CN106592242B - Modified epoxy resin large tow universal carbon fiber sizing agent, preparation method and application thereof - Google Patents
Modified epoxy resin large tow universal carbon fiber sizing agent, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified epoxy resin large tow universal carbon fiber sizing agent, a preparation method and application thereof, wherein the carbon fiber sizing agent comprises the following components: bisphenol A type epoxy resin, aliphatic binary monounsaturated acid with carboxyl at both end groups, phthalate ester non-reactive diluent, p-phenylene phenol polymerization inhibitor and imidazole catalyst. The carbon fiber sizing agent is suitable for sizing large-tow carbon fibers of 48K or more for general industry, the number average molecular weight of a reaction product is 2300-2550, and the sized carbon fibers and thermosetting resin matrixes such as epoxy resin, phenolic resin, bismaleimide resin and the like have good interface bonding strength and strong universality, and particularly the interface bonding strength of the epoxy resin and the bismaleimide resin is remarkably improved.
Description
Technical Field
The invention belongs to the field of carbon fiber sizing agents, and particularly relates to a modified epoxy resin large tow universal carbon fiber sizing agent, a preparation method and application thereof.
Background
The carbon fiber is an advanced structure functional material with high specific strength, high specific modulus and high temperature resistance developed in the 60 th of the 20 th century, and mainly comprises three different types of polyacrylonitrile-based, adhesive-based and asphalt-based, wherein the comprehensive performance of the polyacrylonitrile-based is optimal, and the industrial scale is the largest. The carbon fiber material industry in China breaks through the technology and the industrial bottleneck from inexhaustible to existent at present, and is further developing towards industrialized and generalized carbon fibers. Different from the characteristics of high performance and high cost in the field of traditional aerospace, the cost of general industrial universal carbon fiber is the primary factor restricting the development of the general industrial universal carbon fiber. First, cost reduction requires a carbon fiber production line to greatly increase unit productivity, i.e., a continuous industrialization of 48K or more large tow carbon fibers must be gradually shifted from small batch production of 1K to 12K small tow carbon fibers. Secondly, the matrix resin of the carbon fiber composite material has more types, and the carbon fiber production process must be adjusted according to different types of purposes, so that the production quality is unstable, the machine is frequently started and stopped, the qualification rate of finished products is reduced, and the manufacturing cost of the carbon fiber is indirectly increased. Cost reduction requires that carbon fibers have good versatility with matrix resins.
The carbon fiber sizing agent is a bonding layer of two-phase interfaces of carbon fibers and matrix resin, and the role of the carbon fiber sizing agent is increasingly important in the industrial production process of large-tow carbon fibers of 48K or above. As the number of single filaments in the large tows of 48K or above is multiplied, the volume of the carbon fiber tows is rapidly enlarged, the wetting capacity of the original small-tow carbon fiber sizing agent is insufficient, holes and gaps are easy to generate among the filaments of the fiber tows, and the comprehensive performances of the sizing carbon fiber such as the bundling property, the width expanding property, the uniformity, the interface binding force of matrix resin and the like can not meet the requirements. At present, the sizing agent for the small-tow carbon fibers of 12K or below is an emulsion type sizing agent mainly prepared by taking epoxy resin as a main body and adding an emulsifier, an auxiliary agent, deionized water and the like. Patent 104452303A provides a macromolecular emulsifier self-emulsifying epoxy resin sizing agent for carbon fibers, which comprises main sizing agent, macromolecular emulsifier, diluent and deionized water. The main slurry is glycidyl ether type epoxy resin, and the macromolecular emulsifier is obtained by performing hydrophilic modification on the glycidyl ether type epoxy resin by ethanolamine, allyl polyoxyethylene polyoxypropylene epoxy ether and glacial acetic acid. The mass ratio of the macromolecular emulsifier to the main slurry is 10-40: 60-90, the mass ratio of the diluent to the main slurry is 10-30: 70-90, and the mass ratio of the deionized water to the main slurry is 50-90: 10-50. Patent 104120605A discloses an emulsion sizing agent, its preparation method and application, which is prepared from 50-55 parts of epoxy resin emulsion system, 0.001-2 parts of modified carbon nanotube, 0.001-1 part of surfactant and 45-50 parts of deionized water. The emulsion sizing agent prepared by the patent can be well applied in the production process of carbon fiber engineering lines of 12K and below, and has poor effect when being used as a universal large-tow carbon fiber sizing agent.
Thermosetting resin-based composite materials represented by epoxy resin, phenolic resin, bismaleimide resin and the like have wide application prospects in the industrial fields of buildings, traffic facilities, energy sources, pressure containers and the like due to excellent mechanical properties. The epoxy resin has excellent mechanical property, good dimensional stability, multiple product types and wide application range; the bismaleimide resin has high thermal stability and excellent chemical resistance, and has irreplaceable effects in the fields of severe industrial environments such as high temperature, friction and abrasion and the like. The carbon fiber sizing agent has good interface effect with epoxy resin, phenolic resin and bismaleimide resin, particularly greatly improves the interface strength with the epoxy resin and the bismaleimide resin, and can meet the requirements of the online sizing process of large-tow carbon fibers.
Disclosure of Invention
The invention aims to solve the problem that the existing large-tow carbon fiber sizing agent is only suitable for single matrix resin, and provides a modified epoxy resin large-tow universal carbon fiber sizing agent which can be suitable for multiple matrix resin systems, a preparation method and application thereof. The carbon fiber sizing agent is suitable for sizing large-tow carbon fibers of 48K or above for general industry, and the sized carbon fibers and thermosetting resin matrixes such as epoxy resin, phenolic resin, bismaleimide resin and the like have good interface bonding strength, have strong universality and are particularly remarkably improved with the interface bonding strength of the epoxy resin and the bismaleimide resin.
The carbon fiber sizing agent disclosed by the invention adopts aliphatic binary monounsaturated acid to carry out ring-opening reaction on bisphenol A epoxy resin, and a certain amount of unsaturated functional groups are introduced into a modified molecular main chain, so that intermolecular force between the sizing agent and different matrix resins is improved, and the sized carbon fiber can have good interface strength with epoxy resin, phenolic resin and bismaleimide resin.
The invention provides a modified epoxy resin large tow universal carbon fiber sizing agent, which comprises the following components in percentage by weight:
the total weight of the components meets 100 percent; wherein:
the epoxy resin is bisphenol A epoxy resin which is formed by condensation polymerization of diphenol propane and epoxy chloropropane under the action of an alkaline catalyst and has two end groups of epoxy groups, and the epoxy resin has the following general formula:
wherein n is the average polymerization degree, and n is 0-5;
the unsaturated acid is aliphatic binary monounsaturated acid which contains 4-10C atoms on a main chain and has carboxyl groups at two end groups, and has the following structural general formula:
wherein R is1Selected from monounsaturated aliphatic groups containing 2 to 8 carbon atoms and containing one unsaturated double bond.
The number average molecular weight of the reaction product of the sizing agent is 2300-2550.
The epoxy resin is selected from any one of EPON 820, EPON828, EPON 834, EPON1001, EPON1002 or EPON1004 of Shell company of America.
The unsaturated acid is selected from any one of 2-methyl-2-pentenedioic acid, 3-hexenedioic acid, 2-methyl-2-hexenedioic acid, and 4-methyl-2-heptenedioic acid.
The phthalate ester non-reactive diluent has the following structural general formula:
wherein R2 is selected from aliphatic groups containing 1-5 carbon atoms, including methyl, ethyl, propyl, n-butyl, isobutyl and n-pentyl; the diluent is colorless or light yellow viscous liquid at normal temperature, and the viscosity is 0.001-0.01 Pa.s at 25 ℃.
The phthalate ester inactive diluent is one selected from dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate or diisobutyl phthalate.
The hydroquinone polymerization inhibitor is one or two of hydroquinone, methyl hydroquinone or tert-butyl hydroquinone.
The imidazole catalyst has the following structural general formula:
wherein R is3Selected from H atoms or aliphatic groups containing 1 to 18 carbon atoms, R4Selected from aliphatic groups containing 1 to 4 carbon atoms.
The imidazole catalyst is selected from any one of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-undecylimidazole.
The invention also provides a preparation method of the modified epoxy resin large tow universal carbon fiber sizing agent, which comprises the following specific steps:
(1) vacuum dehydration: and (2) vacuumizing and dehydrating the epoxy resin at high temperature until no bubbles are generated, wherein the vacuum dehydration temperature is 90-120 ℃, the vacuum pressure for dehydration is 100-0.1mmHg, and then gradually cooling the epoxy resin reactant obtained by vacuum dehydration to 60-80 ℃.
(2) And (3) low-temperature reaction: sequentially adding a phthalate ester non-reactive diluent, a p-phenylene diphenol polymerization inhibitor, unsaturated acid and an imidazole catalyst under the protection of dry nitrogen, controlling the temperature of the materials to be 60-80 ℃, and stirring for 5-10 hours;
(3) high-temperature reaction: and gradually heating the temperature of the reaction system to 100-140 ℃, and stopping the reaction after reacting for 1-4 hours. And taking out the materials when the temperature of the materials is reduced to normal temperature to prepare the modified epoxy resin large tow universal carbon fiber sizing agent.
In the step (1), the dehydration temperature is 110 ℃; the vacuum pressure is 10-0.5 mmHg.
In the step (2), the low-temperature reaction temperature is 65-75 ℃; the low-temperature reaction time is 6-8 hours.
In the step (3), the high-temperature reaction temperature is 105-125 ℃; the high-temperature reaction time is 2-3 hours.
The invention further provides an application method of the modified epoxy resin large tow universal carbon fiber sizing agent, which comprises the following specific steps:
preparing a sizing agent: adding acetone into the prepared carbon modified epoxy resin general carbon fiber sizing agent for large tows, and standing for 1-2 hours under a closed condition; slowly stirring until all solids are dissolved in acetone to prepare a sizing agent diluent with the concentration of 0.5-3 wt%;
secondly, online sizing and drying: placing the prepared sizing agent diluent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing; drying the sized carbon fibers by normal-temperature air blowing, and rolling to obtain dried sized carbon fibers; wherein: the carbon fiber which is not sized is 48K or above large-tow polyacrylonitrile-based carbon fiber; the sizing time is 5-60 s, and the drying time is 0.5-2.5 min; the sizing amount of the sized carbon fiber is controlled to be 0.5-1.0%.
In the step I, the concentration of the sizing agent diluent is 1.0-2.0 wt%.
In the second step, the sizing time is 15-35 s; the drying time is 1-2 min.
The invention has the beneficial effects that:
(1) in the invention, phthalate ester non-reactive diluent is introduced in the reaction process, the phthalate ester non-reactive diluent can be uniformly distributed on the surface of the sized carbon fiber to play roles of plasticization and lubrication, the technological properties such as the width expansion property, the wear resistance and the like of the large-tow carbon fiber are effectively improved, and the prepared sizing agent can be applied to online sizing of 48K or more large-tow carbon fibers.
(2) The introduced p-phenylene polymerization inhibitor effectively prevents the crosslinking reaction of unsaturated double bonds in the reaction process, improves the reaction conversion rate, ensures that the total product has high molecular weight, requires low average sizing amount for sizing carbon fibers, reduces the comprehensive cost of the carbon fibers, and is more suitable for the large-scale application of wind power, automobiles, buildings and other general industries.
(3) The sizing agent prepared by the invention contains a certain amount of unsaturated groups, has strong interface acting force with various resin matrixes, has good universality and can be suitable for preparing epoxy resin, phenolic resin and bismaleimide resin matrix composite materials. The p-phenylene terephthalates and imidazoles introduced in the reaction process can form double catalytic curing, so that the interfacial binding capacity of the sizing carbon fiber, the epoxy resin and the bismaleimide resin is improved more remarkably.
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.
Examples
Preparation of sizing agent
Putting a certain amount of epoxy resin (Shell company in America) into a four-neck flask with a mechanical stirring device, heating to 110 ℃, and dehydrating for 2 hours under the vacuum pressure of 10-0.5mmHg until no bubbles are generated in the system. Cooling to 70 ℃, introducing 99.999 percent high-purity nitrogen, and removing the vacuum device. The phthalic acid ester inactive diluent, the p-phenylene phenol polymerization inhibitor, the unsaturated acid and the imidazole catalyst (all adopted from national medicine group chemical reagent Co., Ltd.) are sequentially added into a four-mouth flask, the temperature of the materials is controlled to be 70 ℃ for reaction for 7 hours, then the temperature is increased to 120 ℃ for reaction for 2.5 hours, and then the heating is stopped. And stopping stirring when the temperature of the system is reduced to normal temperature to prepare the unsaturated acid modified epoxy resin sizing agent.
The varieties and the dosage of the epoxy resin phthalate non-reactive diluent, the p-phenylene diphenol polymerization inhibitor, the unsaturated acid and the imidazole catalyst are shown in tables 1-2. The results of the performance tests of the obtained sizing agents are shown in Table 3. The results in the table show that the average molecular weight of the sizing agent resin prepared in the comparative example is less than 1000, while the average molecular weight of the sizing agent resin prepared in the examples is more than 2000 and is between 2300 and 2550, which is greatly improved compared with the comparative example.
The average molecular weight of the sizing agent resin prepared in the embodiment is tested by GPC gel permeation chromatography, the heat resistance is tested by a TGA thermal weight loss analyzer, and the maximum weight loss peak temperature is taken as the maximum decomposition temperature.
Table 1 raw material variety table
Comparative example 1: the sizing resin consisted of neat epoxy EPON828, without any modification or other treatment.
TABLE 2 Scale for raw materials (g)
| Epoxy resin | Unsaturated acid | Diluent | Polymerization inhibitor | Catalyst and process for preparing same | |
| Comparative example 1 | 100 | 0 | 0 | 0 | 0 |
| Example 1 | 50.0 | 18.9 | 30.0 | 0.15 | 0.95 |
| Example 2 | 52.0 | 20.0 | 27.1 | 0.13 | 0.77 |
| Example 3 | 56.5 | 16.1 | 26.5 | 0.06 | 0.84 |
| Example 4 | 58.7 | 15.5 | 24.2 | 0.10 | 1.50 |
| Example 5 | 61.8 | 14.1 | 23.2 | 0.11 | 0.79 |
| Example 6 | 64.2 | 12.7 | 21.6 | 0.05 | 1.45 |
| Example 7 | 70.0 | 10.0 | 19.4 | 0.10 | 0.50 |
| Example 8 | 69.8 | 11.0 | 18.0 | 0.12 | 1.08 |
TABLE 3 sizing agent resin Performance test Table
| Number average molecular weight | Maximum decomposition temperature (. degree. C.) |
| Comparative example 1 | 375 | 228.0 |
| Example 1 | 2523 | 282.9 |
| Example 2 | 2550 | 283.2 |
| Example 3 | 2453 | 280.4 |
| Example 4 | 2438 | 278.9 |
| Example 5 | 2403 | 278.1 |
| Example 6 | 2368 | 276.1 |
| Example 7 | 2300 | 273.5 |
| Example 8 | 2325 | 274.6 |
Second, application of sizing agent
The prepared sizing resin and acetone were added in metered amounts to a 1000ml beaker and the beaker was closed. After 1.5 hours, the sealing device is opened, and the mixture is slowly stirred until all sizing agent resin is dissolved in acetone, and the system is transparent and has no turbidity, so that sizing agent diluent is prepared.
Placing the prepared sizing agent diluent in a sizing tank, adopting a single-tow sizing device, dipping 48K carbon fibers which are not sized in the sizing tank, then drying the carbon fibers by blowing at normal temperature through a blowing device, and then rolling the carbon fibers through a take-up machine to obtain dry sized carbon fibers, wherein the performance evaluation results of the sized carbon fibers are shown in Table 4. The results in the table show that the carbon fibers sized by the sizing agent of the present invention have improved interlaminar shear strength with epoxy resin, phenolic resin and bismaleimide resin, and improved two-phase interface performance. The interlaminar shear strength of the sizing carbon fiber prepared by the embodiment, the epoxy resin and the bismaleimide resin is greatly improved, and the interface bonding capability is remarkably improved.
In this example, the interlaminar shear strength ILSS of the single-direction ply of the sized carbon fiber was tested by referring to GB/T3357-1982 test method for interlaminar shear strength of single-direction fiber reinforced plastic, and the matrix resins selected were thermosetting epoxy resin AG80 (shanghai institute of synthetic resin), thermosetting phenol resin 2123 (nipponfriend chemical corporation), thermosetting bismaleimide resin 6421 (beijing institute of aerospace materials, bimaleimide for short).
Table 4 sizing carbon fiber interlaminar shear strength test data table (Mpa)
| Epoxy resin | Phenolic resin | Bismaleimide resin | |
| Comparative example 1 | 94.2 | 61.3 | 89.2 |
| Example 1 | 130.8 | 72.4 | 121.0 |
| Example 2 | 132.9 | 72.7 | 122.0 |
| Example 3 | 135.0 | 71.5 | 118.5 |
| Example 4 | 136.0 | 71.4 | 118.0 |
| Example 5 | 137.5 | 70.9 | 116.7 |
| Example 6 | 138.6 | 70.5 | 115.4 |
| Example 7 | 141.4 | 69.2 | 113.0 |
| Example 8 | 141.3 | 70.0 | 113.9 |
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 (14)
1. The modified epoxy resin large tow universal carbon fiber sizing agent is characterized by comprising the following raw material components in percentage by weight:
the total weight of the components meets 100 percent; wherein:
the epoxy resin is bisphenol A epoxy resin which is formed by condensation polymerization of diphenol propane and epoxy chloropropane under the action of an alkaline catalyst and has two end groups of epoxy groups, and the epoxy resin has the following general formula:
wherein n is the average polymerization degree, and n is 0-5;
the unsaturated acid is aliphatic binary monounsaturated acid which contains 4-10C atoms on a main chain and has carboxyl groups at two end groups, and has the following structural general formula:
wherein R is1Selected from monounsaturated aliphatic groups containing 2 to 8 carbon atoms and containing one unsaturated double bond;
the phthalate ester non-reactive diluent has the following structural general formula:
wherein R2 is selected from aliphatic groups containing 1-5 carbon atoms, including methyl, ethyl, propyl, n-butyl, isobutyl and n-pentyl; the diluent is colorless or light yellow viscous liquid at normal temperature, and the viscosity is 0.001-0.01 Pa.s at 25 ℃;
the imidazole catalyst has the following structural general formula:
wherein R is3Selected from H atoms or aliphatic groups containing 1 to 18 carbon atoms, R4Selected from aliphatic groups containing 1 to 4 carbon atoms;
the modified epoxy resin large tow universal carbon fiber sizing agent is prepared by the following specific steps:
(1) vacuum dehydration: and (2) vacuumizing and dehydrating the epoxy resin at high temperature until no bubbles are generated, wherein the vacuum dehydration temperature is 90-120 ℃, the vacuum pressure for dehydration is 100-0.1mmHg, and then gradually cooling the epoxy resin reactant obtained by vacuum dehydration to 60-80 ℃.
(2) And (3) low-temperature reaction: sequentially adding a phthalate ester non-reactive diluent, a p-phenylene diphenol polymerization inhibitor, unsaturated acid and an imidazole catalyst under the protection of dry nitrogen, controlling the temperature of the materials to be 60-80 ℃, and stirring for 5-10 hours;
(3) high-temperature reaction: and gradually heating the temperature of the reaction system to 100-140 ℃, and stopping the reaction after reacting for 1-4 hours. And taking out the materials when the temperature of the materials is reduced to normal temperature to prepare the modified epoxy resin large tow universal carbon fiber sizing agent.
2. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the number average molecular weight of the reaction product of the sizing agent is 2300-2550.
3. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the epoxy resin is selected from any one of American Shell company EPON 820, EPON828, EPON 834, EPON1001, EPON1002 or EPON 1004.
4. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the unsaturated acid is selected from any one of 2-methyl-2-pentenedioic acid, 3-hexenedioic acid, 2-methyl-2-hexenedioic acid or 4-methyl-2-heptenedioic acid.
5. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the phthalate ester inactive diluent is selected from one of dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate or diisobutyl phthalate.
6. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the hydroquinone polymerization inhibitor is one or two of hydroquinone, methyl hydroquinone or tert-butyl hydroquinone.
7. The modified epoxy resin large tow universal carbon fiber sizing agent as claimed in claim 1, wherein: the imidazole catalyst is selected from any one of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-undecylimidazole.
8. The preparation method of the modified epoxy resin large tow general-purpose carbon fiber sizing agent according to claim 1 is characterized by comprising the following specific steps:
(1) vacuum dehydration: and (2) vacuumizing and dehydrating the epoxy resin at high temperature until no bubbles are generated, wherein the vacuum dehydration temperature is 90-120 ℃, the vacuum pressure for dehydration is 100-0.1mmHg, and then gradually cooling the epoxy resin reactant obtained by vacuum dehydration to 60-80 ℃.
(2) And (3) low-temperature reaction: sequentially adding a phthalate ester non-reactive diluent, a p-phenylene diphenol polymerization inhibitor, unsaturated acid and an imidazole catalyst under the protection of dry nitrogen, controlling the temperature of the materials to be 60-80 ℃, and stirring for 5-10 hours;
(3) high-temperature reaction: and gradually heating the temperature of the reaction system to 100-140 ℃, and stopping the reaction after reacting for 1-4 hours. And taking out the materials when the temperature of the materials is reduced to normal temperature to prepare the modified epoxy resin large tow universal carbon fiber sizing agent.
9. The method of claim 8, wherein: in the step (1), the dehydration temperature is 110 ℃; the vacuum pressure is 10-0.5 mmHg.
10. The method of claim 8, wherein: in the step (2), the low-temperature reaction temperature is 65-75 ℃; the low-temperature reaction time is 6-8 hours.
11. The method of manufacturing according to claim 10, wherein: in the step (3), the high-temperature reaction temperature is 105-125 ℃; the high-temperature reaction time is 2-3 hours.
12. The application method of the modified epoxy resin large tow general-purpose carbon fiber sizing agent as claimed in claim 1 is characterized by comprising the following specific steps:
preparing a sizing agent: taking a modified epoxy resin large tow universal carbon fiber sizing agent, adding acetone, and standing for 1-2 hours under a closed condition; and slowly stirring until all solids are dissolved in acetone to prepare a sizing agent diluent with the concentration of 0.5-3 wt%.
Secondly, online sizing and drying: and (3) placing the prepared sizing agent diluent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing. Drying the sized carbon fibers by normal-temperature air blowing, and rolling to obtain dried sized carbon fibers; wherein: the carbon fiber which is not sized is 48K or above large-tow polyacrylonitrile-based carbon fiber; the sizing time is 5-60 s, and the drying time is 0.5-2.5 min; the sizing amount of the sized carbon fiber is controlled to be 0.5-1.0%
13. The method of application according to claim 12, characterized in that: in the step I, the concentration of the sizing agent diluent is 1.0-2.0 wt%.
14. The method of application according to claim 12, characterized in that: in the second step, the sizing time is 15-35 s; the drying time is 1-2 min.
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