Bio-based epoxy resin pouring sealant and preparation method thereof
阅读说明：本技术 一种生物基环氧树脂灌封胶及其制备方法 (Bio-based epoxy resin pouring sealant and preparation method thereof ) 是由 刘敬成 黄家峰 顾志伟 于 2021-11-01 设计创作，主要内容包括：本发明公开了一种生物基环氧树脂灌封胶,所述生物基环氧树脂灌封胶含有多臂腰果酚基环三磷腈环氧树脂,所述多臂腰果酚基环三磷腈环氧树脂由六氯环三磷腈与腰果酚反应后再经过环氧化制得。本发明将腰果酚与环三磷腈通过分子设计进行有机结合,制备具有优异热稳定性、阻燃性的功能化腰果酚环氧树脂,并制备出综合性能优异的生物基环氧灌封胶,具有重要的应用价值。(The invention discloses a bio-based epoxy resin pouring sealant which contains multi-arm cardanol cyclotriphosphazene epoxy resin, wherein the multi-arm cardanol cyclotriphosphazene epoxy resin is prepared by reacting hexachlorocyclotriphosphazene with cardanol and then epoxidizing. According to the invention, cardanol and cyclotriphosphazene are organically combined through molecular design, so that the functionalized cardanol epoxy resin with excellent thermal stability and flame retardance is prepared, the bio-based epoxy pouring sealant with excellent comprehensive performance is prepared, and the application value is important.)
1. The bio-based epoxy resin pouring sealant is characterized by containing multi-arm cardanol cyclotriphosphazene epoxy resin, wherein the multi-arm cardanol cyclotriphosphazene epoxy resin is prepared by reacting hexachlorocyclotriphosphazene with cardanol and then epoxidizing.
2. The bio-based epoxy resin pouring sealant as claimed in claim 1, wherein the reaction process of hexachlorocyclotriphosphazene and cardanol is as follows:
dissolving hexachlorocyclotriphosphazene, cardanol and an acid-binding agent in a solvent, uniformly mixing, heating to 90-100 ℃, and stirring and refluxing for reaction for 24-48 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying filtrate to obtain the multi-arm cardanol cyclotriphosphazene resin;
mixing the multi-arm cardanol cyclotriphosphazene resin with formic acid and hydrogen peroxide, and reacting for 2-4h at 45-60 ℃; and after the reaction is finished, extracting, washing, concentrating and drying to obtain the multi-arm cardanol cyclotriphosphazene epoxy resin.
3. The bio-based epoxy resin pouring sealant as claimed in claim 2, wherein the molar ratio of hexachlorocyclotriphosphazene to cardanol is 1: 1-6; the acid-binding agent is one or more of triethylamine, NaH and potassium carbonate; the molar ratio of the acid-binding agent to the cardanol is 1: 1-1.2; the solvent is one or more of THF, 1, 4-dioxane and DMF.
4. The bio-based epoxy resin pouring sealant as claimed in claim 2, wherein the molar ratio of the formic acid to the multi-arm cardanol cyclotriphosphazene resin is 9.6-18: 1; the mass concentration of the hydrogen peroxide is 50%, and the molar ratio of the hydrogen peroxide to the multi-arm cardanol cyclotriphosphazene resin is 12-30: 1.
5. The bio-based epoxy resin pouring sealant as claimed in claim 1, wherein the bio-based epoxy resin pouring sealant comprises a component A and a component B, and the components comprise the following raw materials in parts by weight:
the component A comprises:
and B component:
30-50 parts of curing agent
3-10 parts of a curing accelerator;
the weight ratio of the component A to the component B is 3-5: 1.
6. The bio-based epoxy resin pouring sealant as claimed in claim 5, wherein the epoxy resin is one or more of bisphenol A type epoxy resin E-51, E-44, E42; the bio-based epoxy resin diluent is flame-retardant cardanol glycidyl ether, and the epoxy value of the bio-based epoxy resin diluent is 0.18-0.25.
7. The bio-based epoxy resin pouring sealant as claimed in claim 6, wherein the preparation method of the flame-retardant cardanol glycidyl ether comprises the following steps:
(1) dissolving hydroxyethyl cardanol ether and an acid-binding agent in a solvent, uniformly mixing, cooling in an ice-water bath, gradually dropwise adding phosphorus oxychloride, stirring and reacting for 2-4h, and heating to 30-60 ℃ to continue reacting for 6-8 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate;
(2) mixing the phosphoric acid trihydroxyethyl cardanol ether with formic acid and hydrogen peroxide, reacting for 2-4h at 30-60 ℃, extracting after the reaction is finished, washing, concentrating and drying to obtain the phosphoric acid trihydroxyethyl cardanol ether epoxy resin, namely the flame-retardant cardanol glycidyl ether.
8. The bio-based epoxy resin pouring sealant as claimed in claim 7, wherein in the step (1), the molar ratio of the phosphorus oxychloride to the hydroxyethyl cardanol ether is 1: 1-3; the acid-binding agent is one or more of triethylamine, NaH and potassium carbonate; the molar ratio of the acid-binding agent to the hydroxyethyl cardanol ether is 1: 1-1.2; the solvent is one or more of THF, 1, 4-dioxane, DMF and trichloromethane; in the step (2), the molar ratio of formic acid to phosphoric acid trihydroxyethyl cardanol ether is 4.8-9: 1; the mass concentration of the hydrogen peroxide is 50%, and the molar ratio of the hydrogen peroxide to the trihydroxyethyl cardanol phosphate is 6-15: 1.
9. The bio-based epoxy resin pouring sealant as claimed in claim 5, wherein the filler is one or more of aluminum hydroxide, silicon dioxide, aluminum oxide and calcium carbonate; the defoaming agent is an organic silicon defoaming agent, preferably one or more of BYK530 and BYK 055; the silane coupling agent is one or more of KH550, KH560, KH792 and DL-602; the curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, glutaric anhydride, tung oil anhydride, dodecenyl succinic anhydride and trimellitic anhydride; the curing accelerator is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine, dimethylaniline and imidazole.
10. The preparation method of the bio-based epoxy resin pouring sealant as claimed in claim 5, characterized by comprising the following steps:
(1) mixing 30-60 parts of epoxy resin, 10-40 parts of multi-arm cardanol cyclotriphosphazene epoxy resin, 5-40 parts of bio-based epoxy resin diluent, 50-300 parts of filler, 0.1-1 part of defoaming agent and 1-5 parts of silane coupling agent, uniformly stirring and dispersing, and then carrying out vacuum bubble removal to obtain a component A;
(2) mixing 30-50 parts of curing agent and 3-10 parts of curing accelerator, uniformly stirring and dispersing, and then carrying out vacuum bubble removal to obtain a component B;
(3) and mixing the component A and the component B according to the weight ratio of 3-5:1, and stirring and dispersing uniformly to obtain the bio-based epoxy resin pouring sealant.
Preferably, the stirring dispersion rate is 1000-.
Technical Field
The invention relates to the technical field of epoxy resin adhesives, in particular to a bio-based epoxy resin pouring sealant containing multi-arm cardanol cyclotriphosphazene epoxy resin and a preparation method thereof.
Background
With the rapid development of new energy automobiles and electronic industries, the amount of the pouring sealant is increased, and the epoxy resin pouring sealant is widely used due to the advantages of excellent performance, simple process and the like. The epoxy pouring sealant comprises epoxy resin, a curing agent, an epoxy diluent, a filler and the like. The research on the pouring sealant is mainly concentrated in developed countries such as America, Japan, Germany and the like, the product is complete, the performance is good, the beginning of China is late, most pouring sealant products are in a low-grade level, and the high-grade pouring sealant depends on import.
The bio-based material is prepared by using renewable resources such as trees, crops, other animals and plants and residues thereof as starting materials through biotransformation. Compared with the common petroleum-based materials, the material has the advantages of wide distribution, more sources, low pollution, biodegradable property of most parts and the like. With the development of society, the problems of non-renewable, serious pollution, non-degradability and the like inherent in petroleum-based materials are increasingly prominent. The biobased material is used as a perfect green substitute of petroleum-based materials and has great market prospect.
The epoxy resin has strong adhesive force with various polar materials such as metal, glass, cement, wood, plastics and the like, particularly materials with high surface activity, and simultaneously, the cohesive strength of an epoxy condensate is also high, so that the adhesive strength is high, the curing shrinkage is small, the internal stress is small, the linear expansion coefficient is small, and the dimensional stability is high. These properties make epoxy resins, especially bisphenol a epoxy resins, useful in a large number of applications in potting compounds. However, the pure bisphenol a epoxy resin has high chemical crosslinking density of the cured structure, low molecular chain flexibility and large internal stress, which leads to high brittleness of the cured material and poor impact resistance and fatigue resistance, and limits the application and development of the pure bisphenol a epoxy resin in some high-tech fields with high requirements on durability and reliability. If the bio-based material is used as a raw material, the epoxy resin pouring sealant with excellent performance is developed, which is a more green and more environment-friendly scheme and has important significance for saving resources and protecting environment.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bio-based epoxy resin pouring sealant and a preparation method thereof. According to the invention, a biological base raw material is used as a main raw material, a cyclotriphosphazene structure is introduced, and the heat resistance and halogen-free flame retardance are realized under the synergistic effect of phosphorus and nitrogen in the structure.
The technical scheme of the invention is as follows:
the bio-based epoxy resin pouring sealant contains multi-arm cardanol cyclotriphosphazene epoxy resin, wherein the multi-arm cardanol cyclotriphosphazene epoxy resin is prepared by reacting hexachlorocyclotriphosphazene with cardanol and then epoxidizing.
According to the preferable scheme, the reaction process of hexachlorocyclotriphosphazene and cardanol is as follows:
dissolving hexachlorocyclotriphosphazene, cardanol and an acid-binding agent in a solvent, uniformly mixing, heating to 90-100 ℃, and stirring and refluxing for reaction for 24-48 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain the multi-arm cardanol cyclotriphosphazene resin (CC);
adding multi-arm cardanol cyclotriphosphazene resin (CC) into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, maintaining the temperature below 50 ℃, slowly dropwise adding formic acid and hydrogen peroxide, and reacting for 2-4h at 45-60 ℃ after dropwise adding; cooling to room temperature after the reaction is finished, transferring to a separating funnel, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; with a certain concentration of Na2CO3Washing the solution twice, standing, and removing a water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; and transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at the temperature of 45-60 ℃ for 12-24h to obtain brown oily liquid to obtain the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC).
More preferably, the molar ratio of hexachlorocyclotriphosphazene to cardanol is 1: 1-6; the acid-binding agent is one or more of triethylamine, NaH and potassium carbonate; the molar ratio of the acid-binding agent to the cardanol is 1: 1-1.2; the solvent is one or more of THF, 1, 4-dioxane and DMF.
Further preferably, the molar ratio of the formic acid to the multi-arm cardanol cyclotriphosphazene resin is 9.6-18: 1; the mass concentration of the hydrogen peroxide is 50%, and the molar ratio of the hydrogen peroxide to the multi-arm cardanol cyclotriphosphazene resin is 12-30: 1.
In a preferred scheme, the bio-based epoxy resin pouring sealant comprises a component A and a component B, wherein the components comprise the following raw materials in parts by weight:
the component A comprises:
and B component:
30-50 parts of curing agent
3-10 parts of a curing accelerator;
the weight ratio of the component A to the component B is 3-5: 1.
The epoxy resin is one or more of bisphenol A type epoxy resin E-51, E-44 and E42; the bio-based epoxy resin diluent is flame-retardant cardanol glycidyl ether, and the epoxy value of the bio-based epoxy resin diluent is 0.18-0.25.
More preferably, the preparation method of the flame-retardant cardanol glycidyl ether comprises the following steps:
(1) dissolving hydroxyethyl cardanol ether and an acid-binding agent in a solvent, uniformly mixing, cooling in an ice-water bath, gradually dropwise adding phosphorus oxychloride, stirring and reacting for 2-4h, and heating to 30-60 ℃ to continue reacting for 6-8 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate (PT-HCE);
(2) mixing trihydroxyethyl cardanol phosphate (PT-HCE) with formic acid and hydrogen peroxide in a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, reacting for 2-4h at 30-60 ℃, transferring to a separating funnel after the temperature is reduced to room temperature after the reaction is finished, adding a certain amount of dichloromethane, shaking uniformly, and standing to separate an upper water layer; with a certain concentration of Na2CO3Washing the solution twice, standing, and removing a water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; transfer the solution to a sheetAnd (3) in a flask, removing the solvent by rotary evaporation, and drying in a vacuum drying oven at 45-60 ℃ for 12-24h to obtain brown oily liquid to obtain the trihydroxyethyl cardanol phosphate epoxy resin (EPT-HCE), namely the flame-retardant cardanol glycidyl ether.
Furthermore, in the step (1), the molar ratio of the phosphorus oxychloride to the hydroxyethyl cardanol ether is 1: 1-3; the acid-binding agent is one or more of triethylamine, NaH and potassium carbonate; the molar ratio of the acid-binding agent to the hydroxyethyl cardanol ether is 1: 1-1.2; the solvent is one or more of THF, 1, 4-dioxane, DMF and trichloromethane; in the step (2), the molar ratio of formic acid to phosphoric acid trihydroxyethyl cardanol ether is 4.8-9: 1; the mass concentration of the hydrogen peroxide is 50%, and the molar ratio of the hydrogen peroxide to the trihydroxyethyl cardanol phosphate is 6-15: 1.
Further, the filler is one or more of aluminum hydroxide, silicon dioxide, aluminum oxide and calcium carbonate; the defoaming agent is an organic silicon defoaming agent, preferably one or more of BYK530 and BYK 055; the silane coupling agent is one or more of KH550, KH560, KH792 and DL-602; the curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, glutaric anhydride, tung oil anhydride, dodecenyl succinic anhydride and trimellitic anhydride; the curing accelerator is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), triethanolamine, dimethylaniline and imidazole.
The preparation method of the bio-based epoxy resin pouring sealant comprises the following steps:
(1) mixing 30-60 parts of epoxy resin, 10-40 parts of multi-arm cardanol cyclotriphosphazene epoxy resin, 5-40 parts of bio-based epoxy resin diluent, 50-300 parts of filler, 0.1-1 part of defoaming agent and 1-5 parts of silane coupling agent, uniformly stirring and dispersing, and then carrying out vacuum bubble removal to obtain a component A;
(2) mixing 30-50 parts of curing agent and 3-10 parts of curing accelerator, uniformly stirring and dispersing, and then carrying out vacuum bubble removal to obtain a component B;
(3) and mixing the component A and the component B according to the weight ratio of 3-5:1, and stirring and dispersing uniformly to obtain the bio-based epoxy resin pouring sealant.
Preferably, the stirring dispersion rate is 1000-.
The beneficial technical effects of the invention are as follows:
the epoxy resin pouring sealant is prepared by taking the bio-based material as the main raw material, so that the raw material source of the epoxy resin is widened, and the problem of overuse of petrochemical resources is solved to a certain extent. In addition, a cyclotriphosphazene structure is introduced into the molecular structure, a phosphorus-containing cardanol epoxy resin diluent is added, and the biological epoxy potting adhesive with good flame retardance and mechanical property is prepared by utilizing the synergistic effect of phosphorus and nitrogen.
Cardanol is a biomass liquid extracted from natural cashew shell oil, the benzene ring structure of the cardanol enables the cardanol to have the characteristics of aromatic compounds and high-temperature resistance, the phenolic hydroxyl structure enables the cardanol to have the characteristics of phenolic compounds, and the meta-unsaturated long straight-chain hydrocarbon structure enables the cardanol to have the characteristics of aliphatic compounds, good flexibility, self-drying performance and the like. The cardanol glycidyl ether is a reaction product of cardanol and epoxy chloropropane, can be used as an epoxy resin diluent and a flexibilizer, and can be used for modifying epoxy resin to improve the toughness and mechanical property of the epoxy resin.
The invention also synthesizes the phosphorus-containing cardanol epoxy resin diluent, so that the flame retardance and the mechanical property of the epoxy resin are further improved; therefore, the cardanol and cyclotriphosphazene are organically combined through molecular design, the functionalized cardanol epoxy resin with excellent thermal stability and flame retardance is prepared, the bio-based epoxy pouring sealant with excellent comprehensive performance is prepared, and the application value is important.
Drawings
FIG. 1 shows the IR spectra of HCE, CC and ECC obtained in example 1 of the present invention.
FIG. 2 shows the nuclear magnetic spectra of HCE, CC and ECC obtained in example 1 of the present invention.
FIG. 3 shows the IR spectra of HCE, PT-HCE and EPT-HCE obtained in example 1 of the present invention.
FIG. 4 shows the nuclear magnetic spectra of HCE, PT-HCE, EPT-HCE obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of a biological epoxy resin pouring sealant comprises the following steps:
(1) synthesis of Multi-arm Cardanol cyclotriphosphazene epoxy resin (ECC)
Uniformly mixing 1, 4-dioxane 100mL, cardanol 54.00g (0.18mol) and triethylamine 18.22g (0.18mol), dropwise adding 1, 4-dioxane solution containing hexachlorocyclotriphosphazene 10.43g (0.03mol) into a constant-pressure dropping funnel under stirring at normal temperature, heating the system to 98 ℃, stirring and refluxing for 48 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown yellow oily liquid, namely the multi-arm cardanol cyclotriphosphazene resin (CC);
adding 190 g of CC into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 20g of Formic Acid (FA) and 180g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and continuously controlling the temperature to react for 4 hours after dropwise adding; after the reaction is finished, transferring the mixture to a separating funnel after the temperature is reduced to room temperature, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; using 30% Na2CO3Washing the solution twice, standing, and removing a water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; and transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 45 ℃ for 24 hours to obtain brown oily liquid, namely the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC) with the epoxy value of 0.35.
The infrared and nuclear magnetic spectra of HCE, CC and ECC are shown in figures 1 and 2 respectively, and can be seen from figure 1, 3332cm-1The characteristic peak of phenolic hydroxyl disappears at 600cm-1And 523cm-1The characteristic peak of P-Cl on hexachlorocyclotriphosphazene is basically completely disappearedThe nucleophilic substitution reaction is carried out on phenolic hydroxyl on the benzene ring of the Ming cardanol and chlorine atoms in hexachlorocyclotriphosphazene, and most of chlorine on the phosphonitrile ring is substituted by cardanol, so that the multi-arm cardanol cyclotriphosphazene resin (CC) is successfully synthesized. Complete elimination of the characteristic absorption peak of unsaturated double bond and 760-840cm-1The appearance of epoxy group infrared proves the epoxidation of double bonds, and the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC) is successfully synthesized; from FIG. 2, a single peak (H) at 4.12ppm can be seen1) Representing a characteristic hydrogen proton peak of phenolic hydroxyl on cardanol, wherein the complete disappearance of the phenolic hydroxyl peak in a multi-arm cardanol cyclotriphosphazene nuclear magnetic spectrum shows that nucleophilic substitution reaction is successfully carried out, and chlorine atoms on hexachlorocyclotriphosphazene completely react with phenolic hydroxyl; the complete disappearance of the absorption peak of unsaturated double bonds in the middle of a fatty chain and the absorption peak of hydrogen protons on methylene adjacent to the double bond at the positions of 1.91-2.1ppm on cardanol arms at the positions of 5.29-5.48ppm can be observed in a nuclear magnetic spectrum of the multi-arm cardanol cyclotriphosphazene epoxy resin, and meanwhile, the hydrogen proton peak of epoxy groups appears at the positions of 2.85-3.19ppm, which proves the successful epoxidation of the double bonds.
(2) Synthesis of Trihydroxyethyl phosphate Cardanol Ether epoxy resin (EPT-HCE)
137.18(0.4mol) hydroxyethyl cardanol ether HCE and 40.48g (0.4mol) Triethylamine (TEA) as acid-binding agent are dissolved in 30mL of chloroform, mixed evenly, cooled in ice-water bath, and gradually and dropwise added with 15.3g
(0.1mol) phosphorus oxychloride (POCl)3) Stirring for reaction for 4h, heating to 50 ℃ and continuing to react for 7 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate (PT-HCE);
adding 15g of trihydroxyethyl cardanol phosphate PT-HCE into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 2.21g of Formic Acid (FA) and 16.32g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and after dropwise adding, continuing controlling the temperature to react for 3 hours to finish the reaction. After the temperature is reduced to room temperature, transferring the mixture to a separating funnel, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; with 10 wt% of Na2CO3Washing the solution twice, standing, and removing a water layer; adding anhydrous magnesium sulfate to remove water, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 50 ℃ for 24 hours to obtain brown oily liquid, namely the trihydroxyethyl cardanol ether phosphate epoxy resin (EPT-HCE).
The infrared and nuclear magnetic spectrograms of HCE, PT-HCE and EPT-HCE are respectively shown in figures 3 and 4; as can be seen from FIG. 3, the C-H stretching vibration peak at 3010cm was observed at the unsaturated double bond in the side chain of the hydroxyethylcardanol-1At least one of (1) and (b); and the stretching vibration peaks of methylene and methyl are respectively positioned at 2925cm-1And 2854cm-1At least one of (1) and (b); the characteristic stretching vibration peak of C-C bond on benzene ring is located at 1595cm-1、1454cm-1At least one of (1) and (b); the C-O telescopic absorption peak is 1268cm-1、1152cm-1At least one of (1) and (b); the bending vibration peak of the unsaturated double bond is located at 1073-994cm-1To (3). Complete disappearance of the C-H on the unsaturated double bond and the characteristic absorption peak of the unsaturated double bond, and concomitant 910cm-1The infrared peak of the epoxy group appears and part of the epoxy group appears due to ring opening and is positioned at 3600cm-1-3150cm-1the-OH peak of (A) proves that the epoxidation reaction of the double bond is successfully carried out; it can be seen from fig. 4 that the single peak at 4.83ppm (H1) represents the characteristic hydrogen proton peak of hydroxyl group at the end of hydroxyethyl cardanol ether, the hydroxyl group peak in hydroxyethyl cardanol ether nuclear magnetic spectrum completely disappears, and the proton absorption peaks at δ H2 on carbon connected with hydroxyl group at 3.94ppm and 3.70ppm are very reduced, and the shift to low field is accompanied by the introduction of — P ═ O group, indicating that nucleophilic substitution reaction has been successfully completed, and then the epoxy group hydrogen proton peak at 2.85-3.19ppm can be seen in phosphoric acid trihydroxyethyl cardanol ether epoxy resin, indicating the successful preparation of the product.
(3) Preparation of bio-based epoxy resin pouring sealant
Mixing 40 parts of epoxy resin E-51, 20 parts of ECC obtained in the step (1), 20 parts of EPT-HCE obtained in the step (2), 100 parts of aluminum hydroxide, 0.5 part of BYK530 and 2 parts of KH560, stirring and dispersing uniformly, and then carrying out vacuum bubble removal to obtain a component A;
mixing 40 parts of methyl hexahydrophthalic anhydride and 4 parts of 1, 8-diazabicyclo [5.4.0] undec-7-ene, stirring and dispersing uniformly, and then discharging bubbles in vacuum to obtain a component B;
and mixing the component A and the component B according to the weight ratio of 3:1, stirring and dispersing for 1 hour at 1200rpm, and removing bubbles for 1 hour in vacuum to obtain the bio-based epoxy resin pouring sealant.
Example 2
A preparation method of a biological epoxy resin pouring sealant comprises the following steps:
(1) synthesis of Multi-arm Cardanol cyclotriphosphazene epoxy resin (ECC)
Uniformly mixing 1, 4-dioxane 100mL, cardanol 45.00g (0.15mol) and triethylamine 15.18g (0.15mol), dropwise adding 1, 4-dioxane solution containing hexachlorocyclotriphosphazene 10.43g (0.03mol) into a constant-pressure dropping funnel under stirring at normal temperature, heating the system to 98 ℃, stirring and refluxing for 48 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown yellow oily liquid, namely the multi-arm cardanol cyclotriphosphazene resin (CC);
adding 166.5 g of CC into a mechanically-stirred three-neck round-bottom flask provided with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 15g of Formic Acid (FA) and 135g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and continuously controlling the temperature to react for 4 hours after dropwise adding; after the reaction is finished, transferring the mixture to a separating funnel after the temperature is reduced to room temperature, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; washing twice with 30% Na2CO3 solution, standing, and removing water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 45 ℃ for 24 hours to obtain brown oily liquid, namely the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC)
(2) Synthesis of Trihydroxyethyl phosphate Cardanol Ether epoxy resin (EPT-HCE)
Dissolving 102.89(0.3mol) of hydroxyethyl cardanol ether HCE and 30.36g (0.3mol) of Triethylamine (TEA) as an acid-binding agent in 30mL of trichloromethane, uniformly mixing, and cooling in an ice-water bath15.54g (0.1mol) of phosphorus oxychloride (POCl) are gradually added dropwise3) Stirring for reaction for 4h, heating to 50 ℃ and continuing to react for 7 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate (PT-HCE);
adding 15g of trihydroxyethyl cardanol phosphate PT-HCE into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 3.31g of Formic Acid (FA) and 27.22g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and after dropwise adding, continuing controlling the temperature to react for 3 hours to finish the reaction. After the temperature is reduced to room temperature, transferring the mixture to a separating funnel, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; with 10 wt% of Na2CO3Washing the solution twice, standing, and removing a water layer; adding anhydrous magnesium sulfate to remove water, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 50 deg.C for 24h to obtain brown oily liquid, i.e. to obtain trihydroxyethyl cardanol ether phosphate epoxy resin (EPT-HCE)
(3) Preparation of bio-based epoxy resin pouring sealant
Mixing 40 parts of epoxy resin E-42, 30 parts of bio-based epoxy resin ECC obtained in the step (1), 20 parts of bio-based epoxy resin diluent EPT-HCE obtained in the step (2), 100 parts of aluminum hydroxide, 0.5 part of BYK055 and 2 parts of KH560, stirring and dispersing uniformly, and then carrying out vacuum bubble discharge to obtain a component A;
mixing 40 parts of methyl hexahydrophthalic anhydride and 4 parts of 1, 8-diazabicyclo [5.4.0] undec-7-ene, stirring and dispersing uniformly, and then discharging bubbles in vacuum to obtain a component B;
and (3) mixing the component A and the component B according to the weight ratio of 3:1, wherein the stirring and dispersing speed is 1200rpm, the stirring time is 1 hour, and the vacuum bubble discharging time is 1 hour to obtain the bio-based epoxy resin pouring sealant.
Example 3
A preparation method of a biological epoxy resin pouring sealant comprises the following steps:
(1) synthesis of Multi-arm Cardanol cyclotriphosphazene epoxy resin (ECC)
Uniformly mixing 1, 4-dioxane 100mL, cardanol 54.00g (0.18mol) and triethylamine 18.22g (0.18mol), dropwise adding 1, 4-dioxane solution containing hexachlorocyclotriphosphazene 20.86g (0.06mol) into a constant-pressure dropping funnel under stirring at normal temperature, heating the system to 98 ℃, stirring and refluxing for reaction for 48 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown yellow oily liquid, namely the multi-arm cardanol cyclotriphosphazene resin (CC);
adding 125 g of CC into a mechanically-stirred three-neck round-bottom flask provided with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 10g of Formic Acid (FA) and 90g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and continuously controlling the temperature to react for 4 hours after dropwise adding; after the reaction is finished, transferring the mixture to a separating funnel after the temperature is reduced to room temperature, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; using 30% Na2CO3Washing the solution twice, standing, and removing a water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 45 ℃ for 24 hours to obtain brown oily liquid, namely the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC)
(2) Synthesis of Trihydroxyethyl phosphate Cardanol Ether epoxy resin (EPT-HCE)
137.18(0.4mol) hydroxyethyl cardanol ether HCE and 40.48g (0.4mol) Triethylamine (TEA) as acid-binding agent are dissolved in 30mL of chloroform, mixed evenly, cooled in ice-water bath, and gradually dropwise added with 31.06g (0.2mol) phosphorus oxychloride (POCl)3) Stirring for reaction for 4h, heating to 50 ℃ and continuing to react for 7 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate (PT-HCE);
adding 15g of trihydroxyethyl cardanol phosphate PT-HCE into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 2.76g of Formic Acid (FA) and 24.18g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and continuously controlling the temperature after dropwise adding is finishedAnd reacting for 3h to finish the reaction. After the temperature is reduced to room temperature, transferring the mixture to a separating funnel, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; with 10 wt% of Na2CO3Washing the solution twice, standing, and removing a water layer; adding anhydrous magnesium sulfate to remove water, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 50 deg.C for 24h to obtain brown oily liquid, i.e. to obtain trihydroxyethyl cardanol ether phosphate epoxy resin (EPT-HCE)
(3) Preparation of bio-based epoxy resin pouring sealant
Mixing 40 parts of epoxy resin E-44, 40 parts of bio-based epoxy resin ECC obtained in the step (1), 20 parts of bio-based epoxy resin diluent EPT-HCE obtained in the step (2), 100 parts of aluminum hydroxide, 0.5 part of BYK055 and 2 parts of KH560, stirring and dispersing uniformly, and then carrying out vacuum bubble discharge to obtain a component A;
mixing 40 parts of methyl hexahydrophthalic anhydride and 4 parts of triethanolamine, uniformly stirring and dispersing, and performing vacuum bubble removal to obtain a component B;
and (3) mixing the component A and the component B according to the weight ratio of 3:1, wherein the stirring and dispersing speed is 1200rpm, the stirring time is 1 hour, and the vacuum bubble discharging time is 1 hour to obtain the bio-based epoxy resin pouring sealant.
Example 4
A preparation method of a biological epoxy resin pouring sealant comprises the following steps:
(1) synthesis of Multi-arm Cardanol cyclotriphosphazene epoxy resin (ECC)
Uniformly mixing 1, 4-dioxane 100mL, cardanol 18.00g (0.06mol) and triethylamine 6.07g (0.06mol), dropwise adding 1, 4-dioxane solution containing hexachlorocyclotriphosphazene 10.43g (0.03mol) into a constant-pressure dropping funnel under stirring at normal temperature, heating the system to 98 ℃, stirring and refluxing for 48 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown yellow oily liquid, namely the multi-arm cardanol cyclotriphosphazene resin (CC);
to a three necked round bottom flask equipped with a precision thermometer, with mechanical stirring, was added 87.4 grams of CC and the temperature was warmedThe temperature is stabilized at 50 ℃, 25g of Formic Acid (FA) and 100g of hydrogen peroxide (50%) are slowly dripped at the same time, the reaction temperature is controlled at 50 ℃, and after the dripping is finished, the temperature is continuously controlled for reaction for 4 hours; after the reaction is finished, transferring the mixture to a separating funnel after the temperature is reduced to room temperature, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; using 30% Na2CO3Washing the solution twice, standing, and removing a water layer; adding a certain amount of anhydrous magnesium sulfate, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 45 ℃ for 24 hours to obtain brown oily liquid, namely the multi-arm cardanol cyclotriphosphazene epoxy resin (ECC)
(2) Synthesis of Trihydroxyethyl phosphate Cardanol Ether epoxy resin (EPT-HCE)
Dissolving 34.30(0.1mol) of hydroxyethyl cardanol ether HCE and 10.12g (0.1mol) of Triethylamine (TEA) as an acid-binding agent in 30mL of trichloromethane, uniformly mixing, cooling in an ice-water bath, and gradually dropwise adding 15.54g (0.1mol) of phosphorus oxychloride (POCl)3) Stirring for reaction for 4h, heating to 50 ℃ and continuing to react for 7 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration, concentrating and drying the filtrate to obtain brown oily liquid, namely trihydroxyethyl cardanol phosphate (PT-HCE);
adding 15g of trihydroxyethyl cardanol phosphate PT-HCE into a mechanically-stirred three-neck round-bottom flask equipped with a precision thermometer, stabilizing the temperature at 50 ℃, slowly dropwise adding 1.380g of Formic Acid (FA) and 17.63g of hydrogen peroxide (50%), controlling the reaction temperature at 50 ℃, and after dropwise adding, continuing controlling the temperature to react for 3 hours to finish the reaction. After the temperature is reduced to room temperature, transferring the mixture to a separating funnel, adding a certain amount of dichloromethane, shaking uniformly, and standing to remove an upper water layer; with 10 wt% of Na2CO3Washing the solution twice, standing, and removing a water layer; adding anhydrous magnesium sulfate to remove water, fully stirring, and performing suction filtration to obtain a solution; transferring the solution into a single-neck flask, performing rotary evaporation to remove the solvent, and drying in a vacuum drying oven at 50 deg.C for 24h to obtain brown oily liquid, i.e. to obtain trihydroxyethyl cardanol ether phosphate epoxy resin (EPT-HCE)
(3) Preparation of bio-based epoxy resin pouring sealant
Mixing 40 parts of E-51 epoxy resin, 40 parts of the bio-based epoxy resin ECC obtained in the step (1), 30 parts of the bio-based epoxy resin diluent PT-HCE obtained in the step (2), 100 parts of aluminum hydroxide, 0.5 part of BYK055 and 2 parts of KH560, stirring and dispersing uniformly, and then carrying out vacuum bubble discharge to obtain a component A;
mixing 40 parts of methyl hexahydrophthalic anhydride and 4 parts of curing accelerator imidazole, uniformly stirring and dispersing, and then carrying out vacuum bubble removal to obtain a component B;
and (3) mixing the component A and the component B according to the weight ratio of 3:1, wherein the stirring and dispersing speed is 1200rpm, the stirring time is 1 hour, and the vacuum bubble discharging time is 1 hour to obtain the bio-based epoxy resin pouring sealant.
Test example:
the performance test of the bio-based epoxy resin potting adhesive prepared in examples 1 to 4 was performed, and the results are shown in table 1; it can be seen from table 1 that the prepared epoxy potting adhesive has good bonding strength, good toughness and high limited oxygen index.
TABLE 1
And (3) testing tensile property: the bars were cured in a standard test mold, carefully removed after curing, the actual dimensions of the bars were measured, tensile properties were tested at room temperature at 5mm/min using a model 5967 Instron tensile tester, and the results averaged over 5 replicates.
Vertical burning (UL-94) test was performed according to ASTM D3801 using an oxygen index instrument model CZF-3, with standard dimensions of 130.0X 12.5X 3.2mm for the bars3Evaluation was performed. During testing, the flame height is adjusted to be about 2.0cm, the sample strips are separated after being vertically ignited for 10s, each group is tested for 10 times on average, and each sample needs to be secondarily ignited. The extinguishing time is not more than 5 seconds and no molten drops ignite the cotton balls, namely UL-94 passes V-0 level. The average extinguishing time is less than 25s, the maximum extinguishing time is not more than 30s, and the UL-94 passing V-1 grade is obtained when no molten drop is ignited in the cotton balls.The average extinguishing time exceeds 25s, the maximum extinguishing time is not more than 30s, and molten drops are added to ignite cotton balls, namely UL-94 passes V-2 level.