CN110483742B - Phosphate type epoxy resin-nano clay hydrogel and preparation method thereof - Google Patents

Phosphate type epoxy resin-nano clay hydrogel and preparation method thereof Download PDF

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CN110483742B
CN110483742B CN201910731234.6A CN201910731234A CN110483742B CN 110483742 B CN110483742 B CN 110483742B CN 201910731234 A CN201910731234 A CN 201910731234A CN 110483742 B CN110483742 B CN 110483742B
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epoxy resin
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CN110483742A (en
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周科
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Guangzhou Siqi Polymer Material Technology Co ltd
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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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

Abstract

The invention relates to the technical field of hydrogel composite materials, and discloses phosphate ester type epoxy resin-nano clay hydrogel and a preparation method thereof, wherein the phosphate ester type epoxy resin-nano clay hydrogel comprises the following formula raw materials: hydrogenated bisphenol A, epichlorohydrin, an alkalizer, 1-naphthyl phosphate, an esterification catalyst, ultrapure water, an end-capping agent, a functional auxiliary agent, an initiator and 8-11 parts of nano clay. According to the phosphate ester type epoxy resin-nano clay hydrogel and the preparation method thereof, 1-naphthyl phosphate is added, the phosphate group of the phosphate ester reacts with the hydroxyl of the epoxy resin through esterification to generate phosphate ester type epoxy resin, the phosphate ester contains a large amount of hydrophilic hydroxyl-OH, so that the epoxy resin has better hydrophilicity, the water absorption and water retention of the hydrogel are improved, meanwhile, the-OH group and an ether bond in the epoxy resin form a hydrogen bond with high chemical energy, the chemical stability of the epoxy resin is better, the phase transition temperature of the hydrogel is greatly improved, and the thermal stability of the hydrogel material is enhanced.

Description

Phosphate type epoxy resin-nano clay hydrogel and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogel composite materials, in particular to phosphate ester type epoxy resin-nano clay hydrogel and a preparation method thereof.
Background
The hydrogel is a gel taking water as a dispersion medium, a part of hydrophobic groups and hydrophilic residues are introduced into a water-soluble polymer with a reticular cross-linked structure, the hydrophilic residues are combined with water molecules to connect the water molecules in the reticular interior, and the cross-linked polymer with the hydrophobic residues expanded when meeting water is a polymer network system, has soft property, can keep a certain shape and absorb a large amount of water, the water-soluble or hydrophilic polymers can form the hydrogel through certain chemical cross-linking or physical cross-linking, the polymers can be divided into two categories of nature and synthesis according to the sources, the nature hydrophilic polymers comprise polysaccharides (starch, cellulose, alginic acid, hyaluronic acid, chitosan and the like) and polypeptides (collagen, poly L-lysine, poly L-glutamic acid and the like), the synthesis hydrophilic polymers comprise alcohol, acrylic acid and derivatives thereof (polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-N-polyacrylamide, etc.).
However, the breaking strength of the hydrogel is reduced due to the nature of the high molecular polymer and the plasticizing effect of water molecules, so that the hydrogel material has insufficient toughness and poor mechanical properties, the hydrogel material is easy to break and lose in the practical application process, and although some inorganic materials modify the high molecular hydrogel to improve the mechanical properties, most hydrophobic inorganic materials also reduce the hydrophilicity of the hydrogel.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides phosphate ester type epoxy resin-nano clay hydrogel and a preparation method thereof, which solve the problems of insufficient toughness and poor mechanical property of hydrogel materials due to the nature of high molecular polymers and the plasticizing effect of water molecules and reduction of the breaking strength of the hydrogel,
meanwhile, the problem that the hydrophilicity of the hydrogel is reduced due to the modification of the hydrogel by inorganic materials is solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a phosphate type epoxy resin-nano clay hydrogel and a preparation method thereof comprise the following formula raw materials in parts by weight: 10-13 parts of hydrogenated bisphenol A, 15-18 parts of epoxy chloropropane, 5-8 parts of alkalizer, 6-9 parts of 1-naphthyl phosphate, 0.3-0.6 part of esterification catalyst, 34-53 parts of ultrapure water, 0.5-2 parts of end-capping reagent, 2-4 parts of functional auxiliary agent, 0.2-0.4 part of initiator and 8-11 parts of nano clay, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol and ethyl acetate.
Preferably, the hydrogenated bisphenol A has the structural formula
Figure BDA0002160643370000021
The mass fraction is 96.2%.
Preferably, the structural formula of the epichlorohydrin is shown as
Figure BDA0002160643370000022
The mass fraction is more than or equal to 98.5 percent。
Preferably, the alkalizer is sodium hydroxide, wherein the mass fraction of NaOH is more than or equal to 95.5%.
Preferably, the 1-naphthyl phosphate has the structural formula
Figure BDA0002160643370000023
The mass fraction is more than or equal to 98.8 percent.
Preferably, the esterification catalyst is dicyclohexylcarbodiimide with the structural formula
Figure BDA0002160643370000024
The mass fraction is more than or equal to 98.4 percent.
Preferably, the ultrapure water is obtained by applying distillation, deionization, reverse osmosis techniques and finally introducing N2Removing dissolved oxygen in water to obtain the product.
Preferably, the end capping agent is polyethylene glycol diacrylate with a molecular formula of
Figure BDA0002160643370000025
The mass fraction is more than or equal to 96.4 percent.
Preferably, the functional auxiliary agent is N- (hydroxymethyl) acrylamide with the structural formula
Figure BDA0002160643370000026
The mass fraction is more than or equal to 97.6 percent.
Preferably, the initiator is potassium persulfate, where K is2S2O8The mass fraction is more than or equal to 95.5 percent.
Preferably, the nanoclay is montmorillonite nanoclay composed of aluminosilicate layers and having a particle size of 10-15 um.
Preferably, the preparation method of the phosphate type epoxy resin-nano clay hydrogel comprises the following steps:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked flask, and sequentially weighing 10-13 parts of hydrogenated bisphenol A and 15-18 parts of ringAdding oxychloropropane into a three-necked bottle, stirring uniformly, slowly adding 5-8 parts of an alkalizer sodium hydroxide, placing the three-necked bottle in a constant-temperature oil bath kettle, heating to 70-75 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 5-6h, when a large amount of white floccule precipitated epoxy resin is generated, adding 6-9 parts of 1-naphthyl phosphate and 0.3-0.6 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle, raising the temperature of the oil bath kettle to 85-90 ℃, stirring at a constant speed, reacting for 12-15h, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, taking an ethyl acetate organic phase, adding 500mL of distilled water for extraction twice, taking an ethyl acetate organic phase, slowly adding anhydrous sodium sulfate into the ethyl acetate until the anhydrous sodium sulfate is not agglomerated, removing water, filtering sodium sulfate through filter paper, pressurizing and concentrating the obtained ethyl acetate organic phase by a rotary evaporator, and completely removing the ethyl acetate by vacuum suction filtration of a vacuum suction pump to obtain the light yellow solid phosphate ester type epoxy resin.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 34-53 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 0.5-2 parts of end-capping agent polyethylene glycol diacrylate, 2-4 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.2-0.4 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, ultrasonic frequency is 28KHz, ultrasonic power is 2000W, heating to 60-65 deg.C, ultrasonic processing for 6-8h, then adding 8-11 parts of nano clay, heating to 80-85 ℃, carrying out ultrasonic treatment for 24-28h to obtain a hydrogel prediction, finally placing the hydrogel prediction in a big beaker filled with distilled water, soaking for 3-5 days, and changing the distilled water every 8h to remove impurities to obtain the pure phosphate ester type epoxy resin-nano clay hydrogel.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the phosphate ester type epoxy resin-nano clay hydrogel and the preparation method thereof, 1-naphthyl phosphate is added, the phosphate group of the phosphate ester type epoxy resin and the hydroxyl of the epoxy resin are subjected to esterification reaction to generate the phosphate ester type epoxy resin, and the phosphate ester type epoxy resin has better hydrophilicity compared with the traditional epoxy resin due to the fact that the phosphate ester contains a large amount of hydrophilic hydroxyl-OH, so that the water absorption and water retention of the hydrogel are improved, macromolecular aromatic groups are introduced into the phosphate ester type epoxy resin, and meanwhile, the-OH groups and ether bonds in the epoxy resin form high-chemical-energy hydrogen bonds, so that the chemical stability of the epoxy resin is better, the melting point of the epoxy resin is increased, the phase transition temperature of the hydrogel is greatly improved, and the effect of enhancing the thermal stability of the hydrogel material is achieved.
2. The phosphate type epoxy resin-nano clay hydrogel is prepared by adding montmorillonite nano clay, wherein active hydroxyl groups rich in the nano clay and carbonyl oxygen in functional auxiliary agent N- (hydroxymethyl) acrylamide in epoxy resin form hydrogen bonds with higher chemical bond energy to form a stable three-dimensional network structure，The internal crosslinking density of the hydrogel is enhanced, the movement of epoxy resin molecular chains is limited, and the hydrogel has higher elongation at break and breaking strength, so that the toughness and mechanical property of the hydrogel material are enhanced, and the practicability and durability of the hydrogel material in the actual application process are improved.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: a phosphate type epoxy resin-nano clay hydrogel and a preparation method thereof comprise the following formula raw materials in parts by weight: 10-13 parts of hydrogenated bisphenol A, 15-18 parts of epoxy chloropropane, 5-8 parts of alkalizer, 6-9 parts of 1-naphthyl phosphate, 0.3-0.6 part of esterification catalyst, 34-53 parts of ultrapure water, 0.5-2 parts of end-capping reagent, 2-4 parts of functional auxiliary agent, 0.2-0.4 part of initiator and 8-11 parts of nano clay, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, ethyl acetate, hydrogenated bisphenol A with the structural formula
Figure BDA0002160643370000041
The mass fraction is 96.2 percent, and the structural formula of the epichlorohydrin is shown in the specification
Figure BDA0002160643370000042
The mass fraction is more than or equal to 98.5 percent, the alkalizer is sodium hydroxide, the mass fraction of NaOH is more than or equal to 95.5 percent, the structural formula of the 1-naphthyl phosphate is more than or equal to 98.8 percent, the esterification catalyst is dicyclohexylcarbodiimide, and the structural formula is
Figure BDA0002160643370000051
The mass fraction is more than or equal to 98.4 percent, and the ultrapure water is prepared by applying distillation, deionization and reverse osmosis technologies and finally introducing N2Removing dissolved oxygen in water, and preparing into the product, wherein the end capping agent is polyethylene glycol diacrylate
Figure BDA0002160643370000052
Sub-formula is
Figure BDA0002160643370000053
The mass fraction is more than or equal to 96.4 percent, the functional auxiliary agent is N- (hydroxymethyl) acrylamide, and the structural formula is
Figure BDA0002160643370000054
The mass fraction is more than or equal to 97.6 percent, the initiator is potassium persulfate, wherein K2S2O8The mass fraction is more than or equal to 95.5%, the nano clay is montmorillonite nano clay consisting of aluminosilicate layers, the particle size is 10-15um, and the phosphate type epoxy resin-nano clay hydrogel is prepared by the following steps:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 10-13 parts of hydrogenated bisphenol A and 15-18 parts of epichlorohydrin, adding the hydrogenated bisphenol A and 15-18 parts of epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 5-8 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 70-75 ℃, stirring at constant speed under a magnetic stirrer, reacting for 5-6h, adding 6-9 parts of 1-naphthyl phosphate and 0.3-0.6 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle when a large amount of white floccule precipitated epoxy resin is generated, raising the temperature of the oil bath kettle to 85-90 ℃, stirring at constant speed, reacting for 12-15h, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, and transferring the materials in the three-necked bottle to the separating funnelAdding 800mL of ethyl acetate, standing and extracting, adding 500mL of distilled water into an ethyl acetate organic phase for extraction twice, slowly adding anhydrous sodium sulfate into the ethyl acetate organic phase until the anhydrous sodium sulfate is not caked, removing water, filtering the sodium sulfate by filter paper, and completely removing the ethyl acetate by the organic phase of the obtained ethyl acetate through pressure concentration of a rotary evaporator and suction filtration of a vacuum suction filtration pump to obtain the light yellow solid phosphate type epoxy resin.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 34-53 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 0.5-2 parts of end-capping agent polyethylene glycol diacrylate, 2-4 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.2-0.4 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, ultrasonic frequency is 28KHz, ultrasonic power is 2000W, heating to 60-65 deg.C, ultrasonic processing for 6-8h, then adding 8-11 parts of nano clay, heating to 80-85 ℃, carrying out ultrasonic treatment for 24-28h to obtain a hydrogel prediction, finally placing the hydrogel prediction in a big beaker filled with distilled water, soaking for 3-5 days, and changing the distilled water every 8h to remove impurities to obtain the pure phosphate ester type epoxy resin-nano clay hydrogel.
Example 1:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 10 parts of hydrogenated bisphenol A and 15 parts of epichlorohydrin, adding the hydrogenated bisphenol A and the epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 5 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 70 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 5 hours, adding 6 parts of 1-naphthyl phosphate and 0.3 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle when a large amount of white floccule precipitated epoxy resin is generated, raising the temperature of the oil bath kettle to 85 ℃, stirring at a constant speed, reacting for 12 hours, transferring the materials in the three-necked bottle into a separating funnel after complete reaction, adding 800mL of ethyl acetate, standing and extracting, extracting an ethyl acetate organic phase with 500mL of distilled water twice, and taking an ethyl acetate organic phaseAnd slowly adding anhydrous sodium sulfate until the anhydrous sodium sulfate is not caked, removing water, filtering the sodium sulfate by filter paper, and completely removing the ethyl acetate by pressurizing and concentrating the obtained ethyl acetate organic phase through a rotary evaporator and carrying out suction filtration by a vacuum suction pump to obtain a light yellow solid phosphate type epoxy resin component 1.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 53 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 0.5 part of end capping agent polyethylene glycol diacrylate, 2 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.2 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, heating to 65 ℃ for ultrasonic treatment for 6 hours, then adding 8 parts of nano clay, heating to 85 ℃ for ultrasonic treatment for 24 hours to prepare a hydrogel expected component 1, finally placing the hydrogel expected component into a large beaker filled with distilled water for soaking for 3 days, and replacing distilled water once every 8 hours to remove impurities to obtain the pure phosphate hydrogel type epoxy resin-nano clay material 1.
Example 2:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 11 parts of hydrogenated bisphenol A and 16 parts of epichlorohydrin, adding the hydrogenated bisphenol A and the epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 5 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 70 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 6 hours, when a large amount of white floccule precipitated epoxy resin is generated, adding 6 parts of 1-naphthyl phosphate and 0.4 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle, raising the temperature of the oil bath kettle to 85 ℃, stirring at a constant speed, reacting for 15 hours, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, extracting an ethyl acetate organic phase twice with 500mL of distilled water, slowly adding anhydrous sodium sulfate into the ethyl acetate organic phase until the anhydrous sodium sulfate is not agglomerated, thereby removing water, and filtering out sodium sulfate through filter paper to obtain acetic acidThe ethyl ester is organically communicated with a rotary evaporator for compression and concentration, and ethyl acetate is completely removed by vacuum suction filtration of a vacuum suction filtration pump, so that a light yellow solid phosphate ester type epoxy resin component 2 is obtained.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 50 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 0.8 part of end-capping agent polyethylene glycol diacrylate, 2.5 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.3 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, heating to 65 ℃ for ultrasonic treatment for 6 hours, adding 8 parts of nano clay, heating to 80 ℃ for ultrasonic treatment for 24 hours to prepare a hydrogel expected component 2, finally placing the hydrogel expected component into a large beaker filled with distilled water for soaking for 5 days, and replacing the distilled water once every 8 hours to remove impurities to obtain the phosphate hydrogel type epoxy resin-nano clay material 2.
Example 3:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 12 parts of hydrogenated bisphenol A and 16 parts of epichlorohydrin, adding the hydrogenated bisphenol A and the epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 7 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 75 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 6 hours, adding 7 parts of 1-naphthyl phosphate and 0.4 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle when a large amount of white floccule precipitated epoxy resin is generated, raising the temperature of the oil bath kettle to 90 ℃, stirring at a constant speed, reacting for 15 hours, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, extracting an ethyl acetate organic phase twice with 500mL of distilled water, slowly adding anhydrous sodium sulfate into the ethyl acetate organic phase until the anhydrous sodium sulfate is not agglomerated, removing water, filtering sodium sulfate with filter paper, subjecting the obtained ethyl acetate to pressure concentration with rotary evaporator, and vacuum filtering with vacuum pump to completely remove ethyl acetate to obtain yellowish solid phosphoric ester type epoxy resinAnd (4) a component 3.
(2) Preparing phosphate type epoxy resin-nano clay hydrogel: adding 44 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 1.3 parts of end capping agent polyethylene glycol diacrylate, 3 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.3 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, heating to 65 ℃ for ultrasonic treatment for 8 hours, then adding 9 parts of nano clay, heating to 85 ℃ for ultrasonic treatment for 28 hours to prepare a hydrogel prediction component 3, finally placing the hydrogel prediction component into a large beaker filled with distilled water for soaking for 3 days, and replacing the distilled water once every 8 hours to remove impurities to obtain the phosphate hydrogel type epoxy resin-nano clay material 3.
Example 4:
(1) preparing the phosphate type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 12 parts of hydrogenated bisphenol A and 17 parts of epichlorohydrin, adding the hydrogenated bisphenol A and the epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 7 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 75 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 5 hours, when a large amount of white floccule precipitated epoxy resin is generated, adding 8 parts of 1-naphthyl phosphate and 0.6 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle, raising the temperature of the oil bath kettle to 90 ℃, stirring at a constant speed, reacting for 12 hours, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, extracting an ethyl acetate organic phase twice with 500mL of distilled water, slowly adding anhydrous sodium sulfate into the ethyl acetate organic phase until the anhydrous sodium sulfate is not agglomerated, thus, water was removed, sodium sulfate was filtered out through a filter paper, and the obtained ethyl acetate was subjected to pressure concentration by a rotary evaporator and suction filtration by a vacuum suction pump to completely remove ethyl acetate, thereby obtaining a pale yellow solid phosphoric acid ester type epoxy resin component 4.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 39 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 2 parts of end-capping reagent polyethylene glycol diacrylate, 4 parts of functional assistant N- (hydroxymethyl) acrylamide and 0.4 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, heating to 65 ℃ for ultrasonic treatment for 8 hours, adding 10 parts of nano clay, heating to 85 ℃ for ultrasonic treatment for 24 hours to prepare a hydrogel prediction component 4, finally placing the hydrogel prediction into a large beaker filled with distilled water for soaking for 3 days, and replacing the distilled water once every 8 hours to remove impurities to obtain the pure phosphate type epoxy resin-nano clay hydrogel material 4.
Example 5:
(1) preparing the phosphate type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of glycol into a three-necked bottle, sequentially weighing 13 parts of hydrogenated bisphenol A and 18 parts of epichlorohydrin, adding the hydrogenated bisphenol A and the epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 8 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 75 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 6 hours, when a large amount of white floccule precipitate epoxy resin is generated, adding 9 parts of 1-naphthyl phosphate and 0.6 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle, raising the temperature of the oil bath kettle to 90 ℃, stirring at a constant speed, reacting for 15 hours, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, adding 500mL of distilled water into an ethyl acetate organic phase, extracting twice, slowly adding anhydrous sodium sulfate into the ethyl acetate organic phase until the anhydrous sodium sulfate does not agglomerate, thus, water was removed, sodium sulfate was filtered out through a filter paper, and the obtained ethyl acetate was subjected to pressure concentration by a rotary evaporator and suction filtration by a vacuum suction pump to completely remove ethyl acetate, thereby obtaining a pale yellow solid phosphoric acid ester type epoxy resin component 5.
(2) Preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 35 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 1.1 parts of end capping agent polyethylene glycol diacrylate, 4 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.3 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, heating to 65 ℃ for ultrasonic treatment for 8 hours, then adding 11 parts of nano clay, heating to 85 ℃ for ultrasonic treatment for 28 hours to prepare a hydrogel prediction component 5, finally placing the hydrogel prediction component into a large beaker filled with distilled water for soaking for 5 days, and replacing the distilled water once every 8 hours to remove impurities to obtain the phosphate hydrogel type epoxy resin-nano clay material 5.
Through the water absorption performance test, the water retention performance test, the thermal stability test, the tensile strength test and the durability test of the embodiment 1-5, the phosphate type epoxy resin-nano clay hydrogel and the preparation method thereof are characterized in that 1-naphthyl phosphate is added, phosphate groups of the phosphate type epoxy resin and hydroxyl groups of the epoxy resin are subjected to esterification reaction to generate phosphate type epoxy resin, and the phosphate type epoxy resin has better hydrophilicity compared with the traditional epoxy resin due to the fact that a large amount of hydrophilic hydroxyl-OH is contained in the phosphate, so that the water absorption performance and the water retention performance of the hydrogel are improved, macromolecular aromatic groups are introduced into the phosphate type epoxy resin, meanwhile, hydrogen bonds with high chemical energy are formed by the-OH groups and ether bonds in the epoxy resin, so that the chemical stability of the epoxy resin is better, the melting point of the epoxy resin is increased, and the phase transition temperature of the hydrogel is greatly improved, thereby achieving the effect of enhancing the thermal stability of the hydrogel material.
The phosphate type epoxy resin-nano clay hydrogel and the preparation method thereof are characterized in that montmorillonite nano clay is added, active hydroxyl groups rich in the nano clay and carbonyl oxygen in functional auxiliary agent N- (hydroxymethyl) acrylamide in epoxy resin form hydrogen bonds with higher chemical bond energy, and a stable three-dimensional network structure is formed，The internal crosslinking density of the hydrogel is enhanced, the movement of epoxy resin molecular chains is limited, and the hydrogel has higher elongation at break and breaking strength, so that the toughness and mechanical property of the hydrogel material are enhanced, and the practicability and durability of the hydrogel material in the actual application process are improved.

Claims (1)

1. PhosphorusThe acid ester type epoxy resin-nano clay hydrogel comprises the following formula raw materials in parts by weight, and is characterized in that: 10-13 parts of hydrogenated bisphenol A, 15-18 parts of epoxy chloropropane, 5-8 parts of alkalizer, 6-9 parts of 1-naphthyl phosphate, 0.3-0.6 part of esterification catalyst, 34-53 parts of ultrapure water, 0.5-2 parts of end-capping reagent, 2-4 parts of functional auxiliary agent, 0.2-0.4 part of initiator and 8-11 parts of nano clay, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, ethyl acetate; the hydrogenated bisphenol A has a structural formula
Figure FDA0003211144200000011
The mass fraction is 96.2%; the structural formula of the epichlorohydrin is shown as
Figure FDA0003211144200000012
The mass fraction is more than or equal to 98.5 percent; the alkalizer is sodium hydroxide, wherein the mass fraction of NaOH is more than or equal to 95.5%; the structural formula of the 1-naphthyl phosphate is shown in the specification
Figure FDA0003211144200000013
The mass fraction is more than or equal to 98.8 percent; the esterification catalyst is dicyclohexylcarbodiimide with a structural formula of
Figure FDA0003211144200000014
The mass fraction is more than or equal to 98.4 percent; the ultrapure water is prepared by applying distillation, deionization and reverse osmosis technologies and finally introducing N2Removing dissolved oxygen in water to obtain the product; the end capping agent is polyethylene glycol diacrylate with a molecular formula
Figure FDA0003211144200000015
The mass fraction is more than or equal to 96.4 percent; the functional auxiliary agent is N- (hydroxymethyl) acrylamide with a structural formula
Figure FDA0003211144200000016
The mass fraction is more than or equal to 97.6 percent; the initiator is potassium persulfate, wherein K2S2O8Mass fraction is more than or equal to 95.5Percent; the nano clay is montmorillonite nano clay composed of aluminosilicate layers, and the particle size is 10-15 μm;
the preparation method of the phosphate type epoxy resin-nano clay hydrogel comprises the following steps:
(1) preparing phosphate ester type epoxy resin: introducing N into a 2000mL three-necked bottle2Or Ar inert gas, adding 800mL of distilled water and 600mL of ethylene glycol into a three-necked bottle, sequentially weighing 10-13 parts of hydrogenated bisphenol A and 15-18 parts of epichlorohydrin, adding the hydrogenated bisphenol A and 15-18 parts of epichlorohydrin into the three-necked bottle, stirring uniformly, slowly adding 5-8 parts of alkalinizing agent sodium hydroxide, placing the three-necked bottle into a constant-temperature oil bath kettle, heating to 70-75 ℃, stirring at a constant speed under a magnetic stirrer, reacting for 5-6h, adding 6-9 parts of 1-naphthyl phosphate and 0.3-0.6 part of esterification catalyst dicyclohexylcarbodiimide into the three-necked bottle when a large amount of white floccule precipitates epoxy resin, raising the temperature of the oil bath kettle to 85-90 ℃, stirring at a constant speed, reacting for 12-15h, transferring the materials in the three-necked bottle into a separating funnel after the reaction is completed, adding 800mL of ethyl acetate, standing and extracting, taking an ethyl acetate organic phase, adding 500mL of distilled water for extraction twice, slowly adding anhydrous sodium sulfate into an ethyl acetate organic phase until the anhydrous sodium sulfate is not caked, removing water, filtering out the sodium sulfate through filter paper, and completely removing the ethyl acetate by pressurizing and concentrating the obtained ethyl acetate organic phase through a rotary evaporator and carrying out suction filtration through a vacuum suction filtration pump to obtain a light yellow solid phosphate type epoxy resin;
(2) preparing phosphate ester type epoxy resin-nano clay hydrogel: adding 34-53 parts of ultrapure water into a 1000mL beaker, sequentially adding the phosphate type epoxy resin prepared in the step (1), 0.5-2 parts of end-capping agent polyethylene glycol diacrylate, 2-4 parts of functional auxiliary agent N- (hydroxymethyl) acrylamide and 0.2-0.4 part of initiator potassium persulfate, uniformly stirring, placing the beaker into an ultrasonic treatment instrument, ultrasonic frequency is 28KHz, ultrasonic power is 2000W, heating to 60-65 deg.C, ultrasonic processing for 6-8h, then adding 8-11 parts of nano clay, heating to 80-85 ℃, carrying out ultrasonic treatment for 24-28h to obtain a hydrogel prediction, finally placing the hydrogel prediction in a big beaker filled with distilled water, soaking for 3-5 days, and changing the distilled water every 8h to remove impurities to obtain the pure phosphate ester type epoxy resin-nano clay hydrogel.
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