CN112745670A - Glass fiber composite material and preparation method thereof - Google Patents
Glass fiber composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention discloses a glass fiber composite material which is characterized by comprising the following components in parts by weight: based on 75-85 parts of thiopurine adamantyl polyamide resin, 10-20 parts of end vinyl sulfonated polyether ether ketone, 5-8 parts of 1-allyl-3-vinyl imidazole chloride salt, 1-2 parts of initiator, 12-23 parts of glass fiber and 2-4 parts of coupling agent. The invention also provides a preparation method of the glass fiber composite material. The glass fiber composite material provided by the invention has the advantages of good comprehensive performance, good performance stability and durability, and excellent mechanical properties, aging resistance, weather resistance, high temperature resistance and flame retardance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a glass fiber composite material and a preparation method thereof.
Background
The material is an essential part in the life process of human beings, and various activities of the human beings can not be separated from the material. The material plays a vital role in the development of the human civilization, the development of the human civilization is not realized without the material, and the development of the human civilization promotes the development of the material in turn, so that the history of the human civilization is the development history of the material, and the material and the human civilization have a myriad of connections. The glass fiber composite material is a common material, is a material prepared from glass fibers, other organic resins and auxiliaries, and is a material with new performance in a macroscopic (microscopic) manner by a physical or chemical method. Because various materials mutually make up for deficiencies in performance to generate a synergistic effect, the comprehensive performance of the material is superior to that of the original composition material to meet various requirements, and the material is widely applied to bridges, aerospace and aviation and building materials.
The existing glass fiber composite material has low elastic modulus, often feels insufficient rigidity in the product structure and is easy to deform; the long-term temperature resistance is poor, and the long-term use at high temperature cannot be generally realized; in addition, the glass fiber reinforced plastic composite materials on the market also have the defects of poor ageing resistance, low shear strength, insufficient oxidation resistance and abrasion resistance, and the like, and the flame retardance and the performance stability are required to be further improved.
For example, chinese patent CN107446302A discloses a long glass fiber composite material, which comprises, by weight, 30-50 parts of acrylic acid-butadiene-styrene, 8.7-13.5 parts of thermoplastic polyurethane elastic plastic, 8 parts of DOPO derivative, 0.4-0.6 part of antioxidant, 2.4-3.6 parts of compatibilizer, and 20-30 parts of glass fiber. The long glass fiber composite material prepared by the method has excellent mechanical properties and flame retardant property of V0 grade, and can solve the phenomenon of fiber floating of the short glass fiber reinforced long glass fiber composite material. However, the weather resistance and the high temperature resistance of the composite material still need to be further improved, the addition is complex in components, the dispersibility or the compatibility problem exists more or less, and the composite material has an outward seepage phenomenon in the long-term use process, so that the performance stability is poor, and the service life needs to be further improved.
There is still a need in the art for a more efficient method for preparing a glass fiber composite material with good combination properties, good performance stability and durability, and excellent mechanical properties, aging resistance, weather resistance, high temperature resistance and flame retardance.
Disclosure of Invention
In order to solve the problems described in the background technology, the invention provides a glass fiber composite material with good comprehensive performance, good performance stability and durability, excellent mechanical property, aging resistance, weather resistance, high temperature resistance and flame retardance; meanwhile, the invention also provides a preparation method of the glass fiber composite material, and the preparation method is simple and easy to implement, has low requirements on reaction conditions and equipment, has high preparation efficiency and finished product qualification rate, consumes less energy and is suitable for continuous large-scale production.
The invention adopts the technical scheme that the glass fiber composite material is characterized by comprising the following components in parts by weight: based on 75-85 parts of thiopurine adamantyl polyamide resin, 10-20 parts of end vinyl sulfonated polyether ether ketone, 5-8 parts of 1-allyl-3-vinyl imidazole chloride salt, 1-2 parts of initiator, 12-23 parts of glass fiber and 2-4 parts of coupling agent.
In one embodiment of the invention, 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.
In one embodiment of the invention, the glass fibers have an aspect ratio of 10 to 30; the average diameter is 2-7 μm.
In one embodiment of the present invention, the initiator is at least one of benzoyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
In one embodiment of the present invention, the end-vinyl sulfonated polyetheretherketone is end-vinyl sulfonated polyetheretherketone prepared by the second polymerization step of chinese patent application No. 201811031492.5, example 1.
In one embodiment of the invention, the preparation method of the thiol purine adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantane dicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and reacting at the temperature of 130-150 ℃ under normal pressure for 2-4 hours, then reducing the pressure to 50-120Pa, heating to 270-290 ℃, keeping the temperature and pressure, stirring and reacting for 12-18 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 3-7 times after the crude product is precipitated in water, and finally drying to constant weight in a vacuum drying oven at the temperature of 85-95 ℃ to obtain the thiol-based purine adamantane polyamide resin.
In one embodiment of the invention, the molar ratio of the 1, 3-adamantanedicarboxylic acid to the 2, 6-diamino-9 h-purine-8-thiol to the catalyst to the high-boiling-point solvent is 1:1 (0.8-1.2) to (6-10).
In one embodiment of the invention, the catalyst is at least one of 2- (2 '-pyridyl) ethyl phosphonic acid, diethyl 2- (2' -pyridyl) ethyl phosphonate, thiophosphoryl amide, tetrabutyl titanate, and antimony acetate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
The invention also aims to provide a preparation method of the glass fiber composite material, which is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
The raw materials in the examples of the invention are all purchased commercially.
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 75-85 parts of thiopurine adamantyl polyamide resin, 10-20 parts of end vinyl sulfonated polyether ether ketone, 5-8 parts of 1-allyl-3-vinyl imidazole chloride salt, 1-2 parts of initiator, 12-23 parts of glass fiber and 2-4 parts of coupling agent.
In one embodiment of the invention, 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.
In one embodiment of the invention, the glass fibers have an aspect ratio of 10 to 30; the average diameter is 2-7 μm.
In one embodiment of the present invention, the initiator is at least one of benzoyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
In one embodiment of the present invention, the end-vinyl sulfonated polyetheretherketone is end-vinyl sulfonated polyetheretherketone prepared by the second polymerization step of chinese patent application No. 201811031492.5, example 1.
In one embodiment of the invention, the preparation method of the thiol purine adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantane dicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and reacting at the temperature of 130-150 ℃ under normal pressure for 2-4 hours, then reducing the pressure to 50-120Pa, heating to 270-290 ℃, keeping the temperature and pressure, stirring and reacting for 12-18 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 3-7 times after the crude product is precipitated in water, and finally drying to constant weight in a vacuum drying oven at the temperature of 85-95 ℃ to obtain the thiol-based purine adamantane polyamide resin.
In one embodiment of the invention, the molar ratio of the 1, 3-adamantanedicarboxylic acid to the 2, 6-diamino-9 h-purine-8-thiol to the catalyst to the high-boiling-point solvent is 1:1 (0.8-1.2) to (6-10).
In one embodiment of the invention, the catalyst is at least one of 2- (2 '-pyridyl) ethyl phosphonic acid, diethyl 2- (2' -pyridyl) ethyl phosphonate, thiophosphoryl amide, tetrabutyl titanate, and antimony acetate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
The invention also aims to provide a preparation method of the glass fiber composite material, which is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
The invention has the beneficial effects that:
1. the preparation method of the glass fiber composite material adopted by the invention is simple and easy to implement, has low requirements on reaction conditions and equipment, high preparation efficiency and finished product qualification rate and low energy consumption, and is suitable for continuous large-scale production.
2. The glass fiber composite material adopted by the invention effectively avoids the problems that the existing glass fiber composite material has low elastic modulus, often feels insufficient rigidity in the product structure and is easy to deform due to the synergistic effect of all the components; the long-term temperature resistance is poor, and the long-term use at high temperature cannot be generally realized; the glass fiber composite material has the defects of poor ageing resistance, low shear strength, insufficient oxidation resistance and wear resistance and low flame retardance and performance stability which need to be further improved, so that the prepared glass fiber composite material has good comprehensive performance, good performance stability and durability, and excellent mechanical property, ageing resistance, weather resistance, high temperature resistance and flame retardance.
3. The glass fiber composite material adopted by the invention is based on that thiol groups on thiol purine adamantyl polyamide resin can generate click reaction with vinyl on molecular chains of end vinyl sulfonated polyether ether ketone and 1-allyl-3-vinyl imidazole chloride under the action of an initiator; the sulfonic group on the end vinyl sulfonated polyether ether ketone can be connected with the imidazole cation on the 1-allyl-3-vinyl imidazole chloride salt through ionic bonds, so that the sulfonic group and the imidazole cation form a cross-linked network structure, the comprehensive performance and the performance stability of the composite material can be effectively improved, and the mechanical property, the aging resistance and the weather resistance of the composite material are better, and the high temperature resistance and the flame retardant property of the composite material are better.
4. The glass fiber composite material adopted by the invention contains not only polyamide structure but also adamantane and purine structure based on thiol purine adamantyl polyamide resin, and the structures enter into a resin molecular chain, so that the prepared material has better comprehensive performance and good anti-aging performance and flame retardance improving effect under the multiple actions of electronic effect, steric effect and conjugated effect.
5. The glass fiber composite material adopted by the invention is introduced with 1-allyl-3-vinyl imidazole chloride, and due to the introduction of an imidazole salt structure, the antistatic property and antibacterial property of the material can be improved, so that the durability of the material is prolonged.
Examples
The present invention will be described in further detail with reference to examples.
Example 1
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 75 parts of thiopurine adamantyl polyamide resin, 10 parts of end vinyl sulfonated polyether ether ketone, 5 parts of 1-allyl-3-vinyl imidazole chloride, 1 part of initiator, 12 parts of glass fiber and 2 parts of coupling agent.
The coupling agent is a silane coupling agent KH 550; the length-diameter ratio of the glass fiber is 10; the average diameter is 2 μm; the initiator is benzoyl peroxide.
The preparation method of the thiol purine-based adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantanedicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring at the normal pressure of 130 ℃ for reaction for 2 hours, reducing the pressure to 50Pa, heating to 270 ℃, preserving heat, maintaining pressure, stirring for reaction for 12 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 3 times after the crude product is precipitated in water, and finally drying in a vacuum drying oven at the temperature of 85 ℃ to constant weight to obtain thiol-based purine adamantane polyamide resin; the molar ratio of the 1, 3-adamantanedicarboxylic acid to the 2, 6-diamino-9 h-purine-8-thiol to the catalyst to the high-boiling-point solvent is 1:1:0.8: 6; the catalyst is 2- (2' -pyridyl) ethyl phosphonic acid; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The preparation method of the glass fiber composite material is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Example 2
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 77 parts of thiol purine adamantyl polyamide resin, 13 parts of end vinyl sulfonated polyether ether ketone, 6 parts of 1-allyl-3-vinyl imidazole chloride, 1.2 parts of initiator, 15 parts of glass fiber and 2.5 parts of coupling agent; the coupling agent is a silane coupling agent KH 560; the length-diameter ratio of the glass fiber is 15; the average diameter was 3 μm; the initiator is dicyclohexyl peroxydicarbonate.
The preparation method of the thiol purine-based adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantanedicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and reacting at the temperature of 135 ℃ under normal pressure for 2.5 hours, then reducing the pressure to 70Pa, heating to 275 ℃, preserving heat and maintaining pressure, stirring and reacting for 14 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing a crude product with ethanol for 4 times, and finally drying in a vacuum drying oven at the temperature of 88 ℃ to constant weight to obtain the thiol-based purine adamantyl polyamide resin; the molar ratio of the 1, 3-adamantanedicarboxylic acid, the 2, 6-diamino-9 h-purine-8-thiol, the catalyst and the high-boiling-point solvent is 1:1:0.9: 7.
The catalyst is diethyl 2- (2' -pyridyl) ethylphosphonate; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The preparation method of the glass fiber composite material is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Example 3
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 80 parts of thiopurine adamantyl polyamide resin, 15 parts of end vinyl sulfonated polyether ether ketone, 6.5 parts of 1-allyl-3-vinyl imidazole chloride salt, 1.5 parts of initiator, 19 parts of glass fiber and 3 parts of coupling agent.
The coupling agent is a silane coupling agent KH 570; the length-diameter ratio of the glass fiber is 20; the average diameter is 5 μm; the initiator is dicyclohexyl peroxydicarbonate.
The preparation method of the thiol purine-based adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantanedicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring at the normal pressure of 140 ℃ for reaction for 3 hours, reducing the pressure to 90Pa, heating to 280 ℃, preserving heat, maintaining pressure, stirring for reaction for 15 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 5 times after the crude product is precipitated in water, and finally drying in a vacuum drying oven at the temperature of 90 ℃ to constant weight to obtain thiol-based purine adamantane polyamide resin; the molar ratio of the 1, 3-adamantanedicarboxylic acid to the 2, 6-diamino-9 h-purine-8-thiol to the catalyst to the high-boiling-point solvent is 1:1:1: 8; the catalyst is thiophosphoryl amide; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The preparation method of the glass fiber composite material is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Example 4
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 84 parts of thiopurine adamantyl polyamide resin, 18 parts of terminated vinyl sulfonated polyether ether ketone, 7.5 parts of 1-allyl-3-vinyl imidazole chloride salt, 1.8 parts of initiator, 21 parts of glass fiber and 3.5 parts of coupling agent; 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 28; the average diameter was 6 μm; the initiator is prepared by mixing benzoyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate and dicyclohexyl peroxydicarbonate according to the mass ratio of 1:2:3: 2.
The preparation method of the thiol purine-based adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantanedicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and reacting at 146 ℃ under normal pressure for 3.5 hours, then reducing the pressure to 110Pa, heating to 286 ℃, preserving heat, maintaining pressure, stirring and reacting for 17 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing a crude product for 6 times with ethanol, and finally drying in a vacuum drying oven at 93 ℃ to constant weight to obtain the thiol-based purine adamantyl polyamide resin; the molar ratio of the 1, 3-adamantanedicarboxylic acid, the 2, 6-diamino-9 h-purine-8-thiol, the catalyst and the high-boiling-point solvent is 1:1:1.1: 9.5.
The catalyst is prepared by mixing 2- (2 '-pyridyl) ethyl phosphonic acid, diethyl 2- (2' -pyridyl) ethyl phosphonate, thiophosphoryl amide, tetrabutyl titanate and antimony acetate according to the mass ratio of 1:2:3:2: 3; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:3:2: 1; the inert gas is argon.
The preparation method of the glass fiber composite material is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Example 5
The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 85 parts of thiopurine adamantyl polyamide resin, 20 parts of end vinyl sulfonated polyether ether ketone, 8 parts of 1-allyl-3-vinyl imidazole chloride, 2 parts of initiator, 23 parts of glass fiber and 4 parts of coupling agent; the coupling agent is a silane coupling agent KH 550; the length-diameter ratio of the glass fiber is 30; the average diameter was 7 μm; the initiator is dicyclohexyl peroxydicarbonate.
The preparation method of the thiol purine-based adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantanedicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring at the normal pressure of 150 ℃ for reaction for 4 hours, reducing the pressure to 120Pa, heating to 290 ℃, preserving heat, maintaining pressure, stirring for reaction for 18 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 7 times after the crude product is precipitated in water, and finally drying in a vacuum drying oven at the temperature of 95 ℃ to constant weight to obtain the thiol-based purine adamantane polyamide resin; the molar ratio of the 1, 3-adamantanedicarboxylic acid to the 2, 6-diamino-9 h-purine-8-thiol to the catalyst to the high-boiling-point solvent is 1:1:1.2: 10; the catalyst is antimony acetate; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is nitrogen.
The preparation method of the glass fiber composite material is characterized by comprising the following steps: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
Comparative example 1
A glass fiber composite was prepared using essentially the same procedure and formulation as in example 1, except that no vinyl terminated sulfonated polyetheretherketone was added.
Comparative example 2
A glass fiber composite was prepared using essentially the same procedure and formulation as in example 1, except that no 1-allyl-3-vinylimidazole chloride salt was added.
Comparative example 3
A glass fiber composite material was prepared by a method and formulation substantially the same as those of example 1, except that 2,2 ʹ -dibromospirosilafluorene 5,5 ʹ -methylenedisalicylic acid polyamide resin was used in place of thiol-purine-based adamantyl polyamide resin; the 2,2 ʹ -dibromo spirosilafluorene 5,5 ʹ -methylene disalicylic acid polyamide resin is prepared by the preparation method of the Chinese patent application No. 201810410788.1, namely the patent example 1.
The glass fiber composite materials described in examples 1-5 and comparative examples 1-3 were subjected to performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) notched impact strength: the test was performed according to GB/T1843-2008.
(2) Tensile strength: testing was performed according to GB 1040-1992.
(3) Heat distortion temperature (HDT, 0.45 MPa): testing was carried out according to GB 1634-1979.
(4) Limiting oxygen index: the test was performed according to GB/T2406-1993.
(5) Weather resistance: the carbon arc lamp aging test is carried out according to GB/T16422.4-1996, and a continuous 720-hour illumination test is adopted, wherein the blackboard temperature is (65 +/-3) DEG C, and the relative humidity is (50 +/-5)%. The tensile strength retention of the product was measured, and the tensile strength retention was defined as the post-aging tensile strength/pre-aging tensile strength × 100%.
TABLE 1 Properties of samples of examples and comparative examples
| Item | Notched impact Strength (KJ/m)2) | Tensile Strength (MPa) | Heat distortion temperature (. degree. C.) | Limiting oxygen index (%) | Weather resistance (%) |
| Example 1 | 55 | 273 | 246 | 35 | 99.2 |
| Example 2 | 58 | 276 | 251 | 37 | 99.5 |
| Example 3 | 62 | 280 | 257 | 39 | 99.7 |
| Example 4 | 65 | 283 | 261 | 40 | 99.8 |
| Example 5 | 67 | 285 | 265 | 41 | 99.9 |
| Comparative example 1 | 38 | 233 | 218 | 33 | 92.3 |
| Comparative example 2 | 42 | 240 | 231 | 32 | 96.6 |
| Comparative example 3 | 46 | 246 | 223 | 30 | 96.2 |
As can be seen from table 1, the glass fiber composite material disclosed in the embodiment of the present invention has better mechanical properties, flame retardancy, weather resistance and heat resistance than the product in the comparative example, which are the result of the synergistic effect of the components.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. The glass fiber composite material is characterized by comprising the following components in parts by weight: based on 75-85 parts of thiopurine adamantyl polyamide resin, 10-20 parts of end vinyl sulfonated polyether ether ketone, 5-8 parts of 1-allyl-3-vinyl imidazole chloride salt, 1-2 parts of initiator, 12-23 parts of glass fiber and 2-4 parts of coupling agent.
2. The glass fiber composite material as claimed in claim 1, wherein the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
3. The glass fiber composite material as claimed in claim 1, wherein the aspect ratio of the glass fiber is 10 to 30; the average diameter is 2-7 μm.
4. The glass fiber composite material as claimed in claim 1, wherein the initiator is at least one of benzoyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
5. The glass fiber composite material as claimed in claim 1, wherein the preparation method of the thiol purine adamantyl polyamide resin comprises the following steps: adding 1, 3-adamantane dicarboxylic acid, 2, 6-diamino-9 h-purine-8-thiol and a catalyst into a high-boiling-point solvent, uniformly stirring to obtain a reaction material, transferring the reaction material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and reacting at the temperature of 130-150 ℃ under normal pressure for 2-4 hours, then reducing the pressure to 50-120Pa, heating to 270-290 ℃, keeping the temperature and pressure, stirring and reacting for 12-18 hours, cooling to room temperature after the reaction is finished, washing a crude product with ethanol for 3-7 times after the crude product is precipitated in water, and finally drying to constant weight in a vacuum drying oven at the temperature of 85-95 ℃ to obtain the thiol-based purine adamantane polyamide resin.
6. The glass fiber composite material as claimed in claim 5, wherein the molar ratio of the 1, 3-adamantanedicarboxylic acid, the 2, 6-diamino-9 h-purine-8-thiol, the catalyst and the high boiling point solvent is 1:1 (0.8-1.2) to (6-10).
7. The glass fiber composite material as claimed in claim 5, wherein the catalyst is at least one of 2- (2 '-pyridyl) ethyl phosphonic acid, diethyl 2- (2' -pyridyl) ethyl phosphonate, thiophosphoramide, tetrabutyl titanate, and antimony acetate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
8. A method for preparing a glass fiber composite material according to any one of claims 1 to 7, comprising the steps of: adding the components in parts by weight into a high-speed stirrer, uniformly mixing to obtain a mixed material, adding the mixed material into a double-screw extruder, and carrying out melt extrusion molding to obtain the glass fiber composite material.
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| CN202011482253.9A CN112745670A (en) | 2020-12-16 | 2020-12-16 | Glass fiber composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894053A (en) * | 2022-12-05 | 2023-04-04 | 宁波擎海紧固件有限公司 | Heat-resistant high-strength fastener material and preparation method thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894053A (en) * | 2022-12-05 | 2023-04-04 | 宁波擎海紧固件有限公司 | Heat-resistant high-strength fastener material and preparation method thereof |
| CN115894053B (en) * | 2022-12-05 | 2023-11-17 | 宁波擎海紧固件有限公司 | Heat-resistant high-strength fastener material and preparation method thereof |
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