Carbon fiber resin composite material and preparation method thereof
By using flame retardants containing nitrogen, phosphorus and silicon in carbon fiber resin composite materials, the problem of insufficient flame retardant performance of the material is solved, efficient and long-lasting flame retardant effect is achieved, and the mechanical properties and stability of the material are improved.
Patent Information
- Application Number
- CN202411375666.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2024-12-24
- Estimated Expiration
- 2044-09-30
AI Technical Summary
The flame retardant performance of carbon fiber resin composite materials is poor. When the prior art improves flame retardant by adding inorganic flame retardants, it will affect the physical and mechanical properties and thermal properties of the material, and lead to a reduction in mechanical properties and corrosion resistance.
The flame retardant containing halogen-free flame retardant elements nitrogen, phosphorus and silicon is prepared through specific synthesis steps. The phosphorus element provides an acid source, the nitrogen element provides an air source, and the silicon element generates an inorganic thermal insulation. The protective layer enhances the flame retardant effect of the material and is stable in the material through compatibility and chemical action.
It achieves the efficient, long-lasting and safe flame retardant effect of carbon fiber resin composite materials, improves the flame retardant performance, toughness and tensile strength of the material, while reducing the smoke and harmfulness.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of polymer materials, and in particular, relates to a carbon fiber resin composite material and a preparation method thereof. Background Art
[0002] The material composed of carbon fiber reinforced material and resin matrix is called carbon fiber resin composite material or carbon fiber reinforced plastic. Carbon fiber is usually combined with epoxy resin, phenolic resin, polytetrafluoroethylene and other materials to form composite materials. Carbon fiber resin composite materials have excellent impact resistance, fatigue resistance, corrosion resistance and heat resistance, etc., and are very popular in the market and are becoming popular.
[0003] However, the flame retardant properties of carbon fiber resin composites are relatively poor. Most of the existing technologies use the method of adding flame retardant materials to improve the flame retardancy of composite materials. Usually, inorganic flame retardants and fillers are frequently used flame retardants. In actual use, the addition of inorganic flame retardants will change the physical, mechanical and thermal properties of the composite materials. At the same time, these powders are very easy to agglomerate, which directly affects the flame retardant effect of the inorganic filler particles. At the same time, these agglomerated inorganic flame retardants and fillers will greatly cause void defects inside the material, thereby leading to a decrease in the overall mechanical properties and corrosion resistance of the composite material. Summary of the invention
[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a carbon fiber resin composite material and a preparation method thereof.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A carbon fiber resin composite material comprises the following raw materials in parts by weight: 60-70 parts of polyester resin, 15-40 parts of carbon fiber, 5-10 parts of epoxy resin, 4-9 parts of flame retardant, 2-4 parts of compatibilizer, 1-3 parts of curing agent, 1-3 parts of lubricant, 1-3 parts of antioxidant and 0.02-0.05 parts of initiator.
[0007] Furthermore, the polyester resin is polybutylene terephthalate.
[0008] Furthermore, the carbon fiber is one or both of polyacrylonitrile carbon fiber and pitch carbon fiber.
[0009] Furthermore, the epoxy resin is one or more of glycidyl ether epoxy resin and glycidyl ester epoxy resin.
[0010] Furthermore, the flame retardant is prepared by the following steps:
[0011] S1. A brown three-necked flask was dried and purged with nitrogen to expel air and moisture from the flask, and then 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, N-methyl-4-pentene-1-amine and chloroform were added, and triethylamine was slowly added after stirring to dissolve. After the addition was completed, the temperature was raised to 60°C and stirred for reaction for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1; the dosage ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, N-methyl-4-pentene-1-amine, triethylamine and chloroform was 19.8 mL:9.6 g:17.5 mL:110 mL;
[0012] Under heating, the molar ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and N-methyl-4-pentene-1-amine is controlled to be 1:1.05-1.1, and the -Cl of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the -NH- of N-methyl-4-pentene-1-amine undergo nucleophilic substitution reaction, and triethylamine is used as an acid binding agent. The reaction process is as follows:
[0013]
[0014] S2. Blow nitrogen through a dry three-necked flask for 30 minutes to expel air and moisture from the flask, then add melamine, intermediate 1 and 1,4-dioxane, mix well, then slowly add pyridine, heat to 60°C and stir for 3 hours, cool to room temperature after the reaction, and then distill under reduced pressure to obtain intermediate 2; the usage ratio of melamine, intermediate 1, pyridine and 1,4-dioxane is 10.1 g:24.5 g:9.1 mL:130 mL;
[0015] The molar ratio of melamine to intermediate 1 is controlled to be 1:1 and intermediate 1 is slightly excessive. Under heating, -NH- of melamine and -Cl of intermediate 1 undergo nucleophilic substitution reaction. Pyridine is used as an acid-binding agent. The reaction process is as follows:
[0016]
[0017] S3, replace the air in the four-necked reaction bottle with nitrogen at room temperature, add 2-diethoxyphosphorylethanol and 1,4-dioxane, stir to dissolve, and then slowly add octadecyltrichlorosilane. The system temperature is not higher than 20°C during the addition process. After the addition is completed, stir and react at 30°C for 6 hours. When no HCl gas is released, cool to below 20°C, filter, rinse the filter cake with dioxane, and vacuum dry to obtain intermediate 3; the dosage ratio of octadecyltrichlorosilane, 2-diethoxyphosphorylethanol and 1,4-dioxane is 35.5mL:34.9g:180mL;
[0018] At 30°C, the molar ratio of octadecyltrichlorosilane to 2-diethoxyphosphorylethanol is controlled to be 1:2.1-2.15, and esterification reaction occurs between 2-diethoxyphosphorylethanol and octadecyltrichlorosilane. The reaction process is shown below:
[0019]
[0020] S4. Replace the air in a four-necked reaction bottle with nitrogen at room temperature, add intermediate 2, intermediate 3 and DMF (N,N-dimethylformamide), stir to dissolve, and then slowly add triethylamine. The system temperature is not higher than 30°C during the addition process. After the addition is completed, stir and react at room temperature for 6 hours. After the reaction is completed, distill under reduced pressure to obtain a flame retardant. The amount ratio of intermediate 2, intermediate 3, triethylamine and DMF is 16.5g:27.2g:7.5mL:200mL.
[0021] The molar ratio of intermediate 2 to intermediate 3 is controlled to be 1.05-1.1:1, and intermediate 2 and intermediate 3 undergo substitution reaction at room temperature in the presence of triethylamine. The reaction process is as follows:
[0022]
[0023] The flame retardant contains halogen-free flame retardant elements of nitrogen, phosphorus, and silicon. The three elements work together to retard flames, making the flame retardant highly efficient and safe. The phosphorus element in the flame retardant provides an acid source, reacts with the polymer resin, and promotes the formation of carbonized products; the nitrogen element provides a gas source, which can make the system expand and foam, and also promotes the formation of the carbonized layer, forming porous foam carbon; the silicon element generates an inorganic heat-insulating protective layer containing -Si-O-bonds and -Si-C-bonds during combustion, which not only prevents the decomposition products generated by combustion from escaping, but also inhibits the thermal decomposition of polymer materials, achieving the purpose of high flame retardancy, low smoke emission, and low harmfulness.
[0024] The long carbon chains in the flame retardant that can stretch and rotate freely can improve the mechanical properties such as toughness and tensile strength of carbon fiber resin composites.
[0025] According to the principle of like dissolves like, the lipophilic heterocycles and long carbon chains in the flame retardant increase the compatibility between the flame retardant and the other raw materials. In addition, the flame retardant also contains primary amino groups and multiple secondary amino groups, which can react chemically with the epoxy groups in the epoxy resin during the melt extrusion process. At the same time, the carbon-carbon double bonds at the ends of the flame retardant can react chemically with the unreacted double bonds in the compatibilizer under the action of the initiator. Therefore, the flame retardant of the present invention can stably exist in the carbon fiber resin composite material, is not easy to migrate and escape, and can fully play its role, giving the carbon fiber resin composite material an excellent and stable flame retardant effect.
[0026] Furthermore, the compatibilizer is one or both of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.
[0027] Furthermore, the curing agent is one or more of polyamide resin, dicyandiamide curing agent, and imidazole curing agent.
[0028] Furthermore, the lubricant is one or more of zinc stearate, calcium stearate, magnesium stearate, oleamide, and erucamide.
[0029] Furthermore, the antioxidant is one or more of antioxidant 168, antioxidant 300, antioxidant 1010, and antioxidant 1035.
[0030] Furthermore, the initiator is one or more of dibenzoyl peroxide, diisopropylbenzene peroxide, and azobisisobutyronitrile.
[0031] A method for preparing a carbon fiber resin composite material comprises the following steps:
[0032] The above raw materials are weighed by weight, and all the raw materials except the carbon fiber are added to a high-speed mixer for mixing. After the mixing is uniform, the raw materials are put into an extruder, and the carbon fiber is added at the same time, and melt-extruded to obtain a carbon fiber resin composite material.
[0033] Beneficial effects of the present invention: the flame retardant of the present invention has good compatibility with other raw materials, and there is a chemical reaction between the flame retardant and the epoxy resin and the compatibilizer. Therefore, the flame retardant rich in halogen-free flame retardant elements nitrogen, phosphorus and silicon can be stably present in the carbon fiber resin composite material for a long time and fully play its role. Therefore, the carbon fiber resin composite material of the present invention has a high-efficiency, long-lasting and safe flame retardant effect. DETAILED DESCRIPTION
[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0035] Example 1
[0036] The flame retardant is prepared in the following steps:
[0037] Furthermore, the flame retardant is prepared by the following steps:
[0038] S1. Nitrogen was blown into a 250 mL dry brown three-necked flask to expel air and moisture from the flask, followed by the addition of 19.8 mL of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, 9.6 g of N-methyl-4-penten-1-amine and 110 mL of chloroform. After stirring to dissolve, 17.5 mL of triethylamine was slowly added. After the addition was completed, the temperature was raised to 60° C. and stirred for reaction for 3 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1.
[0039] S2, nitrogen was blown into a 250 mL dry three-necked flask for 30 min to expel air and moisture in the flask, then 10.1 g melamine, 25.3 g intermediate 1 and 130 mL 1,4-dioxane were added, 9.1 mL pyridine was slowly added after mixing, the temperature was raised to 60 ° C and stirred for 3 h, after the reaction was completed, it was cooled to room temperature, and then distilled under reduced pressure to obtain intermediate 2;
[0040] S3, replace the air in a 500mL four-necked reaction bottle with nitrogen at room temperature, add 34.9g of 2-diethoxyphosphorylethanol and 180mL of 1,4-dioxane, stir to dissolve, then slowly add 35.5mL of octadecyltrichlorosilane, the system temperature is not higher than 20°C during the addition process, stir and react at 30°C for 6h after the addition is complete, wait until no HCl gas is released, cool to below 20°C, filter, rinse the filter cake with dioxane, and vacuum dry to obtain intermediate 3;
[0041] S4. Replace the air in a 500mL four-necked reaction bottle with nitrogen at room temperature, add 16.7g of intermediate 2, 27.2g of intermediate 3 and 200mL of DMF, stir to dissolve, then slowly add 7.5mL of triethylamine. During the addition, the system temperature is not higher than 30°C. After the addition is completed, stir and react at room temperature for 6h. After the reaction is completed, distill under reduced pressure to obtain a flame retardant.
[0042] Example 2
[0043] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0044] The above raw materials were weighed by weight, and 60 parts of polybutylene terephthalate resin, 5 parts of bisphenol F epoxy resin, 4 parts of the flame retardant prepared in Example 1, 2 parts of maleic anhydride grafted polyethylene, 1 part of polyamide resin, 1 part of zinc stearate, 1 part of antioxidant 1010, and 0.02 parts of azobisisobutyronitrile were added to a high-speed mixer for mixing. After mixing evenly, the mixture was put into an extruder, and 15 parts of polyacrylonitrile carbon fiber were added at the same time for melt extrusion to obtain a carbon fiber resin composite material.
[0045] Example 3
[0046] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0047] The above raw materials are weighed by weight, and 68 parts of polybutylene terephthalate resin, 9 parts of diglycidyl phthalate, 7 parts of the flame retardant prepared in Example 1, 3 parts of maleic anhydride grafted polypropylene, 2 parts of 2-ethyl-4-methylimidazole, 1 part of calcium stearate, 1 part of erucic acid amide, 0.4 parts of antioxidant 168, 2 parts of antioxidant 1035, and 0.04 parts of diisopropylbenzene peroxide are added to a high-speed mixer for mixing. After mixing evenly, the mixture is put into an extruder, and 30 parts of asphalt carbon fiber are added at the same time, melt-extruded to obtain a carbon fiber resin composite material.
[0048] Example 4
[0049] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0050] The above raw materials were weighed by weight, and 70 parts of polybutylene terephthalate resin, 10 parts of bisphenol A epoxy resin, 9 parts of the flame retardant prepared in Example 1, 4 parts of maleic anhydride grafted polypropylene, 1 part of polyamide resin, 2 parts of DDH-5850 dicyandiamide curing agent, 2 parts of magnesium stearate, 1 part of oleamide, 0.5 parts of antioxidant 168, 0.5 parts of antioxidant 300, 2 parts of antioxidant 1010, and 0.05 parts of dibenzoyl peroxide were added to a high-speed mixer for mixing. After mixing evenly, the mixture was put into an extruder, and 40 parts of polyacrylonitrile carbon fiber were added at the same time for melt extrusion to obtain a carbon fiber resin composite material.
[0051] Comparative Example 1
[0052] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0053] The remaining steps remain unchanged, only the flame retardant in Example 4 is removed to prepare a carbon fiber resin composite material.
[0054] Comparative Example 2
[0055] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0056] The remaining steps remained unchanged, except that the flame retardant in Example 4 was replaced by 9 parts of magnesium hydroxide to prepare a carbon fiber resin composite material.
[0057] Comparative Example 3
[0058] The specific steps of preparing the carbon fiber resin composite material are as follows:
[0059] The remaining steps remained unchanged, except that the flame retardant in Example 4 was replaced by 9 parts of the flame retardant Doher-9812 produced by Dongguan Doher New Material Technology Co., Ltd. to prepare a carbon fiber resin composite material.
[0060] Performance Testing
[0061] The carbon fiber resin composite materials prepared in Examples 2-4 and Comparative Examples 1-3 were subjected to the following performance tests, and the test results are shown in the following table:
[0062]
[0063] “ / ” indicates no flame retardant rating.
[0064] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0065] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.
Claims
1. A carbon fiber resin composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 60-70 parts of polyester resin, 15-40 parts of carbon fiber, 5-10 parts of epoxy resin, 4-9 parts of flame retardant, 2-4 parts of compatibilizer, 1-3 parts of curing agent, 1-3 parts of lubricant, 1-3 parts of antioxidant and 0.02-0.05 parts of initiator; Wherein, the flame retardant is prepared by the following steps: S1. After nitrogen is blown into the flask, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, N-methyl-4-penten-1-amine and chloroform are added, and triethylamine is added after stirring. The mixture is reacted at 60° C. for 3 h, cooled, and distilled under reduced pressure to obtain intermediate 1. The dosage ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, N-methyl-4-penten-1-amine, triethylamine and chloroform is 19.8 mL:9.6 g:17.5 mL:110 mL. S2. After nitrogen is blown into the flask, melamine, intermediate 1 and 1,4-dioxane are added, pyridine is added after mixing, and the mixture is reacted at 60° C. for 3 h, cooled, and distilled under reduced pressure to obtain intermediate 2; the dosage ratio of melamine, intermediate 1, pyridine and 1,4-dioxane is 10.1 g:24.5 g:9.1 mL:130 mL; S3, replace the air in the bottle with nitrogen, add 2-diethoxyphosphorylethanol and 1,4-dioxane, stir, add octadecyltrichlorosilane, react at 30°C for 6h, cool, filter, rinse, and dry to obtain intermediate 3; the dosage ratio of octadecyltrichlorosilane, 2-diethoxyphosphorylethanol and 1,4-dioxane is 35.5mL:34.9g:180mL; S4. Replace the air in the bottle with nitrogen, add intermediate 2, intermediate 3 and DMF, stir, add triethylamine, react at room temperature for 6 hours, and distill under reduced pressure to obtain a flame retardant; the amount ratio of intermediate 2, intermediate 3, triethylamine and DMF is 16.5g:27.2g:7.5mL:200mL.
2. A carbon fiber resin composite material according to claim 1, characterized in that: The polyester resin is polybutylene terephthalate.
3. The carbon fiber resin composite material according to claim 1, characterized in that: The carbon fiber is one or both of polyacrylonitrile carbon fiber and pitch carbon fiber.
4. The carbon fiber resin composite material according to claim 1, characterized in that: The epoxy resin is one or more of glycidyl ether epoxy resin and glycidyl ester epoxy resin.
5. The carbon fiber resin composite material according to claim 1, characterized in that: The compatibilizer is one or both of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.
6. The carbon fiber resin composite material according to claim 1, characterized in that: The curing agent is one or more of polyamide resin, dicyandiamide curing agent and imidazole curing agent.
7. The carbon fiber resin composite material according to claim 1, characterized in that: The lubricant is one or more of zinc stearate, calcium stearate, magnesium stearate, oleamide and erucamide.
8. The carbon fiber resin composite material according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 168, antioxidant 300, antioxidant 1010, and antioxidant 1035; the initiator is one or more of dibenzoyl peroxide, diisopropylbenzene peroxide, and azobisisobutyronitrile.
9. The method for preparing a carbon fiber resin composite material according to claim 1, characterized in that: The following steps are involved: The above raw materials are weighed by weight, and all the raw materials except the carbon fiber are added to a high-speed mixer for mixing. After the mixing is uniform, the raw materials are put into an extruder, and the carbon fiber is added at the same time, and melt-extruded to obtain a carbon fiber resin composite material.