step B1: adding methyl methacrylate, butyl acrylate and potassium persulfate into a reaction kettle, mixing to prepare a mixed solution, adding xylene into the reaction kettle, stirring and dropwise adding the mixed solution at the conditions of the rotation speed of 150-;
step B2: regulating the pH value of the acrylic acid microsphere emulsion prepared in the step B1 to 4-5, adding tetraethoxysilane into the acrylic acid microsphere emulsion, carrying out heat preservation for 15-20h at the temperature of 50-60 ℃, centrifuging for 5-8min at the rotation speed of 4000-5000r/min, removing supernatant, washing the precipitate with deionized water for 2-3 times, and washing for 30-50s each time to prepare acrylic acid/nano silicon composite microspheres;
step B3: and D, adding the acrylic acid/nano-silicon composite microspheres prepared in the step B2 into tetrahydrofuran, dispersing until the acrylic acid/nano-silicon composite microspheres are uniformly dispersed, adding gamma-aminopropyl triethoxysilane, ethanol and sodium dodecyl benzene sulfonate, stirring for 30-40min at the rotation speed of 200-300r/min and the temperature of 40-50 ℃, heating to 60-65 ℃, adding ammonium persulfate, continuously stirring for 3-6h, and distilling to remove ethanol and tetrahydrofuran at the temperature of 80-90 ℃ to obtain the component B.
6. The epoxy resin curing agent according to claim 5, wherein: the mass ratio of the methyl methacrylate, the butyl acrylate and the potassium persulfate in the step B1 is 4:3:0.4-0.6, the mass ratio of the xylene to the mixed solution is 1:1, the mass of the toluene solution is 14-16% of the mass of the xylene, the toluene solution is toluene containing 0.5-0.8 mass percent of potassium persulfate, the mass ratio of the ethyl orthosilicate in the step B2 is 10-15% of the mass of the acrylic microsphere emulsion, the mass ratio of the gamma-aminopropyltriethoxysilane, the ethanol and the sodium dodecyl benzene sulfonate in the step B3 is 5mL:10mL:0.1-0.3g, and the mass ratio of the gamma-aminopropyltriethoxysilane is 3-5% of the mass of the acrylic acid/nano silicon composite microsphere.
7. The method for preparing an epoxy resin curing agent according to claim 1, wherein: the method specifically comprises the following steps:
step S1: adding carbon nano tubes into mixed acid, carrying out ultrasonic treatment for 1-1.5h under the conditions that the temperature is 60-65 ℃ and the frequency is 30-50kHz, then heating to 90-100 ℃, carrying out heat preservation for 3-5h, adding deionized water until the pH value is 6-7, centrifuging the filtrate for 5-10min under the condition that the rotation speed is 10000-12000r/min to remove supernatant, washing precipitates with deionized water until the pH value of a cleaning solution is 7, and drying to obtain modified carbon nano tubes;
step S2: adding the modified carbon nano tube prepared in the step S1 into deionized water, dispersing until the modified carbon nano tube is uniformly dispersed, adding the component A and the component B, stirring for 30-40min under the condition that the rotating speed is 300-500r/min, carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 1-3MHz, filtering to remove filtrate, and drying the filter cake for 5-10h under the condition that the temperature is 70-80 ℃ to prepare the epoxy resin curing agent.
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| CN112544421A (en) * | 2020-12-09 | 2021-03-26 | 安徽南北现代林业科技有限公司 | Soilless culture method for tomato breeding |
| CN113444251A (en) * | 2021-07-16 | 2021-09-28 | 扬州天启新材料股份有限公司 | High-toughness phenolic cyanate resin and preparation method thereof |
| CN114178483A (en) * | 2022-02-15 | 2022-03-15 | 杭州汽轮铸锻有限公司 | Steam turbine component, pouring method thereof and steam turbine |
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