CN111472172A - Aqueous amino modified polyaryletherketone sizing agent and preparation method thereof - Google Patents
Aqueous amino modified polyaryletherketone sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a water-based amino modified polyaryletherketone sizing agent and a preparation method thereof, belonging to the technical field of sizing agents. The sizing agent comprises the following components in parts by weight: 0.5-3 parts of amino modified polyaryletherketone resin, 0.2-5 parts of surfactant, 0.1-1 part of flatting agent, 0.1-1 part of lubricant, 0.1-2 parts of adhesive, 0.2-1 part of antistatic agent and 87-98.8 parts of deionized water; the invention selects polyaryletherketone containing amino as main slurry, and effectively solves the problem of compatibility of the sizing agent and polyaryletherketone matrix resin according to the principle of 'similar compatibility', and the sizing agent has better thermal stability; introducing benzene rings into polymer molecular chains to reduce the regularity of original polyaryletherketone molecular chain segments, so that amino modified polyaryletherketone can be dissolved in partial organic solvent, and finally preparing the water-based sizing agent by an emulsion solvent volatilization method; meanwhile, the amino group can form chemical interaction with ketone bonds in the polyaryletherketone resin to generate imine, so that the interface bonding between the carbon fiber and the resin can be further improved.
Description
Technical Field
The invention belongs to the technical field of sizing agents, and particularly relates to a water-based amino modified polyaryletherketone sizing agent and a preparation method thereof.
Background
The carbon fiber reinforced polyaryletherketone (CF/PAEK) composite material is widely applied to the fields of automobile manufacturing, aerospace, military defense and the like due to the advantages of low density, high specific strength, high thermal stability and the like. However, the carbon fiber has a smooth and inert surface, which makes it difficult to achieve good wetting and bonding with the PAEK resin matrix, resulting in poor interfacial properties of the CF/PAEK composite. In addition, the carbon fiber has the characteristics of low elongation at break and high brittleness, and is easy to generate fluffing and breaking phenomena in the production and manufacturing process, so that the strength of the carbon fiber is reduced.
The sizing method is a common means for solving the above problems. The surface of the carbon fiber is coated with a layer of sizing agent, so that the friction among the fibers can be reduced, fluffing or fracture is avoided, and the effects of bundling, lubricating, isolating air and the like are achieved; secondly, a high-molecular film layer can be formed on the surface of the fiber after sizing modification, so that the wettability and the bonding capacity between the fiber and the resin can be effectively improved, and the interface performance of the composite material is improved. However, most of the sizing agents currently used in the production of carbon fibers are thermosetting sizing agents. The thermosetting sizing agent has relatively poor thermal stability, is easy to decompose when the processing temperature of the composite material exceeds 250 ℃, and does not meet the processing condition requirement of the CF/PAEK composite material. In addition, thermosetting sizing agents are generally poorly compatible with thermoplastic resins. Therefore, the development of PAEK sizing agent matched with PAEK matrix resin has important research significance. Sizing agents can be classified into a solvent type, an emulsion type and a water type according to the kind of the sizing agent solvent. In order to comply with the increasingly strict environmental regulations, the development of aqueous solventless sizing agents has become an important research direction in this field.
It is well known that most PAEK resins are not readily soluble in common organic solvents, such as the representative Polyetheretherketone (PEEK), which is insoluble in organic solvents other than concentrated sulfuric acid. Therefore, in order to prepare an aqueous sizing agent, it is necessary to dissolve it in a common organic solvent and finally obtain a solvent-free aqueous sizing agent by solvent recovery. Researches show that the introduction of non-coplanar groups or molecular chains on the polymeric chain segments of the PAEK resin destroys the regularity of the PAEK structure, and can improve the solubility of the PAEK resin. Meanwhile, if the introduced groups and PAEK resin molecules form hydrogen bond interaction, the interface performance of the composite material can be further improved.
In recent years, a sizing agent for a thermoplastic resin has been partially studied. Patent CN 108004779 a discloses a polyaryletherketone powder suspension sizing agent, which achieves powder dispersion by adding a dispersant, but the dispersant cannot be removed later, the sizing agent prepared by the method is generally poor in dispersion, and the residual dispersant can reduce the thermal stability of the sizing agent. Patent CN 102926204 a discloses an emulsion type sizing agent for reinforcing carbon fiber/PEEK composite material, but the main sizing agent of the sizing agent is epoxy resin, which is easily decomposed during processing, and meanwhile, the epoxy resin and the matrix resin PEEK may have the problem of incompatibility, so that the reinforcing effect is limited. Patent CN 102817241 a discloses a sizing agent of polyaryl ether ketone containing carbon nanotubes, the main component of the sizing agent contains organic solvent, which is easy to cause environmental pollution, and the application may be limited, which does not conform to the current social development concept. Patent CN 102926204 a discloses an epoxy-based sizing agent containing polyarylether structure, which enhances compatibility with PEEK matrix resin by the principle of structural similarity. However, the sizing agent may leave a part of epoxy groups, and the decomposition temperature of the epoxy groups is lower than the PEEK processing temperature, so that the epoxy groups are decomposed at the interface during processing, thereby affecting the interface performance. In conclusion, the development of the high-temperature-resistant and environment-friendly water-based thermoplastic sizing agent suitable for the polyaryletherketone resin has important significance for the development of the carbon fiber industry.
Disclosure of Invention
The invention aims to provide an amino-containing water-based polyaryletherketone sizing agent and a preparation method thereof,
the sizing agent has good compatibility in a thermoplastic polyaryletherketone resin system, and can obviously improve the interface performance of a composite material.
The invention firstly provides a waterborne amino modified polyaryletherketone sizing agent, which comprises the following components in parts by weight:
0.5-3 parts of amino modified polyaryletherketone resin, 0.2-5 parts of surfactant, 0.1-1 part of flatting agent, 0.1-1 part of lubricant, 0.1-2 parts of adhesive, 0.2-1 part of antistatic agent and 87-98.8 parts of deionized water;
the structural formula of the amino modified polyaryletherketone resin is shown as formula 1 or 2:
in formula 1 or 2, x + y is 1, R is one of the following structures,
preferably, the preparation steps of the amino modified polyaryletherketone resin are as follows:
(1) adding a reactant monomer A, a monomer B, 4' -difluorobenzophenone, anhydrous potassium carbonate, toluene and sulfolane into a three-neck flask, mechanically stirring under a nitrogen atmosphere, heating to 130-150 ℃, and carrying out water carrying for 2-5 hours;
(2) discharging the toluene after the water is brought, heating to 180 ℃, reacting for 2-30 h, and pouring the product into deionized water to obtain a solid polymer after the product becomes viscous;
(3) crushing the polymer by a crusher, boiling and washing the crushed polymer by deionized water, and drying the boiled polymer to obtain an amino modified polyaryletherketone polymer;
the structural formula of the reaction monomer A is one of (1) to (5),
the structural formula of the reaction monomer B is one of the following formulas,
preferably, the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, benzalkonium chloride, tween series (tween-20, tween-40, tween-60, tween-80), polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, peregal O series, OP series or castor oil polyoxyethylene ether series (E L-30, E L-40, E L-60, E L-80, etc.).
Preferably, the leveling agent is one or more of hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, acrylic resin, urea-formaldehyde resin or melamine formaldehyde resin.
Preferably, the lubricant is one or more of polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.
Preferably, the adhesive is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylates, ethyl acetate and polyvinyl alcohol.
Preferably, the antistatic agent is one or more of polyethylene glycol methacrylic acid copolymer, polyether ester amide, polyether ester acetamide, polyethylene oxide, propylene oxide copolymer or polyethylene glycol dimaleate monoester.
The invention also provides a preparation method of the waterborne amino modified polyaryletherketone sizing agent, which comprises the following steps:
(1) dissolving amino modified polyaryletherketone resin in a solvent, and fully stirring to completely dissolve the amino modified polyaryletherketone resin to form a uniform solution;
(2) adding a surfactant into deionized water, fully stirring, adding the solution obtained in the step (1), and uniformly mixing; ultrasonic shearing treatment is adopted, and the temperature of the solution is kept at 10-40 ℃ to obtain a mixed solution;
(3) and (3) adding a leveling agent, a lubricant, an adhesive and an antistatic agent into the mixed solution obtained in the step (2), uniformly stirring, and then recovering the organic solvent by distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Preferably, the solvent in step (1) is chloroform.
Preferably, the ultrasonic shearing treatment time in the step (2) is 2-20 min, and the power is 100-1000W.
The invention has the advantages of
The invention provides a water-based amino modified polyaryletherketone sizing agent and a preparation method thereof, wherein the sizing agent takes amino modified polyaryletherketone resin as main sizing agent, the structure of the sizing agent is the same as that of polyaryletherketone matrix resin, and the problem of compatibility of the sizing agent and polyaryletherketone matrix resin is effectively solved according to the principle of similar compatibility, and the sizing agent has better thermal stability; introducing benzene rings into polymer molecular chains to reduce the regularity of original polyaryletherketone molecular chain segments, so that amino modified polyaryletherketone can be dissolved in partial organic solvent, and finally preparing the water-based sizing agent by an emulsion solvent volatilization method; the molecular chains can be intertwined and diffused with each other in the preparation process of the composite material, so that the interaction force among the molecules is improved; meanwhile, amino in the sizing agent can form chemical interaction with ketone bonds in the polyaryletherketone resin to generate imine, and molecular level contact of fibers and the resin at an interface is further improved, so that interface bonding strength of the composite material is further enhanced.
The method is simple, rapid, easy to operate, easy to repeatedly realize, environment-friendly and good in industrialization prospect.
Drawings
FIG. 1 is a scanning electron micrograph of carbon fibers that have been sized and carbon fibers that have not been sized according to example 1 of the present invention;
FIG. 2 is a photograph of the contact angle of carbon fibers after sizing with carbon fibers that were not sized in example 1 of the present invention;
FIG. 3 is a graph of the thermogravimetric plot of the carbon fiber after sizing in example 1 of the present invention;
FIG. 4 shows the particle sizes of the sizing agents obtained in examples 1 to 6 of the present invention;
FIG. 5 shows the results of testing the interlaminar shear strength of the composites of examples 1-6 of the present invention and comparative example 1.
Detailed Description
The invention firstly provides a waterborne amino modified polyaryletherketone sizing agent, which comprises the following components in parts by weight:
0.5-3 parts of amino modified polyaryletherketone resin, 0.2-5 parts of surfactant, 0.1-1 part of flatting agent, 0.1-1 part of lubricant, 0.1-2 parts of adhesive, 0.2-1 part of antistatic agent and 87-98.8 parts of deionized water;
preferably: 1.8-2.4 parts of amino modified polyaryletherketone resin, 0.8-1.2 parts of surfactant, 0.2-0.3 part of flatting agent, 0.5-0.8 part of lubricant, 0.1-1.2 parts of adhesive, 0.5-0.8 part of antistatic agent and 94.7-95.8 parts of deionized water;
the structural formula of the amino modified polyaryletherketone resin is shown as formula 1 or 2:
in formula 1 or 2, x + y is 1, R is one of the following structures,
according to the invention, the preparation steps of the amino modified polyaryletherketone resin are as follows:
(1) adding a reactant monomer A, a monomer B, 4' -difluorobenzophenone, anhydrous potassium carbonate, toluene and sulfolane into a three-neck flask, mechanically stirring under a nitrogen atmosphere, heating to 130-150 ℃, and carrying out water carrying for 2-5 hours; the mass ratio of the monomer A, the monomer B, the 4,4' -difluorobenzophenone and the anhydrous potassium carbonate is preferably (5-15): (4-12): (18-25): (15-20), more preferably (6.2-13.97): (5.41-10): 21.8: 16.5.
(2) discharging the toluene after the water is brought, heating to 180 ℃, reacting for 2-30 h, and pouring the product into deionized water to obtain a solid polymer after the product becomes viscous;
(3) and crushing the polymer by using a crusher, preferably repeatedly boiling and washing the polymer by using deionized water for 8 hours, replacing the water every 1 hour, and finally drying the polymer in a vacuum oven at the temperature of 80-85 ℃ to constant weight to obtain the amino modified polyaryletherketone polymer.
The structural formula of the reaction monomer A is one of (1) to (5),
the structural formula of the reaction monomer B is one of the following formulas,
according to the invention, the surfactant is preferably cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, benzalkonium chloride, Tween series, polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, peregal O series, OP series or castor oil polyoxyethylene ether series, wherein the Tween series is preferably one or more of Tween-20, Tween-40, Tween-60 and Tween-80, and the castor oil polyoxyethylene ether series is preferably E L-30, E L-40, E L-60 or E L-80.
According to the invention, the leveling agent is preferably one or more of hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane, acrylic resin, urea-formaldehyde resin or melamine formaldehyde resin.
According to the invention, the lubricant is preferably one or more of polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.
According to the invention, the adhesive is preferably one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylates, acetates and polyvinyl alcohol.
According to the invention, the antistatic agent is preferably one or more of polyethylene glycol methacrylic acid copolymer, polyether ester amide, polyether ester acetamide, polyethylene oxide, propylene oxide copolymer or polyethylene glycol dimaleate monoester.
The invention also provides a preparation method of the waterborne amino modified polyaryletherketone sizing agent, which comprises the following steps:
(1) dissolving amino modified polyaryletherketone resin in a solvent, wherein the solvent is preferably chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone resin to form a uniform solution;
(2) adding a surfactant into deionized water, fully stirring, adding the solution obtained in the step (1), and uniformly mixing; ultrasonic shearing treatment is adopted, and the temperature of the solution is kept at 10-40 ℃ to obtain a mixed solution; the ultrasonic shearing treatment time is preferably 2-20 min, and the power is preferably 100-1000W;
(3) and (3) adding a leveling agent, a lubricant, an adhesive and an antistatic agent into the mixed solution obtained in the step (2), uniformly stirring, and then recovering the organic solvent by distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
According to the invention, the prepared sizing agent is used for treating carbon fibers, and the treatment method preferably comprises the following steps:
soaking and running carbon fibers in a sizing agent for 5-30 s at a drying temperature of 100-120 ℃, drying, winding the carbon fibers on a rectangular iron frame, then carrying out hot press molding on the carbon fibers and a polyaryletherketone resin film to prepare a prepreg, and finally cutting, laying and hot press molding the prepreg to prepare the carbon fiber/polyaryletherketone composite material.
The present invention will be described in further detail with reference to examples. The examples are intended to illustrate the invention only and do not limit the scope of the invention. Various changes or modifications may be made by one skilled in the art after reading the disclosure of the present invention, and such equivalents are intended to fall within the scope of the appended claims.
Example 1
(1) Preparation of amino modified polyaryletherketone:
firstly, 9.3g of 2-phenyl hydroquinone (monomer A), 10g of 4-aminophenyl hydroquinone (monomer B), 21.8g of 4,4' -difluorobenzophenone, 16.5g of anhydrous potassium carbonate, 150m of L toluene and 130m of L sulfolane are added into a 1000m L three-neck flask, mechanical stirring is carried out under nitrogen atmosphere, the temperature is increased to 140 ℃ and then water is carried out for 4h, the toluene in the three-neck flask is discharged after the water carrying is finished, then the temperature is increased to 180 ℃ for reaction for 10h, when the reactant is changed into a sticky state, the reactant is poured into deionized water to obtain a solid polymer, then a pulverizer is used for crushing the solid polymer, the deionized water is repeatedly boiled and washed for 8h, the water is changed once every 1h, and finally the solid polymer is placed into a vacuum oven to be dried at 80 ℃ to constant weight to obtain the amino modified polyaryletherketone polymer, wherein the amino content is 50 percent, and the specific structural formula is as follows:
(2) dissolving 20g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 10g of hexadecyl trimethyl ammonium bromide into 947m L deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, carrying out ultrasonic shearing treatment for 5min at the power of 200W, and keeping the temperature of the solution at 25 ℃.
(4) And (3) adding 2g of acrylic resin, 8g of butyl stearate, 12g of ethyl cellulose and 5g of polyether ester amide into the mixed solution in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the waterborne amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 1 at a speed of 15m/min, dried at 100 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 1 was 68.6nm, as shown in FIG. 4; the resulting composite was tested and the interlaminar shear strength of the composite was found to be 88.7MPa, as shown in FIG. 5.
Fig. 1 is a scanning electron micrograph of the carbon fiber (a) after sizing and the carbon fiber (b) without sizing obtained in example 1 of the present invention, which shows that the grooves on the surface of the carbon fiber after sizing are shallow and the surface is covered with a uniform and thin sizing agent resin layer.
Fig. 2 is a photograph showing the contact angle between the carbon fiber (a) after sizing and the carbon fiber (b) without sizing obtained in example 1 of the present invention, and it can be seen that the wetting property of the carbon fiber after sizing is significantly improved.
Fig. 3 is a thermogravimetric plot of the sized carbon fiber obtained in example 1 of the present invention, and it can be seen that the temperature when the mass loss is 2% is 456 ℃, demonstrating the excellent thermal stability of the present sizing agent.
Example 2
(1) The monomer A used in this example to prepare the amino-modified polyaryletherketone was 6.2g of 2-methylhydroquinone, the rest being the same as in example 1. The specific structural formula is as follows:
(2) dissolving 18g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 12g of sodium dodecyl sulfate into 953m L deionized water, stirring fully, adding the solution obtained in the step (2), mixing uniformly, performing ultrasonic shearing treatment for 8min at the power of 400W, and keeping the temperature of the solution at 20 ℃.
(4) And (3) adding 3g of hydroxymethyl cellulose, 5g of butyl stearate, 1g of polyacrylamide and 8g of polyethylene oxide into the mixed solution obtained in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 2 at a speed of 20m/min, dried at 100 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 2 was 70.3nm, as shown in FIG. 4; the obtained composite material was subjected to a test, and the interlaminar shear strength of the composite material was measured to be 86.9MPa, as shown in FIG. 5.
Example 3
(1) The monomer A used in this example to prepare the amino-modified polyaryletherketone was 11.4g of bisphenol A, the rest being the same as in example 1. The specific structural formula is as follows:
(2) dissolving 24g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 8g of sodium dodecyl benzene sulfonate into 952m L deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 10min at the power of 200W, and keeping the temperature of the solution at 25 ℃.
(4) And (3) adding 2g of hydroxymethyl cellulose, 5g of polyoxyethylene ether, 1g of polyacrylamide and 8g of polyoxyethylene into the mixed solution in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 3 at a speed of 20m/min, dried at 120 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 3 was 72.5nm, as shown in FIG. 4; the resulting composite was tested and the interlaminar shear strength of the composite was found to be 88.2MPa, as shown in FIG. 5.
Example 4
(1) The monomer A used in this example to prepare the amino-modified polyaryletherketone was 8.3g of tert-butylhydroquinone, the rest being the same as in example 1. The specific structural formula is as follows:
(2) dissolving 18g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 8g of hexadecyl trimethyl ammonium bromide into 958m L deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 10min at the power of 200W, and keeping the temperature of the solution at 25 ℃.
(4) And (3) adding 2g of hydroxymethyl cellulose, 5g of polyoxyethylene ether, 1g of polyacrylamide and 8g of polyoxyethylene into the mixed solution in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 4 at a speed of 15m/min, dried at 120 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 4 was 69.8nm, as shown in FIG. 4; the resulting composite was tested and the interlaminar shear strength of the composite was found to be 87.6MPa, as shown in FIG. 5.
Example 5
(1) The preparation of amino-modified polyaryletherketones in this example was carried out using 13.97g of 2-phenylhydroquinone as monomer A and 5.41g of 2, 4-diaminophenylhydroquinone as monomer B, the other examples being identical to those of example 1. The specific structural formula is as follows:
(2) dissolving 22g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 12g of hexadecyl trimethyl ammonium bromide into 959m L deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 15min at the power of 400W, and keeping the temperature of the solution at 25 ℃.
(4) And (3) adding 4g of hydroxymethyl cellulose, 5g of polyoxyethylene ether, 2g of polyacrylamide and 6g of polyoxyethylene into the mixed solution in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 5 at a speed of 15m/min, dried at 100 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 5 was 70.8nm, as shown in FIG. 4; the obtained composite material was subjected to a test, and the interlaminar shear strength of the composite material was measured to be 86.1MPa, as shown in FIG. 5.
Example 6
(1) The monomer A used in this example to prepare an amino-modified polyaryletherketone was 9.3g of 2-methylhydroquinone, the rest being the same as in example 5. The specific structural formula is as follows:
(2) dissolving 24g of the synthesized amino modified polyaryletherketone polymer in chloroform, and fully stirring to completely dissolve the amino modified polyaryletherketone polymer to form a uniform solution;
(3) adding 10g of hexadecyl trimethyl ammonium bromide into 952m L deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 20min at the power of 400W, and keeping the temperature of the solution at 25 ℃.
(4) And (3) adding 2g of hydroxymethyl cellulose, 5g of polyoxyethylene ether, 2g of polyacrylamide and 5g of polyoxyethylene into the mixed solution in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
Carbon fibers were dipped and run in the sizing agent prepared in example 6 at a speed of 15m/min, dried at 110 ℃ and wound on a rectangular iron frame, and then the carbon fibers and a polyaryletherketone film were compounded to prepare a prepreg, which was cut into appropriate sizes and placed in a mold coated with a release agent (the direction of the fiber lay-up was 0 °) for hot press molding to obtain a composite material.
The particle size of the sizing agent in example 6 was 69.2nm, as shown in FIG. 4; the resulting composite was tested and the interlaminar shear strength of the composite was found to be 88.0MPa, as shown in FIG. 5.
Comparative example 1
In the comparative example, carbon fibers containing epoxy resin sizing agents are wound on a rectangular iron frame, the carbon fibers and a polyaryletherketone film are compounded to prepare a prepreg, the prepreg is cut into a proper size and then placed into a mold coated with a release agent (the layering direction of the fibers is 0 degree), and hot press molding is carried out to obtain the composite material.
The composite material obtained in comparative example 1 was tested, and the interlaminar shear strength of the composite material was measured to be 65.1MPa, as shown in FIG. 5.
It should be understood that the application of the present invention is not limited to the above examples, and the design concept of the present invention is not limited thereto, and any insubstantial modifications made to the present invention using the concept shall fall within the act of infringing the scope of the protection of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The water-based amino modified polyaryletherketone sizing agent is characterized by comprising the following components in parts by weight:
0.5-3 parts of amino modified polyaryletherketone resin, 0.2-5 parts of surfactant, 0.1-1 part of flatting agent, 0.1-1 part of lubricant, 0.1-2 parts of adhesive, 0.2-1 part of antistatic agent and 87-98.8 parts of deionized water;
the structural formula of the amino modified polyaryletherketone resin is shown as formula 1 or 2:
in formula 1 or 2, x + y is 1, R is one of the following structures,
2. the aqueous amino-modified polyaryletherketone sizing agent of claim 1, wherein the amino-modified polyaryletherketone resin is prepared by the following steps:
(1) adding a reactant monomer A, a monomer B, 4' -difluorobenzophenone, anhydrous potassium carbonate, toluene and sulfolane into a three-neck flask, mechanically stirring under a nitrogen atmosphere, heating to 130-150 ℃, and carrying out water carrying for 2-5 hours;
(2) discharging the toluene after the water is brought, heating to 180 ℃, reacting for 2-30 h, and pouring the product into deionized water to obtain a solid polymer after the product becomes viscous;
(3) crushing the polymer by a crusher, boiling and washing the crushed polymer by deionized water, and drying the boiled polymer to obtain an amino modified polyaryletherketone polymer;
the structural formula of the reaction monomer A is one of (1) to (5),
the structural formula of the reaction monomer B is one of the following formulas,
3. the waterborne amino modified polyaryletherketone sizing agent of claim 1, wherein the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, benzalkonium chloride, tween series, polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, peregal O series, OP series or castor oil polyoxyethylene ether series.
4. The water-based amino modified polyaryletherketone sizing agent as claimed in claim 1, wherein the leveling agent is one or more of hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane, acrylic resin, urea-formaldehyde resin or melamine-formaldehyde resin.
5. The aqueous amino-modified polyaryletherketone sizing agent as claimed in claim 1, wherein the lubricant is one or more selected from polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.
6. The sizing agent of claim 1, wherein the binder is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylates, acetates, polyvinyl alcohol.
7. The waterborne amino modified polyaryletherketone sizing agent as claimed in claim 1, wherein the antistatic agent is one or more of polyethylene glycol methacrylic acid copolymer, polyether ester amide, polyether ester acetamide, polyethylene oxide, propylene oxide copolymer or polyethylene glycol bismaleic acid monoester.
8. The preparation method of the aqueous amino-modified polyaryletherketone sizing agent according to claim 1, comprising the following steps:
(1) dissolving amino modified polyaryletherketone resin in a solvent, and fully stirring to completely dissolve the amino modified polyaryletherketone resin to form a uniform solution;
(2) adding a surfactant into deionized water, fully stirring, adding the solution obtained in the step (1), and uniformly mixing; ultrasonic shearing treatment is adopted, and the temperature of the solution is kept at 10-40 ℃ to obtain a mixed solution;
(3) and (3) adding a leveling agent, a lubricant, an adhesive and an antistatic agent into the mixed solution obtained in the step (2), uniformly stirring, and then recovering the organic solvent by distillation or rotary evaporation to obtain the aqueous amino modified polyaryletherketone sizing agent.
9. The method for preparing an aqueous amino modified polyaryletherketone sizing agent according to claim 8, wherein the solvent in step (1) is chloroform.
10. The preparation method of the water-based amino modified polyaryletherketone sizing agent according to claim 8, wherein the ultrasonic shearing treatment time in the step (2) is 2-20 min, and the power is 100-1000W.
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| CN114687213A (en) * | 2022-04-26 | 2022-07-01 | 浙江大学衢州研究院 | Crosslinkable polyarylether nitrile aqueous sizing agent and preparation method and application thereof |
| CN114687213B (en) * | 2022-04-26 | 2024-05-10 | 浙江大学衢州研究院 | Cross-linkable poly (arylene ether nitrile) aqueous sizing agent and preparation method and application thereof |
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