CN103159413B - A kind of glass fibre adds treating compound and the preparation thereof of carbon nanotube - Google Patents

Abstract

The invention relates to a sizing agent for glass fibers with added carbon nanotubes. The sizing agent is composed of the following components by weight percentage: color fixing agent 3%-10%, epoxy resin 3%-10%, cationic surfactant 0.5%-5%, coupling agent 0.1%-5%, carbon nanotubes 0.1%-1%, deionized water 69%-93.3%. Preparation method: add bisphenol A type epoxy resin into ionized water, keep the temperature at 60~80℃, stir at 200~500r/min for 1~2h, then add dicyandiamide formaldehyde resin, cationic surfactant, silane coupler in sequence Coupling agent, modified carbon nanotubes, stirred, and finally deionized water was added, stirred, and the wetting agent was obtained. The formula adopted by the method of the invention is simple and practical, and is suitable for industrial production; the prepared sizing agent can effectively improve the strength of glass fiber; and can improve the strength of glass fiber composite material.

Description

A kind of sizing agent for adding carbon nanotubes for glass fiber and its preparation

technical field

The invention belongs to the field of sizing and its preparation, in particular to a sizing for glass fiber with added carbon nanotubes and its preparation.

Background technique

In the actual production of glass fibers, the sharp drop in temperature during the stretching process will cause surface stress on the glass fibers, thereby forming surface microcracks and degrading the performance of the fibers. Therefore, it is usually sprayed or dipped on the fiber surface while stretching. agent. The sizing has two main functions: on the one hand, it prevents the generation and diffusion of microcracks on the surface of the glass fiber, reduces the friction damage between fibers, and improves the strength of the fiber; on the other hand, the sizing can increase the bonding strength between the fiber and the matrix.

CNTs have excellent mechanical properties, such as tensile strength (200 GPa), elastic modulus (200–500 GPa), and fracture strain (10–30%), making them ideal candidates for interfacial modification. More and more studies on CNTs/resin nanocomposites have reported that adding a small amount of CNTs to the resin can significantly improve the properties of the material. CNTs has a huge specific surface area, which plays an obvious interface effect and bridging role in the resin, preventing cracks from expanding, thereby improving the strength of the material. It has been reported that CNTs are deposited on the surface of glass fibers by electrophoretic deposition (EPD), and it is believed that nanoparticles are similar to minerals in biological bone. Fiberglass reinforces the strength of plastic.

When CNTs are added to the sizing agent, the modified CNTs and glass fibers are closely combined to bridge the cracks and improve the tensile strength of the fibers; at the same time, it can also improve the interface structure between the glass fibers and the resin, improving Bond strength. In conclusion, when CNTs are added to the sizing agent, the quality of glass fiber products can be greatly improved.

Contents of the invention

The technical problem to be solved by the present invention is to provide a carbon nanotube sizing agent for glass fiber and its preparation method. The formula adopted in the present invention is simple and practical, and is suitable for industrial production; the prepared sizing agent can effectively improve the strength of glass fiber ; and can increase the strength of glass fiber composites.

A kind of carbon nanotube sizing agent for glass fibers of the present invention is characterized in that: the sizing agent is composed of the following components by weight percentage:

The color fixing agent is dicyandiamide formaldehyde resin with a density of 1.198g/cm ³ and a viscosity of 500-560mPa·s.

The epoxy resin is a bisphenol A epoxy resin emulsion with a relative molecular mass of 350-1000 and an average particle diameter of 0.2-2.0 μm.

The cationic surfactant is cetyltrimethylammonium chloride.

The coupling agent is a silane coupling agent whose model is KH-550, KH-560 or A186.

The carbon nanotubes are modified carbon nanotubes, and the modification method is as follows: (1) adding a strong oxidizing acid to the carbon nanotubes, heating, stirring for 20-30 hours, and then centrifuging or natural sedimentation to obtain carbon nanotubes and water (2) Add ethylenedienetriamine and polypropylene pyrrolidone to the prepared black mixture, and stir at 70°C~110°C for 5~10h to obtain modified carbon nanotubes, wherein The mass ratio of carbon nanotubes to strong oxidizing acid is 1:50~1:300, the mass ratio of polypropylene pyrrolidone to carbon nanotubes is 1:20~1:10; the mass ratio of ethylenediene triamine to carbon nanotubes The ratio is 1:15~1:10.

The strong oxidizing acid is concentrated nitric acid.

A method for preparing a sizing agent for glass fibers with added carbon nanotubes of the present invention, comprising: adding 3%-10% of bisphenol A type epoxy resin by weight percentage, adding to ionized water, keeping the temperature at 60-80°C, 200 Stir at ~500r/min for 1~2h, then add dicyandiamide formaldehyde resin 3%-10%, cationic surfactant 0.5%-5%, silane coupling agent 0.1%-5%, modified carbon nanotube 0.1%-1%, stirring, and finally adding deionized water, stirring to obtain the wetting agent, wherein the total weight percentage of deionized water is 69%-93.3%.

In the present invention, the strength of glass fiber is tested by multifilament strength meter, and the strength of glass fiber is represented by the strength of original filament (N/TEX). 10 groups of samples are taken to measure the fiber strength, and the average value is taken as the glass fiber strength.

The invention improves the strength of the glass fiber through the organic combination of several raw materials. Dicyandiamide formaldehyde resin is a polymer with low molecular weight and strong positive charge. The -CONH ₂ hydrophilic group cooperates with the unique double quaternary ammonium cationic active group to make it have a strong binding force with the fiber. The film-forming agent epoxy resin and the color-fixing agent form a resin film with high strength on the surface of the fiber, and the modified carbon nanotubes are added to achieve the effect of effectively strengthening the glass fiber. The formula is simple and practical. It can not only increase the strength of glass fiber, but also have higher bonding strength between fiber and resin in the composite material, which can greatly improve the quality of glass fiber products.

Beneficial effect

(1) The formula adopted in the present invention is simple and practical, and is suitable for industrialized production;

(2) The sizing agent prepared by the present invention can effectively improve the strength of glass fibers;

(3) The sizing prepared by the invention can improve the strength of the glass fiber composite material.

Description of drawings

Figure 1 is a field emission scanning electron micrograph of a glass fiber coated with 0.3% carbon nanotube sizing agent.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Put 5g of carbon nanotubes into a three-necked flask, add 250ml of concentrated nitric acid, then stir for 20 hours under heating conditions, then use absolute ethanol, deionized water to centrifuge or wash it by natural sedimentation for several times, and finally get the black color of carbon nanotubes and water. Mixture. 0.5 g of ethylenedienetriamine and 1.0 g of polypropylene pyrrolidone were added to the prepared black mixed solution, and stirred at 70° C. for 10 h to obtain modified carbon nanotubes.

Weigh 5% bisphenol A type epoxy resin according to the proportion by weight, add it into a container with 50% by weight of deionized water, keep the temperature at 60°C, and stir at 500r/min for 1h. Then add 5% of dicyandiamide formaldehyde resin, 1% of cationic surfactant, 0.3% of silane coupling agent KH-550, 0.1% of modified carbon nanotubes successively by weight percentage, each stirring for 0.5h, wherein the cationic surfactant is used in advance Dilute with deionized water, and finally add 38.6% by weight deionized water, and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.52.

Example 2

Put 5g of carbon nanotubes into a three-necked flask, add 300ml of concentrated nitric acid, then stir for 30 hours under heating conditions, then use absolute ethanol, deionized water to centrifuge or wash it by natural sedimentation for many times, and finally get the black color of carbon nanotubes and water. Mixture. 0.7 g of ethylenedienetriamine and 0.9 g of polypropylene pyrrolidone were added to the obtained black mixed solution, and stirred at 110° C. for 5 h to obtain modified carbon nanotubes.

Weigh 5% bisphenol A type epoxy resin according to the proportion by weight, add it into a container with 50% by weight of deionized water, keep the temperature at 80°C, and stir at 200r/min for 2h. Then add 5% of dicyandiamide formaldehyde resin, 1% of cationic surfactant, 0.3% of silane coupling agent KH-560, and 0.3% of modified carbon nanotubes successively by weight percentage, each stirring for 0.5h, wherein the cationic surfactant is used in advance Dilute with deionized water, and finally add 38.4% by weight deionized water, and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.57.

Example 3

Put 5g of carbon nanotubes into a three-necked flask, add 350ml of concentrated nitric acid, then stir for 30h under heating conditions, then use absolute ethanol, deionized water to centrifuge or wash by natural sedimentation for many times, and finally get the black color of carbon nanotubes and water. Mixture. 0.9 g of ethylenedienetriamine and 0.8 g of polypropylene pyrrolidone were added to the prepared black mixed solution, and stirred at 110° C. for 5 h to obtain modified carbon nanotubes.

Weigh 5% bisphenol A type epoxy resin according to the proportion by weight, add it into a container with 50% by weight of deionized water, keep the temperature at 60°C, and stir at 250r/min for 1h. Then add 5% of dicyandiamide formaldehyde resin, 1% of cationic surfactant, 0.3% of silane coupling agent KH-550, and 0.5% of modified carbon nanotubes successively by weight percentage, each stirring for 0.5h, wherein the cationic surfactant is used in advance Dilute with deionized water, and finally add 38.2% by weight deionized water, and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.61.

Example 4

Put 5g of carbon nanotubes into a three-necked flask, add 400ml of concentrated nitric acid, then stir for 30h under heating conditions, then use absolute ethanol, deionized water to centrifuge or wash by natural sedimentation for many times, and finally get the black color of carbon nanotubes and water. Mixture. 1.0 g of ethylenedienetriamine and 0.7 g of polypropylene pyrrolidone were added to the prepared black mixed solution, and stirred at 110° C. for 5 h to obtain modified carbon nanotubes.

Weigh 5% bisphenol A type epoxy resin according to the proportion by weight, add it into a container with 50% by weight of deionized water, keep the temperature at 60°C, and stir at 250r/min for 1h. Then add 5% of dicyandiamide formaldehyde resin, 1% of cationic surfactant, 0.3% of silane coupling agent KH-550, and 0.9% of modified carbon nanotubes successively by weight percentage, each stirring for 0.5h, wherein the cationic surfactant is used in advance Dilute with deionized water, and finally add 37.8% by weight deionized water, and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.60.

Comparative Example 1

Weigh 3.5% bisphenol A epoxy resin by weight percentage, add it into the container that has been added with 50% by weight deionized water, keep the temperature at 60°C, and stir at 250r/min for 1h. Then add 3.5% of dicyandiamide formaldehyde resin, 1% of cationic surfactant, 0.3% of silane coupling agent KH-55, and stir for 0.5h each according to weight percentage. Dilute the cationic surfactant with deionized water in advance, and finally add 41.7% deionized water according to the weight percentage, and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.42.

Comparative Example 2

Weigh 5% bisphenol A type epoxy resin according to the proportion by weight, add it into a container with 50% by weight of deionized water, keep the temperature at 60°C, and stir at 250r/min for 1h. Then add 5% dicyandiamide formaldehyde resin, 1% cationic surfactant, 0.3% silane coupling agent KH-550.3% by weight, and stir for 0.5h each, wherein the cationic surfactant is diluted with deionized water in advance, and finally Add 38.7% deionized water and stir for 2.5 hours to obtain a wetting agent with a strength N/TEX of 0.45.

Claims (4)

1. the glass fibre treating compound adding carbon nanotube, this treating compound is composed of the following components by weight percentage: laking agent 3%-10%, epoxy resin 3%-10%, cats product 0.5%-5%, coupling agent 0.1%-5%, carbon nanotube 0.1%-1%, deionized water 69%-93.3%; Wherein laking agent is Dyhard RU 100 formaldehyde resin, and density is 1.198g/cm ³, viscosity is 500 ~ 560mPas; Epoxy resin is bisphenol A type epoxy resin emulsion, and relative molecular mass is 350 ~ 1000, and median size is 0.2 ~ 2.0 μm; Cats product is palmityl trimethyl ammonium chloride;

Wherein carbon nanotube is modified carbon nano-tube, and method of modifying is: (1) carbon nanotube adds acid with strong oxidizing property, then heats, and stirs 20 ~ 30h, and then centrifugal or natural subsidence cleaning, obtains the black mixed solution of carbon nanotube and water; (2) in obtained black mixed solution, second diene triamine, polyvinyl pyrilodone is added, 5 ~ 10h is stirred under 70 DEG C ~ 110 DEG C conditions, namely the CNT (carbon nano-tube) of modification is obtained, wherein the mass ratio of carbon nanotube and acid with strong oxidizing property is 1:50 ~ 1:300, and the mass ratio of polyvinyl pyrilodone and carbon nanotube is 1:20 ~ 1:10; The mass ratio of second diene triamine and carbon nanotube is 1:15 ~ 1:10.

2. a kind of glass fibre according to claim 1 adds the treating compound of carbon nanotube, and it is characterized in that: described coupling agent is silane coupling agent, model is KH-550, KH-560 or A186.

3. a kind of glass fibre according to claim 1 adds the treating compound of carbon nanotube, it is characterized in that: described acid with strong oxidizing property is concentrated nitric acid.

4. glass fibre as claimed in claim 1 adds a treating compound preparation method for carbon nanotube, comprising:

Add bisphenol A type epoxy resin 3%-10% by weight percentage, add in ionized water, temperature keeps 60 ~ 80 DEG C, stir 1 ~ 2h under 200 ~ 500r/min, then add the carbon nanotube 0.1%-1% of Dyhard RU 100 formaldehyde resin 3%-10%, cats product 0.5%-5%, silane coupling agent 0.1%-5%, modification successively, stir, finally add deionized water, stir, obtain treating compound, wherein the total weight percent of deionized water is 69%-93.3%.