Waterborne epoxy modified naringin, carbon fiber sizing agent, sized carbon fiber and preparation method

Abstract

Waterborne epoxy modified naringin, carbon fiber sizing agent, sized carbon fiber and preparation method, which relate to the technical field of carbon fiber surface modification, and solve the problems of complex use method of existing water-soluble sizing agents and residual organic solvents. Preparation of waterborne epoxy modified naringin: Mix naringin, allyl bromide, anhydrous potassium carbonate, benzyltriethylammonium chloride and ethanol, heat up and react fully; Purify the product, and then react fully with m-chloroperbenzoic acid to obtain a brown-red liquid; Wash, filter and dry to obtain waterborne epoxy modified naringin. Carbon fiber sizing agent, including 0.1 part to 10 parts of waterborne epoxy modified naringin, 0.2 part to 10 parts of surfactant, 0.1 part to 5 parts of lubricant, 0.1 part to 5 parts of binder, 0.2 part to 5 parts of antistatic agent, and 100 parts of water. Preparation of sized carbon fiber: Place the prepared sizing agent in a sizing tank, impregnate the carbon fiber and complete wire drawing and sizing; Use air drying and winding.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon fiber surface modification, and specifically relates to an aqueous epoxy modified naringin, a carbon fiber sizing agent, sized carbon fiber and a preparation method thereof. Background Art

[0002] Compared with traditional materials, carbon fiber composites have characteristics such as high strength, high modulus, low density, chemical corrosion resistance, high thermal conductivity and low resistance. They are one of the important reinforcing materials in advanced composite materials today and are widely used in fields such as aerospace, industrial building materials, and sports equipment. However, during the production and processing of carbon fibers, defects such as easy abrasion with machinery, generation of fuzz and single fiber breakage occur, reducing their properties. To solve the above problems, the sizing method is considered a low-cost, simple and efficient method.

[0003] The sizing agent is a very important auxiliary in the carbon fiber sizing process. During the production and processing process, a suitable sizing agent can effectively protect the carbon fiber surface, reduce fuzz and single fiber breakage, strengthen the fiber bundle, improve the durability and processability of carbon fibers, and improve the interfacial properties of carbon fiber - matrix resin. With the increasing national requirements for environmental protection, aqueous sizing agents have received more and more attention.

[0004] Existing aqueous sizing agents are mainly aqueous modified epoxy resin systems, which are emulsions prepared with epoxy resin as the main body and a certain amount of auxiliary materials such as emulsifiers and lubricants. The surfactants in its components can improve the wettability of the carbon fiber surface, and at the same time, water as a solvent can achieve the purpose of environmental protection. However, due to the use of emulsification to disperse epoxy resin in water for preparation, its storage stability is usually poor, and there are usually problems such as complex usage methods, cumbersome processes, and high production energy consumption. At the same time, when emulsifying epoxy resin-based aqueous sizing agents, it is often necessary to add some organic solvents such as acetone and ethers for solubilization, and these organic solvents in the sizing agents are difficult to remove during use and will also damage the equipment.

[0005] Therefore, developing a water-soluble sizing agent that is easy to use, reduces production energy consumption, does not require additional organic solvents, and can improve the comprehensive performance of carbon fibers after sizing is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] In order to solve the problems of complex usage methods and organic solvent residues of existing water-soluble sizing agents, the present invention proposes a kind of.

[0007] The technical solution of the present invention is as follows:

[0008] An aqueous epoxy modified naringin, the structural formula is as follows:

[0009]

[0010] The preparation method of the above-mentioned waterborne epoxy-modified naringin comprises the following steps:

[0011] S1. Mix naringin, allyl bromide, anhydrous potassium carbonate, benzyltriethylammonium chloride and ethanol, heat up to 40°C - 70°C, and react for 12h - 48h;

[0012] S2. Purify the product in step S1, and then fully react it with m-chloroperbenzoic acid to obtain a brownish-red liquid; the reaction conditions are as follows: first carry out the reaction in an ice-water bath, and after the reaction heat release is stable, heat up to room temperature, and react at room temperature for 24h - 72h;

[0013] S3. Wash, filter and dry with deionized water to obtain waterborne epoxy-modified naringin.

[0014] Preferably, the molar ratio of naringin, allyl bromide, anhydrous potassium carbonate, benzyltriethylammonium chloride and ethanol in step S1 is 1:(1 - 3):(1 - 2):(0.2 - 0.3).

[0015] Preferably, the reaction conditions in step S2 are as follows: first carry out the reaction in an ice-water bath, and after the reaction heat release is stable, heat up to room temperature, and react at room temperature for 24h - 72h.

[0016] A sizing agent for carbon fiber comprises the following components in parts by mass:

[0017] 0.1 part - 10 parts of the above-mentioned waterborne epoxy-modified naringin, 0.2 part - 10 parts of surfactant, 0.1 part - 5 parts of lubricant, 0.1 part - 5 parts of binder, 0.2 part - 5 parts of antistatic agent, and 100 parts of deionized water.

[0018] Preferably, the surfactant is one or a mixture of at least two of cetyltrimethylammonium bromide, sodium dodecylsulfonate, sodium dodecyl sulfate, benzalkonium chloride, Tween series (including Tween-20, Tween-40, Tween-60 and Tween-80), polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, Peregal O series, OP series, castor oil polyoxyethylene ether series (including EL-30, EL-40, EL-60 and EL-80).

[0019] Preferably, the lubricant is one or a mixture of at least two of polyoxyethylene ether, butyl stearate, higher aliphatic amine, higher aliphatic alcohol, higher aliphatic ester.

[0020] Preferably, the binder is one or a mixture of at least two of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylate, ethyl acetate, polyvinyl alcohol.

[0021] Preferably, the antistatic agent is one or a mixture of at least two of polyethylene glycol methacrylate copolymer, polyether ester amide, polyether ester acetamide, polyethylene oxide, propylene oxide copolymer, and polyethylene glycol dimaleate monoester.

[0022] A sized carbon fiber includes a carbon fiber and a sizing agent coating attached to the surface of the carbon fiber, and the sizing agent coating is formed by the above-mentioned carbon fiber sizing agent.

[0023] A method for preparing the sized carbon fiber as described above includes the following steps:

[0024] Step 1: Add waterborne epoxy-modified naringin, surfactant, lubricant, binder, and antistatic agent to deionized water in proportion, and stir evenly at a temperature maintained at 10°C to 60°C;

[0025] Step 2: Place the sizing agent prepared in Step 1 in a sizing tank, and the unsized carbon fiber is sized by passing through the sizing tank for impregnation. The impregnation time is 5 s to 30 s;

[0026] Step 3: The sized carbon fiber is dried by blowing air. The drying temperature is 25°C to 100°C, and the dried sized carbon fiber is obtained after winding.

[0027] Compared with the prior art, the specific beneficial effects of the present invention are as follows:

[0028] 1. The carbon fiber sizing agent provided by the present invention is based on waterborne epoxy-modified naringin prepared from phytoglycosides as raw materials. The raw material source is simple and reliable, the preparation process is simple, and the operability is strong; the sizing agent has a simple usage method and does not involve any organic solvents during use, effectively avoiding the problem of damage to equipment, and has good prospects for large-scale application;

[0029] 2. The sizing agent provided by the present invention has a uniform concentration and high storage stability; by applying the sizing agent provided by the present invention, the surface polarity of the carbon fiber can be effectively improved, the wettability and roughness of the carbon fiber surface are improved, and the interfacial performance of the carbon fiber composite material is enhanced. Description of the Drawings

[0030] Figure 1 It is an infrared spectrum diagram of the waterborne epoxy-modified naringin prepared in Example 1;

[0031] Figure 2 It is a nuclear magnetic resonance hydrogen spectrum diagram of the waterborne epoxy-modified naringin prepared in Example 1;

[0032] Figure 3 It is a scanning electron microscope diagram of the sized carbon fiber prepared in Example 2;

[0033] Figure 4 Scanning electron micrograph of the sized carbon fiber prepared in Example 3;

[0034] Figure 5 Scanning electron micrograph of the sized carbon fiber prepared in Example 4;

[0035] Figure 6 Scanning electron micrograph of the sized carbon fiber prepared in the comparative example. Detailed implementation manners

[0036] To make the technical solutions of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the present invention. It should be noted that the following embodiments are only used to better understand the technical solutions of the present invention and should not be construed as a limitation of the present invention.

[0037] Example 1.

[0038] Synthesis of waterborne epoxy modified naringin:

[0039] (1) 40 g of naringin, 37.6 g of potassium carbonate, 2.164 g of benzyltriethylammonium chloride and 23.6 ml of allyl bromide were added to 400 ml of ethanol solution, heated to 50 °C and reacted for 24 h to obtain a double bond modified naringin solution;

[0040] The solid precipitate was filtered off, the solvent was removed from the filtrate to obtain a dry solid, which was then rinsed 3 times with anhydrous ethanol, and the solid precipitate was repeatedly filtered off. Finally, the filtrate was dried to obtain double bond modified naringin;

[0041] (2) 40 g of the product obtained in step (1) and 31.36 g of m-chloroperbenzoic acid were added to 400 ml of ethanol solution and reacted in an ice bath at 0 °C for 2 h, and then heated to room temperature and reacted for 46 h to obtain a solution of a water-soluble compound based on naringin. After the reaction was completed, the solid precipitate was filtered off, and the solvent was removed from the filtrate to obtain a dry solid;

[0042] (3) It was rinsed 3 times with 400 ml of pure water, the aqueous phase was collected, and the aqueous phase was rotary evaporated to obtain a dry solid; it was then dissolved in 100 ml of water and the insoluble matter was filtered off, and this was repeated 3 times. Finally, the filtrate was dried to obtain waterborne epoxy modified naringin with a yield of 94.5%.

[0043] Figure 1 Infrared spectrum of the final product of this example; Figure 2 1H nuclear magnetic resonance spectrum of the final product of this example. According to Figure 1 and Figure 2 it can be proved that waterborne epoxy modified naringin was successfully synthesized in this example.

[0044] Example 2.

[0045] In this example, an aqueous epoxy-modified naringin carbon fiber sizing agent was prepared. By weight, it includes the following components: 0.5 part of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, 0.2 part of polyethylene oxide, and 100 parts of deionized water.

[0046] The preparation process of the carbon fiber sizing agent is as follows:

[0047] First, heat 100 parts of deionized water to 60 °C, and while stirring, add 0.5 part of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, and 0.2 part of polyethylene oxide. After the naringin is completely dissolved, the carbon fiber sizing agent is obtained.

[0048] In this example, the above sizing agent was used to prepare sized carbon fibers, which mainly included the following steps: Place the above sizing agent in a sizing tank, and the unsized carbon fibers are sized by passing through the sizing tank for wire drawing. The impregnation time is 10 s; the sized carbon fibers are dried by blowing air, and the drying temperature is 60 °C. After winding, the dried sized carbon fibers are obtained.

[0049] The scanning electron microscope image of the carbon fibers prepared in this example is as Figure 3 shown. It can be seen from the picture that there is a little sizing agent coating attached to the surface of the sized carbon fibers.

[0050] Example 3.

[0051] In this example, an aqueous epoxy-modified naringin carbon fiber sizing agent was prepared. By weight, it includes the following components: 1 part of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, 0.2 part of polyethylene oxide, and 100 parts of deionized water.

[0052] The preparation process of the carbon fiber sizing agent is as follows:

[0053] First, heat 100 parts of deionized water to 60 °C, and while stirring, add 1 part of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, and 0.2 part of polyethylene oxide. After the naringin is completely dissolved, the carbon fiber sizing agent is obtained.

[0054] In this example, the above sizing agent was used to prepare sized carbon fibers, which mainly included the following steps: Place the above sizing agent in a sizing tank, and the unsized carbon fibers are sized by passing through the sizing tank for wire drawing. The impregnation time is 15 s; the sized carbon fibers are dried by blowing air, and the drying temperature is 60 °C. After winding, the dried sized carbon fibers are obtained.

[0055] The scanning electron microscope image of the carbon fiber prepared in this example is as Figure 4 shown. It can be seen from the image that there is an obvious sizing agent coating on the surface of the sized carbon fiber.

[0056] Example 4.

[0057] In this example, an aqueous epoxy-modified naringin carbon fiber sizing agent was prepared. By weight, it includes the following components: 2 parts of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, 0.2 part of polyethylene oxide, and 100 parts of deionized water.

[0058] The preparation process of the carbon fiber sizing agent is as follows:

[0059] First, heat 100 parts of deionized water to 60 °C, and while stirring, add 2 parts of aqueous epoxy-modified naringin, 0.2 part of cetyltrimethylammonium bromide, 0.1 part of polyoxyethylene ether, 0.1 part of polyacrylamide, 0.2 part of polyethylene oxide. After the naringin is completely dissolved, the carbon fiber sizing agent is obtained.

[0060] In this example, a sized carbon fiber was prepared using the above sizing agent, mainly including the following steps: Place the above sizing agent in a sizing tank, and the unsized carbon fiber is sized by passing through the sizing tank for wire feeding. The impregnation time is 20 s; the sized carbon fiber is dried by blowing air, and the drying temperature is 80 °C. After winding, the dried sized carbon fiber is obtained.

[0061] The scanning electron microscope image of the carbon fiber prepared in this example is as Figure 5 shown. It can be seen from the image that a relatively uniform sizing agent coating adheres to the surface of the sized carbon fiber, improving the wettability and roughness of the carbon fiber surface. Therefore, it can effectively increase the surface polarity of the carbon fiber and enhance the interfacial properties of the carbon fiber composite material.

[0062] Comparative example.

[0063] In this example, an aqueous epoxy-modified naringin carbon fiber sizing agent was prepared. By weight, it includes the following components: 15 parts of aqueous epoxy-modified naringin, 2 parts of cetyltrimethylammonium bromide, 1 part of polyoxyethylene ether, 1 part of polyacrylamide, 2 parts of polyethylene oxide, and 100 parts of deionized water.

[0064] The preparation process of the carbon fiber sizing agent is as follows:

[0065] First, heat 100 parts of deionized water to 60 °C, and while stirring, add 15 parts of aqueous epoxy-modified naringin, 2 parts of cetyltrimethylammonium bromide, 1 part of polyoxyethylene ether, 1 part of polyacrylamide, 2 parts of polyethylene oxide. After the naringin is completely dissolved, the carbon fiber sizing agent is obtained.

[0066] In this embodiment, a sized carbon fiber was prepared using the above sizing agent, mainly including the following steps: placing the above sizing agent in a sizing tank, and passing the unsized carbon fiber through the sizing tank for wire feeding and sizing by impregnation, with an impregnation time of 30 s; drying the sized carbon fiber by blowing air, with a drying temperature of 100 °C, and obtaining the dried sized carbon fiber after winding.

[0067] The scanning electron microscope image of the obtained carbon fiber is as Figure 6 shown. It can be seen from the image that the addition amount of the waterborne epoxy-modified naringin is relatively large, and a rich slurry coating appears on the surface of the carbon fiber sized at this ratio.

[0068] Although the present invention has been disclosed above with several preferred embodiments, it is not intended to limit the present invention. Any person skilled in this art can make any changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the appended claims.

Claims

1. A carbon fiber sizing agent, characterized in that, Comprising components in the following parts by mass: 0.1 to 10 parts of waterborne epoxy modified naringin, 0.2 to 10 parts of surfactant, 0.1 to 5 parts of lubricant, 0.1 to 5 parts of binder, 0.2 to 5 parts of antistatic agent, and 100 parts of deionized water; The structural formula of the waterborne epoxy modified naringin is as follows:

2. The sizing agent for carbon fiber according to claim 1, wherein The waterborne epoxy modified naringin is obtained through the following steps: S1. Mix naringin, allyl bromide, anhydrous potassium carbonate, benzyltriethylammonium chloride, and ethanol, heat up to 40°C to 70°C, and react for 12h to 48h; S2. Purify the product in step S1, and then fully react it with m-chloroperoxybenzoic acid to obtain a brownish-red liquid; the reaction conditions are as follows: first carry out the reaction in an ice-water bath, and after the reaction heat release is stable, heat up to room temperature and react at room temperature for 24h to 72h; S3. Wash, filter, and dry with deionized water to obtain waterborne epoxy modified naringin.

3. The sizing agent for carbon fiber according to claim 1, characterized in that The surfactant is one or a mixture of at least two of cetyltrimethylammonium bromide, sodium dodecylsulfonate, sodium dodecyl sulfate, benzalkonium chloride, Tween series, polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, Peregal O series, OP series, and castor oil polyoxyethylene ether series.

4. The sizing agent for carbon fiber according to claim 1, wherein, The lubricant is one or a mixture of at least two of polyoxyethylene ether, butyl stearate, higher fatty amine, and higher fatty alcohol.

5. The sizing agent for carbon fiber according to claim 1, characterized in that, The binder is one or a mixture of at least two of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylate, ethyl acetate, and polyvinyl alcohol.

6. The sizing agent for carbon fiber according to claim 1, characterized in that, The antistatic agent is one or a mixture of at least two of polyethylene glycol methacrylate copolymer, polyether ester amide, polyether ester ethylamide, polyethylene oxide, propylene oxide copolymer, and polyethylene glycol dimaleate monoester.

7. A sized carbon fiber, characterized in that, Comprising carbon fibers and a sizing agent coating adhered to the surface of the carbon fibers, and the sizing agent coating is formed by the carbon fiber sizing agent described in any one of claims 1-6.

8. A method for preparing sized carbon fibers as described in claim 7, characterized in that, Comprising the following steps: Step 1. Add waterborne epoxy modified naringin, surfactant, lubricant, binder, and antistatic agent into deionized water in proportion, and stir evenly at a temperature maintained at 10°C to 60°C; Step 2. Place the sizing agent prepared in step 1 in a sizing tank, and the unsized carbon fibers are impregnated through the sizing tank to complete wire sizing, and the impregnation time is 5s to 30s; Step 3. The sized carbon fibers are dried by blowing, the drying temperature is 25°C to 100°C, and the dried sized carbon fibers are obtained after winding.

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