CN112646102B - Polyhexahydrotriazine thermosetting resin containing aromatic amide structure and preparation method thereof - Google Patents
Polyhexahydrotriazine thermosetting resin containing aromatic amide structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of thermosetting high polymer materials, and particularly relates to a polyhexamethylene triazine thermosetting resin containing an aromatic amide structure and a preparation method thereof, wherein the preparation method comprises the following steps: 1) uniformly dissolving formaldehyde and aromatic amine in a water/aprotic mixed solvent, stirring the obtained reaction solution at 20-100 ℃ for 5-120 minutes to perform prepolymerization, and obtaining a prepolymer solution, wherein the aromatic amine at least contains one aromatic diamine with an aromatic amide structure; 2) and drying the prepolymer solution, putting the prepolymer solution into a mold, and performing hot press molding at 150-250 ℃ and 0.5-7 MPa to obtain a resin product. The thermosetting resin is poly-hexahydrotriazine containing an aromatic amide structure, has excellent heat conduction, mechanical and heat resistance, simple preparation process and adjustable structure, can be recycled, and has wide application prospect.
Description
Technical Field
The invention relates to the field of thermosetting high polymer materials, in particular to intrinsic heat conduction poly-hexahydrotriazine resin containing an aromatic amide structure and a preparation method thereof.
Background
Thermosetting resins and composite materials thereof have been widely used in high-tech fields such as aerospace, transportation, electronic packaging and the like. With the continuous development of the technology, the requirements of light weight and miniaturization of scientific and technical products are increasing day by day, and the trend that a high polymer original piece replaces a metal element is developed, so that the problems of heat dissipation, flammability, thermal stability and the like need to be solved more effectively, particularly, the thermal conductivity of common thermosetting resin is generally low, and the development of the thermosetting resin in various fields is severely restricted. In addition, compared with thermoplastic resin, once cured and molded, the traditional thermosetting resin is not melted and dissolved, and cannot be subjected to secondary molding or recycling, so that the composite material is difficult to recycle.
The existing thermosetting resin is difficult to meet the requirements of high heat conductivity, high heat-resistant temperature, easy processing, recycling and the like.
Disclosure of Invention
The invention aims to provide a thermosetting high polymer material with high thermal conductivity, which forms strong interaction of hydrogen bonds among molecular chains by introducing rigid aromatic amide elements, and compared with poly-hexahydrotriazine resin without an aromatic amide structure, the prepared resin has higher thermal conductivity, and simultaneously maintains the functions of high heat-resistant temperature, good mechanical strength, recycling and the like.
The invention also aims to provide a preparation method of the polyhexamethylene triazine thermosetting resin containing the aromatic amide structure.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a polyhexamethylene triazine thermosetting resin containing an aromatic amide structure is characterized by comprising the following steps:
1) uniformly dissolving formaldehyde and aromatic amine in a water/aprotic mixed solvent, stirring the obtained reaction solution at 20-100 ℃ for 5-120 minutes to perform prepolymerization, and obtaining a prepolymer solution, wherein the aromatic amine at least contains one aromatic diamine with an aromatic amide structure;
2) and drying the prepolymer solution, putting the prepolymer solution into a mold, and performing hot press molding at 150-250 ℃ and 0.5-7 MPa to obtain a resin product.
The aromatic amine with the aromatic amide structure is one or more than two of the following structures:
the structure of other types of aromatic amines used in combination with aromatic amines having aromatic amide structure is not limited, and the following can be exemplified: p-phenylenediamine, m-phenylenediamine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-diaminobenzophenone, 4' -diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenylmethane, 4,4'- (9-fluorenylidene) diphenylamine, benzidine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy benzene) ] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] sulfone, 4' -bis (4-aminophenoxy) biphenyl, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene.
The aprotic solvent is one or more than two of N-methylpyrrolidone, dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, 2, 5-dimethylfuran and hexamethylphosphoramide.
The volume content of water in the mixed solvent is 0.5-60%, and the volume of the mixed solvent added in each gram of reactant is 3-20 ml.
The molar ratio of the formaldehyde to the primary amino groups in the aromatic amine is 1: 1, i.e. the molar ratio of formaldehyde to aromatic diamine is 2: 1.
the drying is to coat the prepolymer solution on a flat plate, and dry the prepolymer solution for 0.5 to 24 hours at the temperature of 80 to 150 ℃ to obtain a flaky prepolymer; or pouring the prepolymer solution into water to form a precipitate, and drying the precipitate at the temperature of 60-150 ℃ for 0.5-24 hours to obtain the powdery prepolymer.
The formaldehyde adopts a low molecular weight paraformaldehyde depolymerization solution with polymerization degree lower than 100 or a formaldehyde aqueous solution with mass fraction of 30-55%.
The preparation process of the thermosetting resin by taking an aromatic diamine as a reactant comprises the following steps:
a high thermal conductivity polyhexahydrotriazine thermosetting resin, which has the following structural formula:
the R is1、R2、R3Can be any one of the following structures:
the method for recycling the resin comprises the steps of soaking the resin in a strong acid/aprotic solvent mixed solution, neutralizing with an alkali solution, precipitating, filtering, washing with water, and drying to obtain the aromatic amine.
The use amount of the strong acid/aprotic solvent mixed solution is 5-30 ml per gram of resin, the concentration of the strong acid is 0.5-12 mol/L, the aprotic solvent is one or more than two of N-methylpyrrolidone, dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, 2, 5-dimethylfuran and hexamethylphosphoramide, and the soaking temperature is 20-95 ℃ for 0.5-24 hours.
The strong acid is sulfuric acid and hydrochloric acid; the alkali solution is saturated solution of sodium carbonate or sodium bicarbonate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the poly hexahydrotriazine thermosetting resin containing the aromatic amide structure prepared by the invention has excellent heat conduction, mechanical and heat resistance: the thermal conductivity of the resin can reach 0.42-0.58W/(m.K); the tensile strength, the modulus and the elongation at break can respectively reach 91-103 MPa, 4.0-4.3 GPa and 4.6-5.7 percent; the bending strength can reach 157-167 MPa; the glass transition temperature is 206-232 ℃, and the 5% decomposition temperature is 315-336 ℃. Can be used as an advanced composite material thermosetting resin matrix.
(2) The high-thermal-conductivity polyhexamethylene triazine thermosetting resin prepared by the invention has the characteristics of recycling and secondary forming.
Drawings
FIG. 1 is an infrared spectrum of the polyhexahydrotriazine resin obtained in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Preparing 120mmol of paraformaldehyde and 20ml of N-methylpyrrolidone/water mixed solvent into suspension, stirring and reacting at 80 ℃ for 0.5 hour for depolymerization, and cooling to room temperature to obtain formaldehyde reaction liquid. 60mmol of 4,4' -diaminobenzanilide
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. Mixing the above formaldehyde reaction solution (containing 120mmol of formaldehyde) and aromatic amine reaction solution uniformly (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 deg.C for 30 min for prepolymerization, further coating on a horizontal glass plate, and oven drying at 100 deg.C for 6 hr to obtain sheetA prepolymer. And putting the prepolymer into a mold, and hot-pressing for 2 hours at 200 ℃ and 3MPa to form the light yellow transparent target product. FIG. 1 is an infrared spectrum of the polyhexahydrotriazine resin. The thermal conductivity was measured according to ISO22007-2 standard to be 0.43W/(m.K). The tensile strength, modulus and elongation at break were 93.2MPa, 4.3GPa and 4.6%, respectively (tensile properties were determined according to ASTM D638-14); a flexural strength of 166.7MPa (flexural properties measured according to ASTM D790-10); the glass transition temperature of the resin is 221 ℃ and the initial decomposition temperature is 320 ℃. After each gram of resin is soaked in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution for 24 hours at room temperature, the recovery rate of 4,4' -diaminobenzanilide reaches 95.3 percent after neutralization, precipitation, filtration, water washing and drying treatment by sodium bicarbonate saturated solution.
Example 2
Preparing 120mmol of paraformaldehyde and 20ml of N-methylpyrrolidone/water mixed solvent into suspension, stirring and reacting at 80 ℃ for 0.5 hour for depolymerization, and cooling to room temperature to obtain formaldehyde reaction liquid. 60mmol of 3, 3' -diaminobenzanilide
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. And (3) uniformly mixing the formaldehyde reaction solution (containing 120mmol of formaldehyde) and the aromatic amine reaction solution (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 ℃ for reaction for 30 minutes to perform prepolymerization, further coating on a horizontal glass plate, and drying at 100 ℃ for 6 hours to obtain a sheet prepolymer. And putting the prepolymer into a mold, and hot-pressing for 2 hours at 200 ℃ and 3MPa to form the light yellow transparent target product. The thermal conductivity is 0.42W/(m.K), the tensile strength, the modulus and the elongation at break are 91.4MPa, 4.2GPa and 4.9 percent respectively, the bending strength is 165.2MPa, the glass transition temperature of the resin is 218 ℃, and the initial decomposition temperature is 317 ℃. After each gram of resin is soaked in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution for 24 hours at room temperature, the 3, 3' -diaminobenzanilide recovery rate reaches 94.8 percent after neutralization, precipitation, filtration, water washing and drying treatment by sodium bicarbonate saturated solution.
Example 3
Preparing 120mmol of paraformaldehyde and 20ml of N-methylpyrrolidone/water mixed solvent into suspension, stirring and reacting at 80 ℃ for 0.5 hour for depolymerization, and cooling to room temperature to obtain formaldehyde reaction liquid. 60mmol of N, N' -bis (4-aminophenyl) terephthalamide
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. And (3) uniformly mixing the formaldehyde reaction solution (containing 120mmol of formaldehyde) and the aromatic amine reaction solution (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 ℃ for reaction for 30 minutes to perform prepolymerization, further coating on a horizontal glass plate, and drying at 100 ℃ for 6 hours to obtain a sheet prepolymer. And putting the prepolymer into a mold, and hot-pressing for 2 hours at 200 ℃ and 3MPa to form the light yellow transparent target product. The thermal conductivity is 0.53W/(m.K), the tensile strength, the modulus and the elongation at break are respectively 96.7MPa, 4.1GPa and 5.5 percent, the bending strength is 158.1MPa, the glass transition temperature of the resin is 232 ℃, and the initial decomposition temperature is 336 ℃. After each gram of resin is soaked in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution for 24 hours at room temperature, the N, N' -bis (4-aminophenyl) terephthalamide recovery rate reaches 96.5 percent after neutralization, precipitation, filtration, washing and drying treatment by sodium bicarbonate saturated solution.
Example 4
Preparing 120mmol of paraformaldehyde and 20ml of N-methylpyrrolidone/water mixed solvent into suspension, stirring and reacting at 80 ℃ for 0.5 hour for depolymerization, and cooling to room temperature to obtain formaldehyde reaction liquid. 60mmol of 4- (4-aminophenoxy) phenyl-4-aminobenzamide
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. And (3) uniformly mixing the formaldehyde reaction solution (containing 120mmol of formaldehyde) and the aromatic amine reaction solution (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 ℃ for reaction for 30 minutes to perform prepolymerization, further coating on a horizontal glass plate, and drying at 100 ℃ for 6 hours to obtain a sheet prepolymer. Placing the prepolymer in a mold at 200 deg.CAnd hot pressing for 2h under 3MPa to obtain a light yellow transparent target product. The thermal conductivity is 0.58W/(m.K), the tensile strength, the modulus and the elongation at break are 102.6MPa, 4.0GPa and 5.7 percent respectively, the bending strength is 157.3MPa, the glass transition temperature of the resin is 206 ℃, and the initial decomposition temperature is 315 ℃. After each gram of resin is soaked in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution for 24 hours at room temperature, the recovery rate of the 4- (4-aminophenoxy) phenyl-4-aminobenzamide reaches 97.3 percent after neutralization, precipitation, filtration, washing and drying treatment by sodium bicarbonate saturated solution.
Example 5
Preparing 120mmol of paraformaldehyde and 20ml of N-methylpyrrolidone/water mixed solvent into suspension, stirring and reacting at 80 ℃ for 0.5 hour for depolymerization, and cooling to room temperature to obtain formaldehyde reaction liquid. 30mmol of 4,4' -diaminobenzanilide
And 30mmol of 4- (4-aminophenoxy) phenyl-4-aminobenzamide
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. And (3) uniformly mixing the formaldehyde reaction solution (containing 120mmol of formaldehyde) and the aromatic amine reaction solution (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 ℃ for reaction for 30 minutes to perform prepolymerization, further coating on a horizontal glass plate, and drying at 100 ℃ for 6 hours to obtain a sheet prepolymer. And putting the prepolymer into a mold, and hot-pressing for 2 hours at 200 ℃ and 3MPa to form the light yellow transparent target product. The thermal conductivity is 0.49W/(m.K), the tensile strength, the modulus and the elongation at break are respectively 96.9MPa, 4.2GPa and 5.3 percent, the bending strength is 162.5MPa, the glass transition temperature of the resin is 219 ℃, and the initial decomposition temperature is 317 ℃. After each gram of resin is soaked in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution for 24 hours at room temperature, the aromatic amine recovery rate reaches 96.6 percent after neutralization, precipitation, filtration, water washing and drying treatment by sodium bicarbonate saturated solution.
Comparative example 1
Polymerizing 120mmolFormaldehyde and 20ml of N-methyl pyrrolidone/water mixed solvent are prepared into suspension, stirred and reacted for 0.5 hour at 80 ℃ for depolymerization, and cooled to room temperature to obtain formaldehyde reaction liquid. 60mmol of 2,2' -bis [4- (4-aminophenoxyphenyl)]Propane
The resulting mixture was dissolved in 60ml of N-methylpyrrolidone to obtain an aromatic amine reaction solution. And (3) uniformly mixing the formaldehyde reaction solution (containing 120mmol of formaldehyde) and the aromatic amine reaction solution (the volume content of water in the mixed solvent of the final reaction system is 10%), stirring at 50 ℃ for reaction for 30 minutes to perform prepolymerization, further coating on a horizontal glass plate, and drying at 100 ℃ for 6 hours to obtain a sheet prepolymer. And putting the prepolymer into a mold, and hot-pressing for 2 hours at 200 ℃ and 3MPa to form the light yellow transparent target product. The thermal conductivity is 0.24W/(m.K), the tensile strength, the modulus and the elongation at break are 124.7MPa, 4.8GPa and 3.8 percent respectively, the bending strength is 151.6MPa, the glass transition temperature of the resin is 200 ℃, and the initial decomposition temperature is 368 ℃. Soaking each gram of resin in 10ml of 0.5mol/L tetrahydrofuran hydrochloric acid solution at room temperature for 24 hours, neutralizing by sodium bicarbonate saturated solution, precipitating, filtering, washing with water, and drying to obtain 2,2' -bis [4- (4-aminophenoxyphenyl)]The recovery rate of the propane reaches 96.8 percent.
TABLE 1 thermal conductivity results for aromatic amide structure-containing polyhexahydrotriazine thermosetting resins
| EXAMPLES/COMPARATIVE EXAMPLES | Thermal conductivity (W/(m.K)) | Increased proportion (%) |
| Comparative example 1 | 0.24 | - |
| Example 1 | 0.43 | 79 |
| Example 2 | 0.42 | 75 |
| Example 3 | 0.53 | 121 |
| Example 4 | 0.58 | 142 |
| Example 5 | 0.49 | 104 |
The results in table 1 show that the introduction of aromatic amide structure capable of forming intermolecular hydrogen bond can significantly improve the thermal conductivity of the polyhexamethylene triazine resin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a polyhexamethylene triazine thermosetting resin containing an aromatic amide structure is characterized by comprising the following steps:
1) uniformly dissolving formaldehyde and aromatic amine in a water/aprotic mixed solvent, stirring the obtained reaction solution at 20-100 ℃ to react for 5-120 minutes, and carrying out prepolymerization to obtain a prepolymer solution, wherein the aromatic amine at least contains one aromatic diamine with an aromatic amide structure, and the aromatic structure in the aromatic diamine is phenyl; the molar ratio of formaldehyde to aromatic diamine is 2: 1;
2) and drying the prepolymer solution, putting the prepolymer solution into a mold, and performing hot press molding at 150-250 ℃ and 0.5-7 MPa to obtain a resin product.
2. The method according to claim 1, wherein the aromatic diamine having an aromatic amide structure is one or more of the following structures:
3. the production method according to claim 1 or 2, wherein the aprotic solvent is one or more of N-methylpyrrolidone, dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, 2, 5-dimethylfuran, and hexamethylphosphoramide.
4. The preparation method according to claim 1 or 2, wherein the volume content of water in the mixed solvent in the step (1) is 0.5-60%, and the volume of the mixed solvent added in each gram of reactant is 3-20 ml.
5. The preparation method according to claim 1 or 2, wherein the drying is to coat the prepolymer solution on a flat plate, and to dry the prepolymer solution at 80 to 150 ℃ for 0.5 to 24 hours to obtain a sheet-like prepolymer; or pouring the prepolymer solution into water to form a precipitate, and drying the precipitate at the temperature of 60-150 ℃ for 0.5-24 hours to obtain the powdery prepolymer.
6. The method according to claim 1 or 2, wherein the formaldehyde is a low molecular weight paraformaldehyde depolymerization solution having a degree of polymerization of less than 100 or an aqueous formaldehyde solution having a mass fraction of 30% to 55%.
7. The polyhexamethylene triazine thermosetting resin containing an aromatic amide structure is characterized by having the following structural formula:
the R is1、R2、R3Can be any one of the following structures:
8. the method for recycling and reusing the resin as claimed in claim 7, wherein the aromatic amine is obtained by soaking the resin in a mixed solution of a strong acid and an aprotic solvent, and then neutralizing, precipitating, filtering, washing with water, and drying the resin with an alkali solution.
9. The method for recycling and utilizing resin according to claim 8, wherein the amount of the mixed solution of the strong acid and the aprotic solvent is 5 to 30ml per gram of the resin, the concentration of the strong acid is 0.5 to 12mol/L, the aprotic solvent is one or more of N-methylpyrrolidone, dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, 2, 5-dimethylfuran and hexamethylphosphoramide, and the soaking temperature is 20 to 95 ℃ for 0.5 to 24 hours.
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