CN109722899B - Polyetherimide resin-based carbon fiber suspension sizing agent and preparation method thereof - Google Patents
Polyetherimide resin-based carbon fiber suspension sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyetherimide resin-based carbon fiber suspension sizing agent and a preparation method thereof. The polyetherimide resin-based carbon fiber suspension sizing agent consists of polyetherimide resin powder, sodium polyacrylate, alkylphenol ethoxylates and deionized water; based on the total mass of the solid components as 100 percent, wherein: 65-75 wt% of polyetherimide resin powder, 12-17 wt% of sodium polyacrylate and 13-18 wt% of alkylphenol polyoxyethylene. The carbon fiber sizing agent prepared by the invention is suitable for intermediates such as carbon fiber fabrics and prepreg for polyetherimide resin matrix composite materials, and has the advantages of good technological properties, excellent temperature resistance and excellent interface bonding capability.
Description
Technical Field
The invention belongs to the technical field of carbon fiber sizing agents, and particularly relates to a polyetherimide resin base suspension type sizing agent and a preparation method thereof.
Background
The polyetherimide resin is composed of regularly and alternately repeated ether and imide rings, has excellent mechanical properties, high temperature resistance and dimensional stability, and is widely applied to high-end manufacturing fields such as high-temperature-resistant electronics and electrical, industrial equipment and the like. Carbon fibers are added to the polyetherimide resin as a reinforcing phase, and a carbon fiber reinforced polyetherimide resin matrix composite material with excellent performance can be prepared. The material combines the respective characteristics of the carbon fiber and the polyetherimide resin, and has wide application prospect.
The interface layer of the carbon fiber reinforced polyetherimide resin matrix composite material is an important factor influencing the performance of the composite material product. The interface layer is usually composed of three phases of carbon fiber-sizing agent-matrix resin, wherein the sizing agent plays a key transition transfer role and has the characteristics of high compatibility, good high-temperature stability, no obvious chemical change in the processing process and the like. The carbon fiber sizing agent commonly used at present is an epoxy resin-based emulsion sizing agent, and is prepared by compounding epoxy resin, a surfactant, water, a functional auxiliary agent and the like. The carbon fiber prepared by adopting the sizing agent has better compatibility and interface strength with an epoxy resin matrix, but the carbon fiber is not suitable for preparing a polyetherimide resin system composite material in practical application. On one hand, the bonding strength of the epoxy resin and the polyetherimide resin is not high; on the other hand, because a large number of high-activity epoxy groups exist in the epoxy resin, the epoxy resin is easy to open a ring, age and solidify in the high-temperature processing process, so that the fiber is agglomerated or hardened, the wettability of the resin is poor, and the defects and defects of the product are increased.
Chinese patent 201410012914.X discloses a polyetherimide aqueous emulsion type carbon fiber sizing agent which consists of 20-35% of main sizing agent, 2-7% of emulsifier and 58-78% of deionized water, wherein the main sizing agent consists of polyetherimide resin and a dichloromethane solvent. The method can improve the interface bonding strength between the carbon fiber and the polyetherimide, but the method contains a large amount of volatile solvent with low boiling point, so that the safety and the environmental protection are poor, and the stability of the product is easily influenced.
Disclosure of Invention
In order to solve various problems of the prior epoxy resin sizing agent in the polyetherimide resin matrix composite material, the invention provides a stable suspension type carbon fiber sizing agent taking polyetherimide resin powder as a main body and a preparation method thereof. The polyetherimide resin powder adopted by the invention has mature preparation process and can be applied in an industrial scale. The pure polyetherimide resin-based carbon fiber sizing agent prepared by the traditional method usually needs chemical grafting modification treatment on the polyetherimide resin or adopts a large amount of organic solvent for dissolution, the preparation process is complex, various solvents, hazardous wastes and other pollutants are involved, the environmental impact is large, and the economical efficiency is poor. The sizing agent component only introduces polyetherimide resin powder with a structure similar to that of matrix resin as a main agent, does not contain epoxy resin or other resin components, has high compatibility and matching property with the matrix resin, and avoids various application problems of aging hardening of the epoxy-based sizing agent and the like. The preparation method of the sizing agent provided by the invention avoids the problems of difficult preparation, large pollution and the like of the traditional chemical grafting modification, does not need chemical synthesis modification treatment, adopts a physical mixing mode for processing and preparation, and is environment-friendly and lower in comprehensive cost. The carbon fiber sizing agent prepared by the method can be uniformly coated on the surface of carbon fiber, and the prepared sized carbon fiber can be used for preparing polyetherimide resin matrix composite materials, and has good technological properties, excellent temperature resistance and excellent interface bonding capability.
In the invention, in order to ensure that the polyetherimide powder can be well dispersed in an aqueous medium, sodium polyacrylate is introduced as a main dispersing agent, and the sodium polyacrylate is negatively charged after ionization and can be adsorbed on the surface of the powder, so that electrostatic repulsion force is generated among powder particles, an electric double layer is formed, and a good dispersing effect is achieved. Meanwhile, alkylphenol ethoxylates with aryl groups are introduced as a stabilizing auxiliary agent, the stabilizing auxiliary agent has better adsorption binding capacity with polyetherimide with a molecular structure containing a large number of aromatic ring structures, and the good amphipathy of the stabilizing auxiliary agent is utilized to promote the stable existence of micelle particle water consisting of polyphenylene sulfide powder and sodium polyacrylate.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a polyetherimide resin-based carbon fiber suspension sizing agent which is composed of polyetherimide resin powder, sodium polyacrylate, alkylphenol ethoxylates and deionized water; based on the total mass of the solid components as 100 percent, wherein:
65-75 wt% of polyetherimide resin powder
12-17 wt% of sodium polyacrylate
13-18 wt% of alkylphenol polyoxyethylene ether.
In the present invention, the structure of the polyetherimide resin powder is represented by the formula (1):
wherein: and n is the polymerization degree of the polyetherimide.
In the present invention, the polyether imide resin powder has a number average molecular weight of 2.5 to 3.5 ten thousand.
In the present invention, the number average molecular weight of the polyetherimide resin powder is preferably 3.0 to 3.3 ten thousand.
In the invention, the average diameter of the polyetherimide resin powder is 10-60 microns.
In the invention, the number average molecular weight of the sodium polyacrylate is 1000-5000.
In the invention, the number average molecular weight of the sodium polyacrylate is preferably 2000-4000.
In the invention, the structure of the alkylphenol polyoxyethylene is shown as the formula (2):
wherein: r is selected from C10～C25Any of alkyl groups; the polymerization degree m is an integer between 25 and 45.
In the invention, the mass content of the solid component in the polyetherimide resin-based carbon fiber suspension sizing agent is between 5 and 30 percent.
The invention also provides a preparation method of the polyetherimide resin-based carbon fiber suspension sizing agent, which comprises the following specific steps:
(1) putting polyetherimide resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting mechanical stirring when the water adding amount reaches 20-30 wt% of the total feeding amount of the polyetherimide resin powder and the sodium polyacrylate, and continuously adding the rest amount of water; controlling the stirring speed to be 100-200 rpm, and stirring for 20-60 min for homogeneous dispersion to obtain a uniform white emulsion;
(2) transferring the materials into a closed device provided with a high-speed emulsifier, and adding quantitative alkylphenol polyoxyethylene ether to ensure that the mass percentage of all the solid components in the suspension sizing agent is 5-30%;
(3) starting a high-speed emulsifying machine, and continuously stirring at the rotating speed of 3000-8000 rpm for 10-30 min to obtain the uniform and stable milky white suspension sizing agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polyether imide resin powder is used as a main body, the components do not contain epoxy resin, other modifier components and organic solvent, the temperature resistance is good, and the aging and hardening phenomena cannot occur after long-term storage and application.
(2) The suspension carbon fiber sizing agent disclosed by the invention introduces sodium polyacrylate as a main dispersing agent, and resin powder is well dispersed under the action of a double electric layer; meanwhile, alkylphenol ethoxylates with aryl groups are introduced to serve as a stabilizing auxiliary agent, the stability of polyetherimide resin powder particles in water is further improved, and the prepared polysulfone-based suspension sizing agent is excellent in storage and application stability, simple and convenient to prepare and environment-friendly.
(3) The carbon fiber sized by the sizing agent can be used for preparing intermediates such as carbon fiber fabrics, prepreg and the like for polyetherimide resin matrix composite materials, and has good process performance, excellent temperature resistance and excellent interface bonding capability.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
The modified epoxy resin emulsion type carbon fiber sizing agent is adopted to carry out an online sizing test on a carbon fiber engineering line. The sizing agent is SP-2P (produced by Shanghai organic of Chinese academy of sciences), and the main components are modified bisphenol F type epoxy resin and anionic surfactant. And (3) adopting dipping type sizing, wherein the concentration of a sizing agent is 3.2%, the dipping time is 40s, and drying and then reeling to prepare the epoxy resin-based sizing carbon fiber.
Comparative example 2
The traditional epoxy resin emulsion type carbon fiber sizing agent is adopted to carry out an online sizing test on a carbon fiber engineering line. The sizing agent is SP-4A (produced by Shanghai organic of Chinese academy of sciences), and the main components are bisphenol A type/bisphenol F type composite epoxy resin and anionic surfactant. And (3) adopting dipping type sizing, wherein the concentration of a sizing agent is 5.1%, the dipping time is 45s, drying and then reeling to prepare the epoxy resin-based sizing carbon fiber.
Examples 1 to 8
Sequentially adding quantitative polyetherimide resin powder and sodium polyacrylate into a stirring kettle A, gradually dropwise adding quantitative deionized water, starting mechanical stirring when the added water amount reaches 25 wt% of the total feeding amount, continuously stirring at a certain rotating speed, continuously adding the rest amount of water, stirring for a certain time to obtain uniform white emulsion, discharging and transferring to a stirring kettle B provided with a high-speed emulsifier, adding quantitative alkylphenol polyoxyethylene, starting the high-speed emulsifier, continuously stirring at a fixed rotating speed, and discharging to obtain the milky suspension sizing agent.
The polyetherimide powder is from general electric company of America, and the sodium polyacrylate and alkylphenol polyoxyethylene are from Pasteur company Limited. The solid components of the suspension sizing agents prepared in the examples 1 to 8 are shown in table 1, the composition and the dosage of the sizing agents are shown in table 2, and the preparation process parameters of the sizing agents are shown in table 3.
By adopting the polyetherimide resin base suspension sizing agent prepared by the embodiment, dipping sizing is carried out on a carbon fiber engineering line for 50s, and the sized carbon fiber is obtained after drying and filament winding.
TABLE 1 solid components of sizing agent
TABLE 2 sizing agent composition amounts
TABLE 3 sizing agent preparation Process parameters
Test analysis
The pH value of the sizing agent is tested by adopting a Mettler pH meter; the rotational viscosity of the sizing agent was measured using a BROOKFIELD DV PROVISCOMETER viscometer; observing whether the prepared sizing agent has obvious layering by adopting a visual inspection method; the concentration of the prepared suspension is tested by adopting a drying and weighing method, the stability of the prepared sizing agent is characterized by the change rate of the concentration of the lower layer relative to the concentration of the upper layer, and the stability is calculated according to the following formula:
lower layer concentration change rate (%) - (lower layer concentration-upper layer concentration)/upper layer concentration 100%
The results of evaluating the properties of the obtained suspension sizing agent are shown in Table 4. As can be seen from the results in the table, the pH of the prepared suspension sizing agent is totally neutral, stable and reliable. Low viscosity, good fluidity, easy cleaning and no roller sticking. The sizing agent has no layering, the change rate of the concentration of the lower layer relative to the concentration of the upper layer is less than 4 percent, and the change rate of the concentration of the lower layer of the emulsion type sizing agent is in the same level, which shows that the agglomeration condition of polyetherimide powder is lighter, the dispersibility among the powder is good, the stability is high, the online storage and the production are easier to manage, and the product is more uniform and stable.
TABLE 4 evaluation results of performance of suspension sizing agent
| pH | Viscosity (mPa. s) | Whether or not to stratify | Lower layer concentration change (%) | |
| Comparative example 1 | 7.5 | 76.8 | Not delaminating | 3.0 |
| Comparative example 2 | 6.4 | 69.9 | Not delaminating | 2.8 |
| Example 1 | 7.9 | 41.8 | Not delaminating | 1.1 |
| Example 2 | 7.3 | 55.0 | Not delaminating | 2.4 |
| Example 3 | 6.8 | 46.0 | Not delaminating | 1.7 |
| Example 4 | 7.2 | 43.0 | Not delaminating | 1.3 |
| Example 5 | 7.7 | 50.5 | Not delaminating | 2.3 |
| Example 6 | 7.2 | 48.1 | Not delaminating | 2.0 |
| Example 7 | 6.4 | 40.0 | Not delaminating | 0.9 |
| Example 8 | 7.8 | 52.0 | Not delaminating | 2.5 |
Testing by using an OCA20 contact angle measuring instrument to obtain a contact angle between the polyetherimide resin and the sized carbon fiber; the interfacial shear strength between the polyetherimide resin and the sized carbon fiber was measured by a MODEL HM410 interfacial property evaluation device of Donglong industries, Japan, and the thermal decomposition temperature of the sized carbon fiber was measured by TA Q500 of America.
And (3) mixing the sized carbon fibers with polyetherimide resin according to the ratio of 4: 6, extruding and granulating by using a double-screw extruder, and preparing a carbon fiber reinforced polyetherimide composite material standard sample strip according to related test standards. And (3) performing sample preparation test on the tensile strength and the elongation at break of the sample strip according to the national standard GB/T1040-2006, and testing the bending strength of the sample strip according to the national standard GB/T9341-2008.
The performance test results of the sized carbon fibers and the prepared composite material are shown in table 5. As can be seen from the data in Table 5, compared with comparative examples 1-2, the contact angle between the sized carbon fiber prepared in the examples and the polyetherimide resin is smaller, the temperature resistance is stronger, the technological properties such as infiltration and spreading between the polyetherimide matrix resin and the fiber are better, the uniformity and stability of the product are good, and the interfacial shear strength, the tensile strength, the elongation at break, the bending strength and the like are obviously improved.
TABLE 5 evaluation results of performance of sized carbon fiber and carbon fiber reinforced polyetherimide composite material
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The polyetherimide resin-based carbon fiber suspension sizing agent is characterized by consisting of polyetherimide resin powder, sodium polyacrylate, alkylphenol ethoxylates and deionized water; based on the total mass of the solid components as 100 percent, wherein:
65-75 wt% of polyetherimide resin powder;
the structure of the polyetherimide resin powder is shown as the formula (1):
wherein: n is the degree of polymerization of the polyetherimide;
12-17 wt% of sodium polyacrylate
13-18 wt% of alkylphenol polyoxyethylene ether;
the structure of the alkylphenol polyoxyethylene is shown as the formula (2):
wherein: r is selected from C10～C25Any of alkyl groups; the polymerization degree m is an integer between 25 and 45;
the preparation method comprises the following specific steps:
(1) putting polyetherimide resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting mechanical stirring when the water adding amount reaches 20-30 wt% of the total feeding amount of the polyetherimide resin powder and the sodium polyacrylate, and continuously adding the rest amount of water; controlling the stirring speed to be 100-200 rpm, and stirring for 20-60 min for homogeneous dispersion to obtain a uniform white emulsion;
(2) transferring the materials into a closed device provided with a high-speed emulsifier, and adding quantitative alkylphenol polyoxyethylene ether to ensure that the mass percentage of all the solid components in the suspension sizing agent is 5-30%;
(3) starting a high-speed emulsifying machine, and continuously stirring at the rotating speed of 3000-8000 rpm for 10-30 min to obtain the uniform and stable milky white suspension sizing agent.
2. The polyetherimide resin-based carbon fiber suspension sizing agent according to claim 1, wherein the polyetherimide resin powder has a number average molecular weight of between 2.5 and 3.5 ten thousand.
3. The polyetherimide resin-based carbon fiber suspension sizing agent according to claim 1 or 2, wherein the polyetherimide resin powder has a number average molecular weight of between 3.0 and 3.3 ten thousand.
4. The polyetherimide resin-based carbon fiber suspension sizing agent of claim 1, wherein: the average diameter of the polyetherimide resin powder is 10-60 micrometers.
5. The polyetherimide resin-based carbon fiber suspension sizing agent as claimed in claim 1, wherein the number average molecular weight of the sodium polyacrylate is 1000-5000.
6. The polyetherimide resin-based carbon fiber suspension sizing agent according to claim 1 or 5, characterized in that the number average molecular weight of the sodium polyacrylate is between 2000 and 4000.
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