CN112961463A - Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof - Google Patents
Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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Abstract
The invention relates to a green environment-friendly catalyst-free super-tough self-repairing epoxy resin glass polymer material and a preparation method thereof, belonging to the field of thermosetting materials. The invention provides a super-tough self-repairing epoxy resin glass polymer material which is prepared from the following raw materials in percentage by mass: 100 parts of epoxy resin glass high polymer material and 1-15 parts of polysebacic dianhydride. According to the invention, polysebacic anhydride is selected as a toughening agent, and the epoxy resin glass macromolecules without catalysts are added at high content, so that the phase separation is avoided, the toughness of the material can be greatly improved, and the self-repairing performance of the material is not influenced; thereby preparing the super-tough self-repairing epoxy resin glass polymer material.
Description
Technical Field
The invention relates to a green environment-friendly catalyst-free super-tough self-repairing epoxy resin glass polymer material and a preparation method thereof, belonging to the field of thermosetting materials.
Background
Epoxy resin is one of thermosetting resins with the largest demand and excellent comprehensive performance, and a cured product of the epoxy resin has the advantages of good dimensional stability, mechanical performance, chemical resistance and the like, and is widely applied to the fields of aerospace, buildings, electronic packaging materials, transportation and the like in the forms of coating, adhesive, potting material, matrix resin of composite materials and the like. However, the epoxy resin is cured to form a three-dimensional covalent network structure, which is very brittle and has poor crack resistance due to high crosslinking density. Further, the epoxy resin cannot be processed again after once cured and molded. In addition, the epoxy resin is difficult to repair in time due to internal cracks and surface abrasion caused by the mechanical force action of external force such as scraping, extrusion, impact and the like, so that the service life of the epoxy resin is shortened and the mechanical property of the epoxy resin is reduced. In recent years, researchers have proposed epoxy resin glass polymer materials based on internal dynamic reversible covalent bonds such as transesterification, disulfide bond exchange, siloxane exchange, transamination, etc., which offer the possibility of reworking molding and self-repair of epoxy resins. Generally, these epoxy resin glass polymers need to be added with catalysts such as zinc acetylacetonate, 1-methylimidazole, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD), etc., and these catalysts are expensive and toxic, which not only increase production cost, but also are not very beneficial to environmental protection. Compared with common epoxy resin, the mechanical property of the epoxy resin glass polymer material also has the defect of large brittleness. At present, the epoxy resin glass macromolecules are toughened by mainly adding filler particles such as glass fibers, silica nanoparticles, carbon nanotubes and the like. However, the dispersion of the filler particles is difficult, and no method for solving the dispersion problem has been found in the industry.
Disclosure of Invention
Aiming at the defects that the existing epoxy resin is difficult to recover, the catalyst type glass polymer is not beneficial to environmental protection, the brittleness is high and the like, the invention aims to provide a catalyst-free super-tough epoxy resin glass polymer material which has good comprehensive properties (such as mechanical properties, heat resistance and the like), high self-repairing efficiency and can be recycled, and a preparation method thereof.
The technical scheme of the invention is as follows:
the invention aims to solve the first technical problem of providing a super-tough self-repairing epoxy resin glass polymer material, which comprises the following raw materials in percentage by mass: 100 parts of epoxy resin glass high polymer material and 1-15 parts of polysebacic dianhydride.
Further, the epoxy resin glass polymer material is prepared by adopting the following preparation method: firstly, uniformly stirring and mixing epoxy resin, acid anhydride and alcohol at 60-150 ℃ (preferably 120) until the acid anhydride and the alcohol are completely dissolved; then vacuumizing the reaction system in the stirring process until no obvious bubbles emerge; then curing the mixture at 130 to 220 ℃ to obtain the epoxy resin glass polymer material.
Further, in the preparation method of the epoxy resin glass polymer material, the molar ratio of the acid anhydride to the epoxy group in the epoxy resin is 1: 1, the molar ratio of alcohol to anhydride is 1: 1.
further, the acid anhydride is selected from one of glutaric anhydride, succinic anhydride or phthalic anhydride; glutaric anhydride is preferred.
Further, the alcohol is selected from one of terephthalyl alcohol, glycerol or polyhydroxy hyperbranched polymer; preferably terephthalyl alcohol.
Further, the epoxy resin is selected from one of glycidyl ether epoxy resin, glycidyl ester epoxy resin or alicyclic epoxy resin.
Further, in the above preparation method, the method of stirring and mixing the epoxy resin, the acid anhydride and the alcohol at 60 to 150 ℃ (preferably 120 ℃) until the acid anhydride and the alcohol are completely dissolved comprises the following steps: adding anhydride into epoxy resin, stirring for 5-30 min (preferably 10min) at 60-150 ℃ until the anhydride is completely dissolved to form a mixed solution, adding glycol into a reaction system, and continuously stirring for 30-60 min (preferably 30 min).
Further, in the method, the curing is carried out for 6 to 12 hours (preferably 10 hours) at 130 to 220 ℃.
The second technical problem to be solved by the invention is to provide a preparation method of the super-tough self-repairing epoxy resin glass polymer material, wherein the preparation method comprises the following steps: firstly, mixing epoxy resin, anhydride, diol and polysebacic anhydride at 60-150 ℃ (preferably 120 ℃) to obtain epoxy resin blend; then the epoxy resin blend is completely cured; wherein the polysebacic anhydride accounts for 1-25% of the mass of the epoxy resin.
Further, the molar ratio of the acid anhydride to the epoxy group in the epoxy resin is 1: 1, the molar ratio of alcohol to anhydride is 1: 1.
the third technical problem to be solved by the invention is to provide a preparation method of a catalyst-free epoxy resin glass polymer material, which comprises the following steps: firstly, uniformly stirring and mixing epoxy resin, acid anhydride and alcohol at 60-150 ℃ (preferably 120) until the acid anhydride and the alcohol are completely dissolved; then vacuumizing the reaction system in the stirring process until no obvious bubbles emerge; and then completely curing at 130-220 ℃ to obtain the catalyst-free epoxy resin glass polymer material.
Further, the molar ratio of the acid anhydride to the epoxy group in the epoxy resin is 1: 1, the molar ratio of alcohol to anhydride is 1: 1.
further, the acid anhydride is selected from one of glutaric anhydride, succinic anhydride or phthalic anhydride; glutaric anhydride is preferred.
Further, the alcohol is selected from one of terephthalyl alcohol, glycerol or polyhydroxy hyperbranched polymer; preferably terephthalyl alcohol.
Further, the epoxy resin is selected from one of glycidyl ether epoxy resin, glycidyl ester epoxy resin or alicyclic epoxy resin.
The fourth technical problem to be solved by the invention is to provide a catalyst-free epoxy resin glass polymer material which is prepared by adopting the method.
The fifth technical problem to be solved by the invention is to provide a method for improving the toughness of an epoxy resin glass polymer material without influencing the self-repairing efficiency of the epoxy resin glass polymer material, which comprises the following steps: selecting polysebacic anhydride as a toughening agent to prepare a super-tough epoxy resin glass high polymer material; wherein the addition amount of the polysebacic polyanhydride is 1-15% of the mass of the epoxy resin glass high polymer material. In the invention, polysebacic anhydride is selected as the toughening agent, so that the toughness of the epoxy resin glass polymer material can be improved, and the obtained super-tough epoxy resin glass polymer material does not generate a phase separation structure, so that the self-repairing efficiency of the epoxy resin glass polymer material is not influenced. The microphase separation structure is as follows: matrix-dispersed phase structure, the size of dispersed phase is nanometer level or micron level.
Further, the method for improving the toughness of the epoxy resin glass polymer material without affecting the self-repairing efficiency comprises the following steps: adding anhydride, diol and polysebacic anhydride into epoxy resin, mixing the epoxy resin with glutaric anhydride, terephthalic alcohol and polysebacic anhydride to obtain epoxy resin blend, and finally completely curing the epoxy resin blend. Namely adding polysebacic polyanhydride in the process of preparing epoxy resin glass high molecular material to obtain a blend, and then completely curing.
Furthermore, the method for improving the toughness of the epoxy resin glass polymer material without affecting the self-repairing efficiency comprises the following steps: mixing and stirring epoxy resin, acid anhydride, diol and polysebacic anhydride at 60-150 ℃ until the epoxy resin, the acid anhydride, the diol and the polysebacic anhydride are uniformly mixed; then completely curing at 130-220 ℃.
The invention has the beneficial effects that:
the invention adopts a simple method of adding anhydride and diol (such as glutaric anhydride and terephthalyl alcohol) into epoxy resin, thereby constructing the epoxy resin glass macromolecule with self-repairing performance; because the rigid benzene ring of the terephthalyl alcohol and the benzene ring in the epoxy resin form pi-pi conjugation, the thermal stability of a cured product is effectively improved, and better tensile strength is kept. The ester bond is a reversible covalent bond with definite reaction mechanism, mild condition, high speed and controllable degree, and the epoxy resin glass macromolecule constructed by the method has good self-repairing efficiency and structural stability.
In addition, polysebacic anhydride is selected as a flexibilizer, and the epoxy resin glass macromolecules without catalysts are added at high content without phase separation, so that the toughness of the material can be greatly improved without influencing the self-repairing performance of the material; and has the advantages of low price, good compatibility, good biodegradability and the like,
the impact toughness of the super-tough self-repairing epoxy resin glass polymer material obtained by the invention can reach 30kJ/m 220 times of the non-toughened catalyst-free epoxy resin glass polymer; the breaking elongation is 67-110%, which is 10 times of that of the non-toughened catalyst-free epoxy resin glass polymer; the self-repairing efficiency is 87-95%.
Drawings
FIG. 1 shows the elongation at break of the material obtained in example 1 of the present invention and a blank of a non-toughened catalyst-free epoxy resin glass polymer.
FIG. 2 shows the impact toughness of the material obtained in example 1 and the blank of the non-toughened catalyst-free epoxy resin glass polymer.
FIG. 3 shows the self-repairing efficiency of the material obtained in example 1 and the un-toughened catalyst-free epoxy resin glass polymer blank.
FIG. 4 is a graph showing the thermal decomposition temperatures of the material obtained in example 1 of the present invention and a blank of an un-toughened catalyst-free epoxy resin glass polymer.
FIG. 5 shows the elongation at break of the material obtained in example 2 of the present invention and a blank of a non-toughened catalyst-free epoxy resin glass polymer.
FIG. 6 shows the impact toughness of the material obtained in example 2 of the present invention and a blank of a non-toughened catalyst-free epoxy resin glass polymer.
FIG. 7 shows the self-repairing efficiency of the material obtained in example 2 and the un-toughened catalyst-free epoxy resin glass polymer blank.
FIG. 8 is a thermal decomposition curve of the material obtained in example 2 of the present invention and a blank of a non-toughened catalyst-free epoxy resin glass polymer.
Detailed Description
The key point of the invention for preparing the catalyst-free super-tough epoxy resin glass polymer material is as follows: firstly, uniformly dispersing anhydride such as glutaric anhydride and diol such as terephthalyl alcohol in epoxy resin, then adding polysebacic anhydride with different mass fractions, and curing the mixed solution at high temperature after vacuumizing; the polysebacic polyanhydride has good compatibility with epoxy resin at high temperature, and does not generate phase separation behavior in the curing process, so that the toughness and tensile strength of the catalyst-free epoxy resin glass macromolecules can be regulated and controlled by controlling the content of the polysebacic polyanhydride, and the high performance and functionalization of the epoxy resin are realized.
In addition, the polysebacic anhydride is long-carbon-chain aliphatic dibasic acid polycondensation anhydride, has higher reaction activity, not only promotes the curing of epoxy resin glass macromolecules, but also can be used as a long-chain molecular structure to increase the difficulty of molecular migration, so that the heat resistance of the material is improved, and meanwhile, the high-content polysebacic anhydride is filled in the epoxy resin glass macromolecules to form no microphase separation structure, so that other performances are not influenced; the epoxy resin has good biodegradability, acid anhydride is subjected to ring opening induced by hydroxyl to form carboxylic acid, the carboxylic acid reacts with epoxy groups to form ester bonds, and a cured product has a self-repairing function at high temperature and can be recovered through reaction with alcohol.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A method for toughening catalyst-free epoxy resin glass macromolecules by using polysebacic anhydride and improving comprehensive properties such as elongation at break, impact toughness, self-repairing efficiency and thermal stability comprises the following specific steps:
preparation of catalyst-free super-tough epoxy resin glass polymer
1) Preheating 40g of epoxy resin at 120 ℃ for 10 min;
2) sequentially adding 23.3g of glutaric anhydride and 14.1g of terephthalyl alcohol into the epoxy resin until the glutaric anhydride and the terephthalyl alcohol are completely dissolved, vacuumizing to remove bubbles, and stirring and mixing uniformly;
3) adding 4g (in the embodiment, the content of polysebacic polyanhydride accounts for 10 percent of the mass ratio of the epoxy resin) of polysebacic polyanhydride into the system until the polysebacic polyanhydride is uniformly mixed;
4) and casting the mixture, and curing at the curing temperature of 130-220 ℃ for 10h to obtain the catalyst-free super-tough self-repairing epoxy resin glass polymer material.
The tensile property of the obtained catalyst-free super-tough epoxy resin glass polymer is tested by adopting a 5967Instron universal testing machine, the tensile rate is 5mm/min, and the test method adopts the ASTM D638 standard for testing. The impact performance of the obtained catalyst-free super-tough epoxy resin glass polymer is tested by adopting an XJUD-5.5 cantilever beam impact tester. The self-repairing performance of the catalyst-free super-toughened epoxy resin glass polymer after heat preservation for 4 hours at 180 ℃ is tested by adopting an Olympus BX51 polarizing microscope. And testing the thermal stability of the obtained catalyst-free super-tough epoxy resin glass polymer by adopting a TA Q550 thermogravimetric analyzer.
The performance test results of the prepared epoxy resin material are shown in the attached drawings 1-4, and it can be known from the drawings that the breaking elongation of the obtained catalyst-free super-toughened epoxy resin glass polymer material is 67%, which is improved by 857% compared with a blank sample (non-toughened epoxy resin glass polymer); the impact toughness is 29.3kJ/m 220 times of blank sample; the self-repairing rate is 87%, and is improved by 2% compared with a blank sample; the thermal decomposition temperature is 381 ℃, which is 2 ℃ higher than that of the blank sample, and the good thermal stability is maintained.
Example 2
A method for toughening catalyst-free epoxy resin glass macromolecules by using polysebacic anhydride and improving comprehensive properties such as elongation at break, impact toughness, self-repairing efficiency and thermal stability comprises the following specific steps:
preparation of catalyst-free super-tough epoxy resin glass polymer
1) Preheating 40g of epoxy resin at 120 ℃ for 10 min;
2) sequentially adding 23.3g of glutaric anhydride and 14.1g of terephthalyl alcohol into the epoxy resin until the glutaric anhydride and the terephthalyl alcohol are completely dissolved, vacuumizing to remove bubbles, and stirring and mixing uniformly;
3) adding 10g (in the embodiment, the content of polysebacic polyanhydride accounts for 25 percent of the mass ratio of the epoxy resin) of polysebacic polyanhydride into the system until the polysebacic polyanhydride is uniformly mixed;
4) and casting the mixture, and curing at the curing temperature of 130-220 ℃ for 10h to obtain the catalyst-free super-tough epoxy resin glass polymer material.
The tensile property of the obtained catalyst-free super-tough epoxy resin glass polymer is tested by adopting a 5967Instron universal testing machine, the tensile rate is 5mm/min, and the test method adopts the ASTM D638 standard for testing. The impact performance of the obtained catalyst-free super-tough epoxy resin glass polymer is tested by adopting an XJUD-5.5 cantilever beam impact tester. The self-repairing performance of the catalyst-free super-toughened epoxy resin glass polymer after heat preservation for 4 hours at 180 ℃ is tested by adopting an Olympus BX51 polarizing microscope. And testing the thermal stability of the obtained catalyst-free super-tough epoxy resin glass polymer by adopting a TA Q550 thermogravimetric analyzer.
The performance test results of the prepared epoxy resin material are shown in the attached figures 5-8, and it can be seen from the figures that the breaking elongation of the obtained catalyst-free super-toughened epoxy resin glass polymer material is 115%, which is improved by 1816% compared with the blank sample (non-toughened epoxy resin glass polymer); the impact toughness is 31.1kJ/m222 times of blank sample; the self-repairing rate is 95%, which is improved by 10% compared with the blank sample; the thermal decomposition temperature is 378 ℃, which is 1 ℃ lower than that of the blank sample, but the good thermal stability is maintained.
Claims (10)
1. The super-tough self-repairing epoxy resin glass polymer material is characterized by comprising the following raw materials in percentage by mass: 100 parts of epoxy resin glass high polymer material and 1-15 parts of polysebacic dianhydride.
2. The super-tough self-repairing epoxy resin glass polymer material as claimed in claim 1, which is prepared by the following preparation method: firstly, stirring and uniformly mixing epoxy resin, acid anhydride and alcohol at the temperature of 60-150 ℃ until the acid anhydride and the alcohol are completely dissolved; then vacuumizing the reaction system in the stirring process until no obvious bubbles emerge; then curing the mixture at 130 to 220 ℃ to obtain the epoxy resin glass polymer material.
3. The super tough self-repairing epoxy glass polymer material of claim 2,
the molar ratio of the acid anhydride to the epoxy group in the epoxy resin is 1: 1, the molar ratio of alcohol to anhydride is 1: 1;
further, the acid anhydride is selected from one of glutaric anhydride, succinic anhydride or phthalic anhydride;
further, the alcohol is selected from one of terephthalyl alcohol, glycerol or polyhydroxy hyperbranched polymer;
further, the epoxy resin is selected from one of glycidyl ether epoxy resin, glycidyl ester epoxy resin or alicyclic epoxy resin.
4. The super-tough self-repairing epoxy resin glass polymer material as claimed in claim 2 or 3, wherein the method for uniformly stirring and mixing the epoxy resin, the acid anhydride and the alcohol at the temperature of 60-150 ℃ until the acid anhydride and the alcohol are completely dissolved comprises the following steps: adding anhydride into epoxy resin, stirring for 5-30 min at 60-150 ℃ until the anhydride is completely dissolved to form a mixed solution, adding glycol into a reaction system, and continuing stirring for 30-60 min;
further, curing for 6-12 h at 130-220 ℃ to obtain the epoxy resin glass polymer material.
5. The preparation method of the super-tough self-repairing epoxy resin glass polymer material of any one of claims 1 to 4, which is characterized by comprising the following steps: firstly, mixing epoxy resin, anhydride, diol and polysebacic anhydride at 60-150 ℃ to obtain epoxy resin blend; then the epoxy resin blend is completely cured; wherein the polysebacic anhydride accounts for 1-25% of the mass of the epoxy resin.
6. A preparation method of a catalyst-free epoxy resin glass polymer material is characterized by comprising the following steps: firstly, stirring and uniformly mixing epoxy resin, acid anhydride and alcohol at the temperature of 60-150 ℃ until the acid anhydride and the alcohol are completely dissolved; then vacuumizing the reaction system in the stirring process until no obvious bubbles emerge; and then completely curing at 130-220 ℃ to obtain the catalyst-free epoxy resin glass polymer material.
7. The method of claim 6, wherein the molar ratio of the acid anhydride to the epoxy group in the epoxy resin is 1: 1, the molar ratio of alcohol to anhydride is 1: 1;
further, the acid anhydride is selected from one of glutaric anhydride, succinic anhydride or phthalic anhydride;
further, the alcohol is selected from one of terephthalyl alcohol, glycerol or polyhydroxy hyperbranched polymer;
further, the epoxy resin is selected from one of glycidyl ether epoxy resin, glycidyl ester epoxy resin or alicyclic epoxy resin.
8. A catalyst-free epoxy glass polymer material, characterized in that it is obtained by the process according to claim 6 or 7.
9. A method for improving the toughness of an epoxy resin glass polymer material without influencing the self-repairing efficiency of the epoxy resin glass polymer material is characterized by comprising the following steps: polysebacic anhydride is selected as a toughening agent to prepare the super-tough epoxy resin glass high polymer material, and the addition amount of the polysecanoic anhydride is 1-15% of the mass of the epoxy resin glass high polymer material.
10. The method for improving the toughness of the epoxy resin glass polymer material without affecting the self-repairing efficiency of the epoxy resin glass polymer material as claimed in claim 9, is characterized in that the method comprises the following steps: adding anhydride, diol and polysebacic anhydride into epoxy resin, mixing the epoxy resin with glutaric anhydride, terephthalic alcohol and polysebacic anhydride to obtain epoxy resin blend, and finally completely curing the epoxy resin blend;
further, the method comprises the following steps: mixing and stirring epoxy resin, acid anhydride, diol and polysebacic anhydride at 60-150 ℃ until the epoxy resin, the acid anhydride, the diol and the polysebacic anhydride are uniformly mixed; then completely curing at 130-220 ℃.
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