CN111303640A - Anti-shearing flame-retardant glass fiber composite material - Google Patents
Anti-shearing flame-retardant glass fiber composite material Download PDFInfo
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Abstract
The invention discloses a shear-resistant flame-retardant glass fiber composite material which is characterized by comprising the following components in parts by weight: 70-90 parts of hyperbranched borate, 4-8 parts of epoxy fluorophenyl sulfone based calixarene, 20-30 parts of glass fiber, 1-3 parts of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 1-2 parts of coupling agent and 0.2-0.5 part of phosphorus pentoxide. The invention also discloses a preparation method of the anti-shearing flame-retardant glass fiber composite material. The anti-shearing flame-retardant glass fiber composite material disclosed by the invention has the advantages of better comprehensive performance, better performance stability, higher shearing force strength, more excellent heat resistance and flame retardance and easier processing and forming.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an anti-shearing flame-retardant glass fiber composite material and a preparation method thereof.
Background
In recent years, with the development of economy and the progress of science and technology, various materials with high added values come, and more wonderful colors are brought to the lives of people. The composite material is a common one, and is a material with new performance composed of two or more materials with different properties by a physical or chemical method on a macroscopic (microscopic) scale. Because various materials mutually make up for deficiencies in performance, a synergistic effect is generated, so that the comprehensive performance of the composite material is superior to that of the original composition material and various requirements are met.
The glass fiber composite material is a novel composite material formed by taking high-strength glass fibers as a reinforcing material, taking synthetic resin, an auxiliary agent and the like as matrix materials and carrying out pultrusion and traction molding. The material has the excellent characteristics of light weight, high mechanical strength, good insulativity and corrosion resistance, good corrosion resistance and fatigue damage resistance and the like, is widely applied to various fields of port and navigation, traffic, civil engineering, new energy, chemical industry and the like, becomes the mainstream trend of the development of the composite material industry in modern and future for a period of time, and has very high potential value. However, the glass fiber material in the prior art is relatively expensive, has poor long-term high temperature resistance, low shear strength, poor oxidation resistance and aging resistance, and is brittle, and the wear resistance needs to be further improved.
The Chinese invention patent with the application number of 201710971000.X discloses a light organic glass fiber composite material, which is composed of the following raw materials in parts by weight: 1-2 parts of palm wax, 0.7-1 part of epoxy chloropropane, 30-40 parts of glass fiber, 7-9 parts of abienol, 0.5-1 part of polybenzimidazole, 1-2 parts of ammonium molybdate, 2-3 parts of hexamethylphosphoric triamide, 2-4 parts of caprylic/capric triglyceride, 2-3 parts of melamine, 0.7-1 part of p-toluenesulfonic acid, 7-10 parts of light calcium carbonate, 2-3 parts of calcium ricinoleate and 50-60 parts of polycarbonate. According to the invention, calcium carbonate and glass fiber are respectively subjected to cyanamide treatment and epoxidation treatment, the surfaces of the calcium carbonate and the glass fiber are sufficiently organized, and then the calcium carbonate and the glass fiber are blended and dispersed in polycarbonate, so that the compatibility of the calcium carbonate and the glass fiber in organic polycarbonate is effectively improved, and the stability of a finished product is improved.
Therefore, a more effective method is sought, and the prepared glass fiber composite material has the milestone significance, and has better comprehensive performance, better performance stability, higher shearing strength, more excellent heat resistance and flame retardance, and easier processing and forming.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the anti-shearing flame-retardant glass fiber composite material and the preparation method thereof, and the preparation method has low dependence on equipment, high preparation efficiency and high yield and is suitable for continuous large-scale production; the prepared glass fiber composite material has better comprehensive performance, better performance stability, larger shearing force strength, more excellent heat resistance and flame retardance and easier processing and forming.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 70-90 parts of hyperbranched borate, 4-8 parts of epoxy fluorophenyl sulfone based calixarene, 20-30 parts of glass fiber, 1-3 parts of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 1-2 parts of coupling agent and 0.2-0.5 part of phosphorus pentoxide.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the glass fibers have an aspect ratio of 50 to 150.
Preferably, the preparation method of the hyperbranched borate ester is as follows: chinese patent application No. 200710017753.3, example 1.
Further, the preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into a high boiling point solvent, adding an alkaline catalyst into the solvent, stirring and reacting for 6-8 hours at 80-90 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy group modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 50-70 ℃ for 8-10 hours to obtain the epoxy fluorophenyl sulfone calix.
Preferably, the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, the epichlorohydrin, the high boiling point solvent and the basic catalyst in the step S1 is 1:4 (15-25) to (1-2).
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the molar ratio of the epoxy-modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, the 2-chloroethyl 4-fluorophenyl sulfone and the N-methyl pyrrolidone in the step S2 is 1:4 (16-24).
The invention also aims to provide a preparation method of the anti-shearing flame-retardant glass fiber composite material, which is characterized by comprising the following steps: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a coupling agent in N-methyl pyrrolidone, stirring for 2-4 hours at 70-80 ℃, then adding glass fiber, kneading and impregnating, carrying out heat treatment, and carrying out hot die pressing to obtain the glass fiber composite material.
Preferably, the heat treatment specifically comprises: first heat-treated at 90-110 ℃ for 1-3 hours, then at 170-180 ℃ for 2-4 hours, then at 210-220 ℃ for 1-3 hours, and finally at 250-260 ℃ for 2-3 hours.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the anti-shearing flame-retardant glass fiber composite material provided by the invention has the advantages of low dependence on equipment, high preparation efficiency and high yield, and is suitable for continuous large-scale production; the preparation method does not need special large-scale equipment like the traditional preparation method of the composite material, and also avoids the defect that the high-melting-point material is not easy to flow and form.
(2) The anti-shearing flame-retardant glass fiber composite material provided by the invention overcomes the defects that a glass fiber material in the prior art is relatively expensive, poor in long-term high-temperature resistance, low in shearing strength, poor in oxidation resistance and aging resistance, crisp in property and further improved in wear resistance, and has the advantages of better comprehensive performance, better performance stability, higher shearing strength, more excellent heat resistance and flame retardance, and easier processing and forming.
(3) According to the anti-shearing flame-retardant glass fiber composite material provided by the invention, the hyperbranched borate is used as the base material, the heat resistance and the flame retardance of the composite material are improved while the technological property and the mechanical property of the composite material are improved, phenolic hydroxyl at the tail end of a hyperbranched borate molecular chain can chemically react with epoxy groups on epoxy group fluorophenyl sulfone-based calixarene to form a three-dimensional network structure, and the comprehensive performance of the composite material is effectively improved; the sulfonic group on the added 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and the benzene ring on the hyperbranched borate molecular chain can generate a crosslinking reaction under the catalytic action of phosphorus pentoxide, so that the comprehensive performance is further improved.
(4) According to the anti-shearing flame-retardant glass fiber composite material provided by the invention, the epoxy group fluorophenyl sulfone based califorrole is added, the califorrole structure is introduced, and the self-assembly can be carried out on the califorrole structure and a branched chain on hyperbranched borate through the interaction of a host and an object, so that the structure is more compact, and the supermolecular structure can effectively improve the flame retardant property of the material and the shape compatibility with other components due to the existence of a cavity, so that the material is not easy to phase separate; the molecular chain of the calixarene is modified with fluorophenyl sulfone group, so that the weather resistance, the aging resistance, the flame retardance, the mechanical property and the chemical corrosion resistance are improved.
(5) According to the anti-shearing flame-retardant glass fiber composite material provided by the invention, the added 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid is introduced into a molecular chain, so that the ultraviolet aging resistance of the material can be effectively improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The preparation of the hyperbranched boronic acid esters referred to in the following examples of the invention is described in: chinese invention patent example 1 with application number 200710017753.3; other raw materials were all purchased commercially.
Example 1
The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 70 parts of hyperbranched borate, 4 parts of epoxy fluorophenyl sulfone based calixarene, 20 parts of glass fiber, 1 part of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 1 part of silane coupling agent KH5501 part and 0.2 part of phosphorus pentoxide; the aspect ratio of the glass fiber is 50.
The preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into dimethyl sulfoxide, adding sodium hydroxide into the dimethyl sulfoxide, stirring the mixture at 80 ℃ for reaction for 6 hours, filtering the mixture to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the epichlorohydrin to the dimethyl sulfoxide to the sodium hydroxide is 1:4:15: 1;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 50 ℃ for 8 hours to obtain epoxy fluorophenyl sulfone calix; the molar ratio of the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 2-chloroethyl 4-fluorophenyl sulfone to the N-methyl pyrrolidone is 1:4: 16.
The preparation method of the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following steps of: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a silane coupling agent KH550 in N-methyl pyrrolidone, stirring for 2 hours at 70 ℃, adding glass fiber, kneading and impregnating, performing heat treatment, and performing hot die pressing to obtain the glass fiber composite material.
The heat treatment specifically comprises the following steps: first heat treated at 90 ℃ for 1 hour, then at 170 ℃ for 2 hours, then at 210 ℃ for 1 hour, and finally at 250 ℃ for 2 hours.
Example 2
The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 75 parts of hyperbranched borate, 5 parts of epoxy fluorophenyl sulfone based calixarene, 22 parts of glass fiber, 1.5 parts of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 5601.2 parts of silane coupling agent KH and 0.3 part of phosphorus pentoxide; the aspect ratio of the glass fiber is 80.
The preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into N, N-dimethylformamide, adding potassium hydroxide into the N, N-dimethylformamide, stirring and reacting for 6.5 hours at 83 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy group modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole; the molar ratio of Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, epichlorohydrin, N-dimethylformamide and potassium hydroxide is 1:4:18: 1.2;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 55 ℃ for 8.5 hours to obtain epoxy fluorophenyl sulfone calix pyrrole; the molar ratio of the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 2-chloroethyl 4-fluorophenyl sulfone to the N-methyl pyrrolidone is 1:4: 18.
The preparation method of the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following steps of: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a silane coupling agent KH560 in N-methyl pyrrolidone, stirring for 2.5 hours at 73 ℃, then adding glass fiber, kneading and impregnating, carrying out heat treatment, and carrying out hot die pressing to obtain the glass fiber composite material.
The heat treatment specifically comprises the following steps: first heat treated at 95 ℃ for 1.5 hours, then at 173 ℃ for 2.5 hours, then at 213 ℃ for 1.5 hours, and finally at 252 ℃ for 2.2 hours.
Example 3
The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 80 parts of hyperbranched borate, 6 parts of epoxy fluorophenyl sulfone based calixarene, 25 parts of glass fiber, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 2 parts of silane coupling agent KH5701.5 parts and 0.35 part of phosphorus pentoxide; the aspect ratio of the glass fiber is 100.
The preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into N, N-dimethylacetamide, adding sodium carbonate into the N, N-dimethylacetamide, stirring and reacting for 7 hours at 85 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole; the molar ratio of Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, epichlorohydrin, N-dimethylacetamide and sodium carbonate is 1:4:20: 1.5;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 60 ℃ for 9 hours to obtain epoxy fluorophenyl sulfone calix; the molar ratio of the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 2-chloroethyl 4-fluorophenyl sulfone to the N-methyl pyrrolidone is 1:4: 20.
The preparation method of the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following steps of: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a silane coupling agent KH570 in N-methyl pyrrolidone, stirring for 3 hours at 75 ℃, adding glass fiber, kneading and impregnating, performing heat treatment, and performing hot die pressing to obtain the glass fiber composite material.
The heat treatment specifically comprises the following steps: first at 100 ℃ for 2 hours, then at 175 ℃ for 3 hours, then at 215 ℃ for 2 hours, and finally at 255 ℃ for 2.5 hours.
Example 4
The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 85 parts of hyperbranched borate, 7 parts of epoxy fluorophenyl sulfone based calixarene, 28 parts of glass fiber, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 1.8 parts of coupling agent and 0.4 part of phosphorus pentoxide.
The coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 2; the aspect ratio of the glass fiber is 130.
The preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into a high boiling point solvent, adding an alkaline catalyst into the solvent, stirring and reacting for 7.5 hours at 88 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy group modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the epichlorohydrin to the high boiling point solvent to the basic catalyst is 1:4:23: 1.8; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:1:3: 2; the alkaline catalyst is prepared by mixing sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate according to the mass ratio of 2:3:1: 2;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 65 ℃ for 9.5 hours to obtain epoxy fluorophenyl sulfone calix pyrrole; the molar ratio of the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 2-chloroethyl 4-fluorophenyl sulfone to the N-methyl pyrrolidone is 1:4: 22.
The preparation method of the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following steps of: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a coupling agent into N-methyl pyrrolidone, stirring for 3.5 hours at 78 ℃, then adding glass fiber, kneading and impregnating, performing heat treatment, and performing hot die pressing to obtain the glass fiber composite material.
The heat treatment specifically comprises the following steps: first at 105 ℃ for 2.8 hours, then at 178 ℃ for 3.5 hours, then at 218 ℃ for 2.5 hours, and finally at 258 ℃ for 2.8 hours.
Example 5
The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 90 parts of hyperbranched borate, 8 parts of epoxy fluorophenyl sulfone based calixarene, 30 parts of glass fiber, 3 parts of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 2 parts of silane coupling agent KH5502 parts and 0.5 part of phosphorus pentoxide; the aspect ratio of the glass fiber is 150.
The preparation method of the epoxy fluorophenyl sulfone calixazole comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into N-methylpyrrolidone, adding potassium carbonate into the N-methylpyrrolidone, stirring and reacting for 8 hours at 90 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy group modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole; the molar ratio of Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, epichlorohydrin, N-methylpyrrolidone and potassium carbonate is 1:4:25: 2;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 70 ℃ for 10 hours to obtain epoxy fluorophenyl sulfone calix; the molar ratio of the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 2-chloroethyl 4-fluorophenyl sulfone to the N-methyl pyrrolidone is 1:4: 24.
The preparation method of the anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following steps of: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a silane coupling agent KH550 in N-methyl pyrrolidone, stirring for 4 hours at 80 ℃, adding glass fiber, kneading and impregnating, performing heat treatment, and performing hot die pressing to obtain the glass fiber composite material.
The heat treatment specifically comprises the following steps: first at 110 ℃ for 3 hours, then at 180 ℃ for 4 hours, then at 220 ℃ for 3 hours, and finally at 260 ℃ for 3 hours.
Comparative example 1
A glass fiber composite material, the formulation and the preparation method are basically the same as those of the glass fiber composite material in the example 1, except that Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole is used for replacing epoxy fluorophenyl sulfuryl calix.
Comparative example 2
A glass fiber composite material, formulation and preparation method were substantially the same as in example 1, except that 2,2' -dihydroxy-4, 4' -dimethoxybenzophenone-5, 5' -disulfonic acid was not added.
Comparative example 3
The formula and the preparation method of the glass fiber composite material are the same as those of the embodiment 1 of the Chinese patent with the application number of 201710971000. X.
To further illustrate the beneficial technical effects of the embodiments of the present invention, the performance test, the test method and the test results of the glass fiber composite materials of the embodiments 1 to 5 of the present invention and the comparative examples 1 to 3 are respectively shown in table 1.
TABLE 1
| Item | Tensile strength | Bending strength | Flame retardancy test | Heat distortion temperature |
| Unit of | MPa | MPa | Stage | ℃ |
| Test standard | GB/T1040.1-2006 | GB/T9341-2000 | UL94 | GB/T1634-1979 |
| Example 1 | 214 | 252 | V0 | 234 |
| Example 2 | 221 | 257 | V0 | 239 |
| Example 3 | 229 | 264 | V0 | 243 |
| Example 4 | 235 | 270 | V0 | 248 |
| Example 5 | 243 | 275 | V0 | 256 |
| Comparative example 1 | 155 | 218 | V1 | 182 |
| Comparative example 2 | 180 | 223 | V1 | 194 |
| Comparative example 3 | 70 | 97 | V1 | 172 |
As can be seen from Table 1, the anti-shearing flame-retardant glass fiber composite material disclosed by the embodiment of the invention has more excellent flame retardance, mechanical properties and heat resistance; this is a result of the synergistic effect of the components.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The anti-shearing flame-retardant glass fiber composite material is characterized by comprising the following components in parts by weight: 70-90 parts of hyperbranched borate, 4-8 parts of epoxy fluorophenyl sulfone based calixarene, 20-30 parts of glass fiber, 1-3 parts of 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid, 1-2 parts of coupling agent and 0.2-0.5 part of phosphorus pentoxide.
2. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
3. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 1, wherein the aspect ratio of the glass fiber is 50-150.
4. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 1, wherein the preparation method of the epoxy fluorophenyl sulfone-based calixarene comprises the following steps:
step S1, adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and epichlorohydrin into a high boiling point solvent, adding an alkaline catalyst into the solvent, stirring and reacting for 6-8 hours at 80-90 ℃, filtering to remove insoluble substances, and performing rotary evaporation to remove the solvent to obtain epoxy group modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole;
step S2, adding the epoxy modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole and 2-chloroethyl 4-fluorophenyl sulfone prepared in the step S1 into N-methyl pyrrolidone, and stirring and reacting at 50-70 ℃ for 8-10 hours to obtain the epoxy fluorophenyl sulfone calix.
5. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 4, wherein the molar ratio of Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, epichlorohydrin, high-boiling-point solvent and basic catalyst in step S1 is 1:4 (15-25) to (1-2).
6. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 4, wherein the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
7. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 4, wherein the basic catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
8. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 4, wherein the molar ratio of the epoxy-modified Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, the 2-chloroethyl 4-fluorophenyl sulfone and the N-methyl pyrrolidone in the step S2 is 1:4 (16-24).
9. The shear-resistant flame-retardant glass fiber composite material according to any one of claims 1 to 8, wherein the preparation method of the shear-resistant flame-retardant glass fiber composite material comprises the following steps: dissolving hyperbranched borate, epoxy fluorophenyl sulfone-based california, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonic acid and a coupling agent in N-methyl pyrrolidone, stirring for 2-4 hours at 70-80 ℃, then adding glass fiber, kneading and impregnating, carrying out heat treatment, and carrying out hot die pressing to obtain the glass fiber composite material.
10. The shear-resistant flame-retardant glass fiber composite material as claimed in claim 9, wherein the heat treatment is specifically: first heat-treated at 90-110 ℃ for 1-3 hours, then at 170-180 ℃ for 2-4 hours, then at 210-220 ℃ for 1-3 hours, and finally at 250-260 ℃ for 2-3 hours.
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