CN113637286A - Toughened and flame-retardant hot-melt phenolic resin, prepreg and composite material and preparation method thereof - Google Patents
Toughened and flame-retardant hot-melt phenolic resin, prepreg and composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a toughened and flame-retardant hot-melt phenolic resin, a prepreg, a composite material and a preparation method thereof, wherein the toughened and flame-retardant hot-melt phenolic resin is prepared from the following components in parts by mass: 0-100 parts of thermoplastic phenolic resin, 0-100 parts of thermosetting phenolic resin, 1-15 parts of flame retardant, 5-100 parts of toughening agent, 0.05-1 part of coupling agent and 0-20 parts of curing agent; wherein the thermoplastic phenolic resin and the thermosetting phenolic resin are not 0 part at the same time. The hot-melt phenolic resin and the prepreg have stable and reliable quality, good toughness and flame retardant property, low smoke and low toxicity, and the performance of the composite material product meets the use performance requirements of interior trim parts and secondary structural parts of transportation tools such as airplanes, high-speed trains and the like.
Description
Technical Field
The invention belongs to the technical field of phenolic resin composite materials, and particularly relates to a toughened and flame-retardant hot-melt phenolic resin, a prepreg, a composite material and a preparation method thereof.
Background
The phenolic resin has over 100 years of industrial production and application history, and the prepreg composite material taking the phenolic resin as the matrix has good process performance, excellent flame retardant performance and cost performance superior to other engineering resins, is widely applied in the fields of national defense and military industry, aerospace, rail transit, electronic and electrical appliances and buildings at present, and the application requirement of the fiber reinforced phenolic resin matrix composite material still presents a gradually expanding trend along with the improvement of the industrial production technology.
The traditional phenolic resin structure has more rigid groups such as benzene rings and the like, so that the cured product has high brittleness; in addition, water molecules are released due to further condensation and crosslinking of the phenolic resin in the curing and forming process of the phenolic resin material, and the water molecules are usually difficult to be completely discharged, so that more micropores exist in the material, the mechanical property of the phenolic resin material is also influenced, and the phenolic resin material is always limited in various application fields. Therefore, the toughening modification of the phenolic resin to improve the mechanical properties thereof is still a hot spot of research of scholars at home and abroad nowadays, and is also an important research work for determining the future development direction of the phenolic resin. Around the toughening and strength improvement of phenolic materials, a great deal of research is carried out by researchers, but the performance of the currently obtained product cannot meet the application requirement.
The prepreg preparation methods are mainly two types, a solution impregnation method (wet method) and a hot melt adhesive film method (dry method or hot melt method). The solution impregnation method is a process of impregnating fibers or fabrics with a resin solution, heating the impregnated fibers or fabrics through a subsequent working section, volatilizing a solvent in the resin, and enabling the prepreg to reach a certain curing stage. The hot melt adhesive film method is that firstly a hot melt resin matrix is heated and melted to prepare a hot melt adhesive film with a certain surface weight, and then the hot melt resin adhesive film and a fiber reinforced material are heated and pressurized together to compound into the hot melt prepreg. Therefore, the prepreg production process adopting the hot melting method gradually becomes the development direction of the current high-precision prepreg preparation.
Therefore, in order to meet the requirement of the application development of phenolic resin materials in higher technical fields, the research on the modification optimization of phenolic resin matrixes and the novel process for preparing prepregs is always a hot spot of attention. At present, few researches on hot-melt phenolic resin-based prepreg are needed, and the researches on the hot-melt manufacturability are needed while the comprehensive application performances such as toughness and flame retardance of a phenolic resin system are effectively improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a toughened and flame-retardant hot-melt phenolic resin, a prepreg, a composite material and a preparation method thereof, wherein the prepared hot-melt phenolic resin and the prepreg have stable and reliable quality, good toughness and flame-retardant property, low smoke and low toxicity, and the performance of a composite material product meets the use performance requirements of interior parts and secondary structural parts of transportation vehicles such as airplanes and high-speed trains.
In order to solve the above problems, one aspect of the present invention provides a toughened and flame retardant hot melt phenolic resin, which comprises the following components in parts by weight:
0-100 parts of thermoplastic phenolic resin, 0-100 parts of thermosetting phenolic resin, 1-15 parts of flame retardant, 5-100 parts of toughening agent, 0.05-1 part of coupling agent and 0-20 parts of curing agent;
wherein the thermoplastic phenolic resin and the thermosetting phenolic resin are not 0 part at the same time.
Preferably, the preparation raw materials comprise the following components in parts by weight
20-80 parts of thermoplastic phenolic resin, 20-80 parts of thermosetting phenolic resin, 2-8 parts of flame retardant, 10-30 parts of toughening agent, 0.1-0.15 part of coupling agent and 0-10 parts of curing agent.
Preferably, the raw materials for preparing the thermosetting phenolic resin comprise: phenol, aldehyde, first catalyst, the molar ratio of phenol to aldehyde being (0.55-0.9): 1; the mass of the first catalyst is 0.5-8% of that of phenol.
Preferably, the phenol is one or a combination of more of phenol, cresol, p-tert-butylphenol, octylphenol and cardanol.
Preferably, the aldehyde is formaldehyde.
Preferably, the first catalyst is one or a combination of more of ammonia water, magnesium oxide, aniline, barium hydroxide and sodium hydroxide.
Preferably, the raw materials for preparing the thermoplastic phenolic resin comprise: phenol, aldehyde, a second catalyst, the molar ratio of phenol to aldehyde being (1.1-1.5): 1; the mass of the second catalyst is 0.5-3% of the mass of the phenol.
Preferably, the phenol is one or a combination of more of phenol, cresol, p-tert-butylphenol, octylphenol and cardanol.
Preferably, the aldehyde is formaldehyde.
Preferably, the second catalyst is one or a combination of oxalic acid, hydrochloric acid and phosphoric acid.
Preferably, the flame retardant is one or a combination of more of ammonium polyphosphate, red phosphorus, aluminum hydroxide, magnesium hydroxide and tricresyl phosphate;
the toughening agent is a mixed glue solution prepared from at least one of carboxyl-terminated polybutadiene, polyvinyl acetal and nitrile rubber and at least one of methanol, ethanol, acetone, butanone and ethyl acetate according to the mass ratio of 1 (1-3);
wherein, the nitrile rubber can be one or the combination of more of hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber and common nitrile rubber (NBR).
The coupling agent is one or a combination of more of KH-550, KH-560 and KH-570;
the curing agent is one or a combination of more of sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, epoxy resin, paraformaldehyde, melamine, hexamethylenetetramine and 2,2' - (1, 3-phenylene) -bisoxazoline.
In another aspect of the present invention, a method for preparing the above toughened, flame retardant hot melt phenolic resin is provided, which comprises the following steps:
and mixing and stirring the thermoplastic phenolic resin, the thermosetting phenolic resin, the flame retardant, the toughening agent, the coupling agent and the curing agent to obtain the toughened and flame-retardant hot-melt phenolic resin.
Preferably, the method specifically comprises the following steps:
s1, mixing the thermoplastic phenolic resin with the thermosetting phenolic resin, and stirring at 60-85 ℃ for 20-60min to obtain mixed resin;
s2, mixing the mixed resin obtained in the step S1 with the flame retardant, the toughening agent and the coupling agent, and stirring for 3-6h at 60-80 ℃ to obtain modified resin;
s3, mixing the modified resin obtained in the step S2 with the curing agent, and stirring for 1-3h at 40-90 ℃ to obtain the toughened and flame-retardant hot-melt phenolic resin.
Preferably, in step S3, the obtained toughened and flame-retardant hot-melt phenolic resin has a gel time of 80-200 seconds at the temperature of 120-150 ℃.
Preferably, the preparation method of the thermosetting phenolic resin comprises the following steps:
mixing the cresol and the formaldehyde, adding a catalyst at 35-40 ℃, heating to 70-95 ℃ at the heating rate of 1-2 ℃/min, carrying out heat preservation condensation reaction for 1-5h, cooling to 65-90 ℃ after the reaction is finished, dehydrating for 3-6h, and stopping dehydrating when the resin is gelled at the temperature of 120-150 ℃ for 450s, thereby obtaining the thermosetting phenolic resin.
Preferably, the preparation method of the thermoplastic phenolic resin comprises the following steps:
mixing the cresol and the formaldehyde, adding a catalyst at 35-40 ℃, heating to 65-95 ℃ at the heating rate of 1-2 ℃/min, carrying out heat preservation condensation reaction for 1-3h, heating to 95-110 ℃ after the reaction is finished, dehydrating for 1-4h, and stopping dehydrating when the viscosity of the resin is 200-1500mPa & s at 100 ℃ to obtain the thermosetting phenolic resin.
The invention further provides a toughened and flame-retardant hot-melt phenolic resin prepreg, and the preparation raw materials comprise the toughened and flame-retardant hot-melt phenolic resin.
Preferably, the preparation raw materials further comprise a reinforcing material, and the mass content of the toughened and flame-retardant hot-melt phenolic resin in the toughened and flame-retardant hot-melt phenolic resin prepreg is 30-50%.
Preferably, the reinforcing material is one or a combination of several of glass fiber, quartz fiber, unidirectional fiber of carbon fiber or fiber fabric.
Preferably, the weaving mode of the fiber fabric is plain weave, twill weave or satin weave.
Preferably, the fibrous fabric is a uniaxial, biaxial or multiaxial hemming fabric.
Preferably, the areal density of the fiber fabric is 100-420g/m2。
In another aspect, the invention provides a method for preparing the toughened and flame-retardant hot-melt phenolic resin prepreg, which comprises the following steps:
preparing the toughened and flame-retardant hot-melt phenolic resin into an adhesive film, and then compounding the adhesive film with the reinforcing material to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg.
Preferably, the method specifically comprises the following steps:
A1. preparing the toughened and flame-retardant hot-melt phenolic resin into a glue film by adopting a glue film method, wherein the coating temperature is 60-90 ℃, the coating speed is 2-5m/min, and the areal weight of the glue film is controlled to be 50-150g/m2Obtaining a hot melt adhesive film;
A2. and B, compounding the hot-melt adhesive film in the step A1 with the reinforcing material to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg, wherein the compounding temperature is 40-90 ℃, the compounding speed is 4-10m/min, and the compounding roller gap is 0.2-0.8 mm.
Preferably, the toughened and flame-retardant hot-melt phenolic resin prepreg obtained in the step A2 has a volatile content of 1-10%, preferably 3-6%, and has a gel time of 80-200 seconds at 120-150 ℃.
The invention further provides a toughened and flame-retardant hot-melt phenolic resin composite material which is prepared by using the toughened and flame-retardant hot-melt phenolic resin prepreg.
Preferably, the toughened and flame-retardant hot-melt phenolic resin composite material is obtained by putting the toughened and flame-retardant hot-melt phenolic resin prepreg into an autoclave for curing after being subjected to hot press or vacuum coating, and the curing conditions are as follows: the curing temperature is 120-180 ℃, preferably 120-150 ℃, the curing pressure is 0.5-1.0MPa, and the curing time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the toughening and flame-retardant hot-melt phenolic resin, the thermosetting phenolic resin, the toughening agent, the flame retardant, the coupling agent and the curing agent in the phenolic resin formula are prepared, so that the modified phenolic resin which is suitable for a hot-melt pre-dipping process and has the characteristics of high toughness, flame retardance, low smoke, low toxicity and the like is obtained, after the resin is coated into a film, the film has certain toughness and is not easy to break, the phenomenon of crushing and slag removal is avoided, the film has certain ductility at room temperature, the film can be well stripped from materials such as release paper and the like, the resin system has good film forming property, the toughness of a cured product is good, and the mixed resin of the thermoplastic phenolic resin and the thermosetting phenolic resin is further adopted, so that the heat resistance and the toughness of a product are optimally regulated and controlled;
2. the toughening and flame-retardant hot-melt phenolic resin further improves the impact resistance toughness and flame-retardant property of a cured phenolic resin through optimization of process design, realizes organic unification of toughening and flame-retardant modification in the same resin system, and improves the comprehensive application performance of the modified phenolic resin;
3. the toughened and flame-retardant hot-melt phenolic resin prepreg provided by the invention can be prepared by reasonably designing and optimizing the hot-melt prepreg technological parameters, has uniform prepreg texture, high control precision of resin content and low volatile content in the prepreg, and obviously improves the spreadability and the use manufacturability of the prepreg;
4. the toughening and flame-retardant hot-melt phenolic resin, the prepreg and the composite material are designed aiming at the use performance requirements of interior parts and secondary structural parts of high-end transportation equipment such as civil aviation and high-speed rail trains, and the composite material has excellent comprehensive use performances such as impact resistance, flame retardance, low smoke, low toxicity and the like, is very suitable for producing and manufacturing interior parts such as floors of cargo holds of airplanes, cargo hold liners, ceilings and side wall plates of high-speed rail trains, and has very considerable application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
20 parts of thermoplastic phenolic resin, 80 parts of thermosetting phenolic resin, 2 parts of flame retardant aluminum hydroxide, 10 parts of toughening agent (glue solution prepared from common nitrile-butadiene rubber (NBR) and ethyl acetate according to the mass ratio of 1: 1) and KH-5500.1 parts of coupling agent.
The thermosetting phenolic resin is prepared from the following raw materials: the catalyst comprises cresol, formaldehyde and a first catalyst ammonia water, wherein the molar ratio of the cresol to the formaldehyde is 0.83: 1; the mass of the first catalyst is 1.5 percent of that of the cresol.
Wherein the preparation raw materials of the thermoplastic phenolic resin comprise: phenol, formaldehyde and a second catalyst hydrochloric acid, wherein the molar ratio of the phenol to the formaldehyde is 1.11: 1; the mass of the second catalyst was 2% of the mass of phenol.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin comprises the following steps:
s01 preparation of thermosetting phenolic resin, namely mixing cresol and formaldehyde according to a molar ratio of 0.83: 1, adding the mixture into a reaction kettle, adding ammonia water with the mass of 1.5% of phenol as a catalyst when the system temperature is 36 ℃, stirring, heating to 80 ℃ at the speed of 2 ℃/min, carrying out heat preservation reaction for 3.5h, reducing the system temperature to 70 ℃ after the reaction is finished, starting to carry out pressure-maintaining dehydration for 3.5h under the pressure of-0.08 to-0.09 MPa, starting to test the gel time of the phenolic resin at 150 ℃ at intervals of 5-10 min when the system temperature starts to gradually rise, and stopping dehydration when the gel time is 120s to obtain the thermosetting phenolic resin;
s02. preparing thermoplastic phenolic resin, namely adding phenol and formaldehyde into a reaction kettle according to the molar ratio of 1.11:1, adding hydrochloric acid accounting for 2% of the mass of the phenol as a catalyst when the temperature of the system is 40 ℃, stirring, heating to 80 ℃ at the speed of 1.5 ℃/min, carrying out heat preservation reaction for 2h, raising the temperature of the system to 95 ℃ after the reaction is finished, starting to carry out pressure-maintaining dehydration for 2.5h under the pressure of-0.08 to-0.09 MPa, starting to test the viscosity of the phenolic resin at 100 ℃ at the interval of 5 to 10min when the temperature of the system gradually rises, and stopping dehydration when the viscosity is 400 and 430 mPas, thus obtaining the thermoplastic phenolic resin;
s1, mixing the raw materials in parts by mass as 4:1, adding 20 parts of thermoplastic phenolic resin into 80 parts of thermosetting phenolic resin, and stirring and mixing for 30min at 80 ℃ to obtain mixed resin;
s2, adding 10 parts of toughening agent (the toughening agent is a liquid nitrile rubber and ethyl acetate which are prepared into glue solution according to the mass ratio of 1: 1) into 100 parts of the mixed resin obtained in the step S1, adding 2 parts of aluminum hydroxide flame retardant, adding 0.1 part of KH-550 coupling agent, and stirring at 70 ℃ for 4 hours to obtain the toughened flame-retardant hot-melt phenolic resin.
The toughened and flame-retardant hot-melt phenolic resin prepreg of the embodiment comprises the toughened and flame-retardant hot-melt phenolic resin and a reinforcing material, wherein the reinforcing material is 240g/m in gram weight2The high-strength glass fiber satin cloth.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin prepreg comprises the following steps:
A1. preparing the toughened and flame-retardant hot-melt phenolic resin into an adhesive film by adopting an adhesive film method, putting the toughened and flame-retardant hot-melt phenolic resin into an adhesive coater, coating at 70-75 ℃, adjusting the coating speed to 3-4m/min according to actual conditions, and controlling the surface density of the adhesive film to be 90g/m2Obtaining a hot melt adhesive film;
A2. compounding the hot-melt adhesive film obtained in the step A1 and alternative glass fiber cloth by using a hot-melt pre-dipping machine under the conditions of heating and pressurizing, wherein the compounding temperature is 65 ℃, the compounding speed is 4m/min, the gaps between 4 groups of compounding rollers are respectively 0.58mm, 0.53mm, 0.53mm and 0.48mm, so as to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg, and the surface weight of the obtained hot-melt prepreg is 400 +/-20 g/m2The mass content of the prepreg resin is 44-47%.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin composite material comprises the following steps:
laying the toughened and flame-retardant hot-melt phenolic resin prepreg according to the design requirement, heating, pressurizing, curing and molding the 3 layers of the laid prepreg by adopting a press, wherein the curing temperature is 140 ℃, the pressure is 0.6MPa, the heating rate is 2 ℃/min, and the temperature is kept for 1.5h when the temperature reaches 140 ℃.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 15 FT-LB; the 60-second vertical burning length is 109 mm; the 30-second 45-degree combustion time is 2 s; a smoke density (4 min Ds) of 18; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe content was detected to be 15 ppm.
Example 2
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
80 parts of thermoplastic phenolic resin, 20 parts of thermosetting phenolic resin, 7 parts of flame retardant aluminum hydroxide, 30 parts of toughening agent (glue solution prepared from carboxyl-terminated polybutadiene and ethyl acetate according to the mass ratio of 1: 2), KH-5500.15 parts of coupling agent and 3 parts of curing agent melamine.
The thermosetting phenolic resin is prepared from the following raw materials: phenol, formaldehyde and a first catalyst ammonia water, wherein the molar ratio of the cresol to the formaldehyde is 0.77: 1; the mass of the first catalyst was 1.5% of the mass of phenol.
Wherein the preparation raw materials of the thermoplastic phenolic resin comprise: phenol, p-tert-butylphenol, formaldehyde and a second catalyst oxalic acid, wherein the molar ratio of the phenol to the p-tert-butylphenol is 4:1, and the molar ratio of the phenol to the formaldehyde is 1.13: 1; the mass of the second catalyst was 1.5% of the mass of phenol.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin comprises the following steps:
s01 preparation of thermosetting phenolic resin, namely mixing phenol and formaldehyde according to a molar ratio of 0.77: 1, adding the mixture into a reaction kettle, adding ammonia water with the mass of 1.5% of phenol as a catalyst when the system temperature is 36 ℃, stirring, heating to 80 ℃ at the speed of 2 ℃/min, carrying out heat preservation reaction for 4 hours, reducing the system temperature to 70 ℃ after the reaction is finished, starting to carry out pressure-maintaining dehydration for 4 hours under the pressure of-0.08 to-0.09 MPa, starting to test the gel time of the phenolic resin at 150 ℃ at intervals of 5 to 10 minutes when the system temperature starts to gradually rise, and stopping dehydration when the gel time is 120s to obtain the thermosetting phenolic resin;
s02 preparation of thermoplastic phenolic resin, namely mixing phenol and p-tert-butyl phenol according to a molar ratio of 4:1, adding the mixture and formaldehyde into a reaction kettle according to a molar ratio of 1.13:1, adding oxalic acid with the mass of 1.5% of that of phenol as a catalyst at the temperature of a system of 40 ℃, stirring, heating to 80 ℃ at the speed of 1.5 ℃/min, carrying out heat preservation reaction for 2 hours, raising the temperature of the system to 95 ℃ after the reaction is finished, carrying out pressure-maintaining dehydration for 3 hours under the pressure of-0.08 to-0.09 MPa, testing the viscosity of the phenolic resin at 100 ℃ at intervals of 5-10 minutes when the temperature of the system begins to gradually rise, and stopping dehydration when the viscosity is 400-450mPa · s, thus obtaining the thermoplastic phenolic resin;
s1, mixing the raw materials in parts by mass as 1: 4, adding 80 parts of thermoplastic phenolic resin into 20 parts of thermosetting phenolic resin, and stirring and mixing for 30min at 80 ℃ to obtain mixed resin;
s2, adding 30 parts of toughening agent (the toughening agent is carboxyl-terminated polybutadiene and ethyl acetate are prepared into glue solution according to the mass ratio of 1: 1) into 100 parts of the mixed resin obtained in the step S1, adding 7 parts of aluminum hydroxide flame retardant, adding 0.15 part of KH-550 coupling agent, and stirring at 75 ℃ for 4 hours to obtain the toughened flame-retardant hot-melt phenolic resin;
and S3, mixing the modified resin obtained in the step S2 with 3 parts of curing agent melamine, and stirring for 1 hour at 75 ℃ to obtain the toughened and flame-retardant hot-melt phenolic resin.
The toughened and flame-retardant hot-melt phenolic resin prepreg of the embodiment comprises the toughened and flame-retardant hot-melt phenolic resin and a reinforcing material, wherein the reinforcing material is 240g/m in gram weight2The high-strength glass fiber satin cloth.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin prepreg comprises the following steps:
A1. preparing the toughened and flame-retardant hot-melt phenolic resin into an adhesive film by adopting an adhesive film method, putting the toughened and flame-retardant hot-melt phenolic resin into an adhesive coater, and carrying out adhesive coating at the temperature of 65-70 DEG CCoating, adjusting the coating speed to 3-4m/min according to the actual condition, and controlling the surface density of the adhesive film to be 85g/m2Obtaining a hot melt adhesive film;
A2. compounding the hot-melt adhesive film obtained in the step A1 and alternative glass fiber cloth by using a hot-melt pre-dipping machine under the conditions of heating and pressurizing, wherein the compounding temperature is 65 ℃, the compounding speed is 4m/min, the gaps between 4 groups of compounding rollers are respectively 0.58mm, 0.53mm, 0.53mm and 0.48mm, so as to obtain the toughened and flame-retardant hot-melt phenolic resin pre-dip material, and the surface weight of the obtained hot-melt pre-dip material is 400 +/-15 g/m2The mass content of the prepreg resin is 38-42%.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin composite material comprises the following steps:
laying the toughened and flame-retardant hot-melt phenolic resin prepreg according to the design requirement, heating, pressurizing, curing and molding the 3 layers of the laid prepreg by adopting a press, wherein the curing temperature is 120 ℃, the pressure is 0.6MPa, the heating rate is 2 ℃/min, and the temperature is kept for 2h when the temperature reaches 120 ℃.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 15 FT-LB; the 60-second vertical combustion length is 85 mm; the 30-second 45-degree combustion time is 0 s; smoke density (4 min Ds) 13; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 9 ppm.
Example 3
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
80 parts of thermoplastic phenolic resin, 20 parts of thermosetting phenolic resin, 5 parts of flame retardant aluminum hydroxide, 3 parts of ammonium polyphosphate, 20 parts of toughening agent (glue solution prepared from polyvinyl butyral and ethanol according to the mass ratio of 1: 2.5), KH-5500.15 parts of coupling agent and 5 parts of curing agent melamine.
The thermosetting phenolic resin is prepared from the following raw materials: phenol, formaldehyde and a first catalyst ammonia water, wherein the molar ratio of the cresol to the formaldehyde is 0.83: 1; the mass of the first catalyst was 1.5% of the mass of phenol.
Wherein the preparation raw materials of the thermoplastic phenolic resin comprise: phenol, formaldehyde and a second catalyst hydrochloric acid, wherein the molar ratio of the phenol to the formaldehyde is 1.18: 1; the mass of the second catalyst was 1.5% of the mass of phenol.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin comprises the following steps:
s01 preparation of thermosetting phenolic resin, namely mixing phenol and formaldehyde according to a molar ratio of 0.83: 1, adding the mixture into a reaction kettle, adding ammonia water with the mass of 1.5% of phenol as a catalyst when the system temperature is 36 ℃, stirring, heating to 80 ℃ at the speed of 2 ℃/min, carrying out heat preservation reaction for 4 hours, reducing the system temperature to 70 ℃ after the reaction is finished, carrying out pressure-maintaining dehydration for 3.5 hours under the pressure of-0.08 to-0.09 MPa, starting to test the gel time of the phenolic resin at 150 ℃ at intervals of 5-10 min when the system temperature starts to gradually rise, and stopping dehydration when the gel time is 110s to obtain the thermosetting phenolic resin;
s02. preparing thermoplastic phenolic resin, namely adding phenol and formaldehyde into a reaction kettle according to the molar ratio of 1.18:1, adding hydrochloric acid accounting for 1.5% of the mass of the phenol as a catalyst when the temperature of a system is 40 ℃, stirring, heating to 80 ℃ at the speed of 1.5 ℃/min, carrying out heat preservation reaction for 2h, raising the temperature of the system to 95 ℃ after the reaction is finished, starting to carry out pressure-maintaining dehydration for 2.5h under the pressure of-0.08 to-0.09 MPa, starting to test the viscosity of the phenolic resin at 100 ℃ at the interval of 5 to 10min when the temperature of the system gradually rises, and stopping the dehydration when the viscosity is 400-plus 450mPa S, so as to obtain the thermoplastic phenolic resin;
s1, mixing the raw materials in parts by mass as 1: 4, adding 80 parts of thermoplastic phenolic resin into 20 parts of thermosetting phenolic resin, and stirring and mixing for 30min at 80 ℃ to obtain mixed resin;
s2, adding 20 parts of toughening agent (the toughening agent is polyvinyl butyral and ethanol which are prepared into glue solution according to the mass ratio of 1: 2.5) into 100 parts of the mixed resin obtained in the step S1, adding 5 parts of aluminum hydroxide and 3 parts of ammonium polyphosphate as flame retardants, adding 0.15 part of KH-550 coupling agent, and stirring at 75 ℃ for 4 hours to obtain the toughened and flame-retardant hot-melt phenolic resin;
and S3, mixing the modified resin obtained in the step S2 with 5 parts of curing agent melamine, and stirring for 1 hour at 75 ℃ to obtain the toughened and flame-retardant hot-melt phenolic resin.
The toughened and flame-retardant hot-melt phenolic resin prepreg of the embodiment comprises the toughened and flame-retardant hot-melt phenolic resin and a reinforcing material, wherein the reinforcing material is prepared from the toughened and flame-retardant hot-melt phenolic resin with the gram weight of 200g/m2The high silica glass fiber cloth.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin prepreg comprises the following steps:
A1. preparing the toughened and flame-retardant hot-melt phenolic resin into an adhesive film by adopting an adhesive film method, putting the toughened and flame-retardant hot-melt phenolic resin into an adhesive coater, coating at the temperature of 75-80 ℃, adjusting the coating speed to be 2-3m/min according to actual conditions, and controlling the surface density of the adhesive film to be 80g/m2Obtaining a hot melt adhesive film;
A2. compounding the hot-melt adhesive film obtained in the step A1 and alternative glass fiber cloth by using a hot-melt pre-dipping machine under the conditions of heating and pressurizing, wherein the compounding temperature is 65 ℃, the compounding speed is 3m/min, the gaps between 4 groups of compounding rollers are respectively 0.58mm, 0.53mm, 0.53mm and 0.48mm, so as to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg, and the surface weight of the obtained hot-melt prepreg is 360 +/-10 g/m2The mass content of the prepreg resin is 42-45%.
The preparation method of the toughened and flame-retardant hot-melt phenolic resin composite material comprises the following steps:
laying the toughened and flame-retardant hot-melt phenolic resin prepreg according to the design requirement, heating, pressurizing, curing and molding the 3 layers of the laid prepreg by adopting a press, wherein the curing temperature is 140 ℃, the pressure is 0.4MPa, the heating rate is 2 ℃/min, and the temperature is kept for 2h when the temperature reaches 140 ℃.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 16.5 FT-LB; the 60-second vertical burning length is 55 mm; the 30-second 45-degree combustion time is 0 s; smoke density (4 min Ds) of 7; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 5 ppm.
Example 4
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
50 parts of thermosetting phenolic resin, 50 parts of thermoplastic phenolic resin, 5 parts of flame retardant aluminum hydroxide, 15 parts of toughening agent (glue solution prepared from common nitrile-butadiene rubber (NBR) and ethyl acetate according to the mass ratio of 1: 1), KH-5500.12 parts of coupling agent and 2 parts of curing agent melamine.
The preparation methods and other raw materials of the toughened flame-retardant hot-melt phenolic resin, the toughened flame-retardant hot-melt phenolic resin prepreg, the toughened flame-retardant hot-melt phenolic resin composite material and the other raw materials in the embodiment are the same as those in the embodiment 1.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 14 FT-LB; the 60-second vertical burning length is 107 mm; the 30-second 45-degree combustion time is 1 s; smoke density (4 min Ds) 19; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 14 ppm.
Example 5
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
100 parts of thermosetting phenolic resin, 2 parts of flame retardant aluminum hydroxide, 10 parts of toughening agent (glue solution prepared from common nitrile-butadiene rubber (NBR) and ethyl acetate according to the mass ratio of 1: 1) and KH-5500.1 parts of coupling agent.
The preparation methods and other raw materials of the toughened flame-retardant hot-melt phenolic resin, the toughened flame-retardant hot-melt phenolic resin prepreg, the toughened flame-retardant hot-melt phenolic resin composite material and the other raw materials in the embodiment are the same as those in the embodiment 1.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 12 FT-LB; the 60-second vertical combustion length is 108 mm; the 30-second 45-degree combustion time is 3 s; smoke density (4 min Ds) 19; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 18 ppm.
Example 6
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
100 parts of thermoplastic phenolic resin, 2 parts of flame retardant aluminum hydroxide, 10 parts of toughening agent (glue solution prepared from common nitrile-butadiene rubber (NBR) and ethyl acetate according to the mass ratio of 1: 1), KH-5500.1 parts of coupling agent and 10 parts of curing agent hexamethylenetetramine.
The preparation methods and other raw materials of the toughened flame-retardant hot-melt phenolic resin, the toughened flame-retardant hot-melt phenolic resin prepreg, the toughened flame-retardant hot-melt phenolic resin composite material and the other raw materials in the embodiment are the same as those in the embodiment 1.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 12 FT-LB; the 60-second vertical burning length is 119 mm; the 30-second 45-degree combustion time is 3 s; smoke density (4 min Ds) 24; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 19 ppm.
Example 7
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
20 parts of thermoplastic phenolic resin, 80 parts of thermosetting phenolic resin, 15 parts of flame retardant aluminum hydroxide, 5 parts of toughening agent (glue solution prepared from carboxyl-terminated polybutadiene and ethyl acetate according to the mass ratio of 1: 2) and KH-5501 parts of coupling agent.
The preparation methods and other raw materials of the toughened flame-retardant hot-melt phenolic resin, the toughened flame-retardant hot-melt phenolic resin prepreg, the toughened flame-retardant hot-melt phenolic resin composite material and the other raw materials in the embodiment are the same as those in the embodiment 1.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop hammer impact strength of the composite material test plate is 10.5 FT-LB; the 60-second vertical burning length is 110 mm; the 30-second 45-degree combustion time is 2 s; smoke density (4 min Ds) 17; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 13 ppm.
Example 8
The toughened and flame-retardant hot-melt phenolic resin provided by the embodiment is prepared from the following raw materials in parts by mass:
20 parts of thermoplastic phenolic resin, 80 parts of thermosetting phenolic resin, 1 part of flame retardant aluminum hydroxide, 100 parts of toughening agent (glue solution prepared by carboxyl-terminated polybutadiene and ethyl acetate according to the mass ratio of 1: 2) and KH-5500.05 parts of coupling agent.
The preparation methods and other raw materials of the toughened flame-retardant hot-melt phenolic resin, the toughened flame-retardant hot-melt phenolic resin prepreg, the toughened flame-retardant hot-melt phenolic resin composite material and the other raw materials in the embodiment are the same as those in the embodiment 1.
And (3) carrying out impact strength test on the cured composite material test board according to BSS7326 standard requirements, carrying out flame retardant property test according to CCAR 25 annex F standard requirements, and carrying out toxic gas content test according to BSS7239 standard requirements.
The drop weight impact strength of the composite material test plate is 14FT-LB; the 60-second vertical burning length is 145 mm; the 30-second 45-degree combustion time is 5 s; smoke density (4 min Ds) 25; the flame is not penetrated; the content of toxic gases HCN, HCl and HF is 0, NOXThe detected content was 18 ppm.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The toughened and flame-retardant hot-melt phenolic resin is characterized by comprising the following components in parts by weight:
0-100 parts of thermoplastic phenolic resin, 0-100 parts of thermosetting phenolic resin, 1-15 parts of flame retardant, 5-100 parts of toughening agent, 0.05-1 part of coupling agent and 0-20 parts of curing agent;
wherein the thermoplastic phenolic resin and the thermosetting phenolic resin are not 0 part at the same time.
2. The toughened and flame-retardant hot-melt phenolic resin as claimed in claim 1, wherein the preparation raw materials comprise the following components in parts by weight:
20-80 parts of thermoplastic phenolic resin, 20-80 parts of thermosetting phenolic resin, 2-8 parts of flame retardant, 10-30 parts of toughening agent, 0.1-0.15 part of coupling agent and 0-10 parts of curing agent.
3. The toughened, flame retardant hot melt phenolic resin of claim 1, wherein:
the flame retardant is one or a combination of more of ammonium polyphosphate, red phosphorus, aluminum hydroxide, magnesium hydroxide and tricresyl phosphate;
the toughening agent is a mixed glue solution prepared from at least one of carboxyl-terminated polybutadiene, polyvinyl acetal and nitrile rubber and at least one of methanol, ethanol, acetone, butanone and ethyl acetate according to the mass ratio of 1 (1-3);
the coupling agent is one or a combination of more of KH-550, KH-560 and KH-570;
the curing agent is one or a combination of more of sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, epoxy resin, paraformaldehyde, melamine, hexamethylenetetramine and 2,2' - (1, 3-phenylene) -bisoxazoline.
4. A method of preparing the toughened, flame retardant hot melt phenolic resin of claim 1, comprising the steps of:
and mixing and stirring the thermoplastic phenolic resin, the thermosetting phenolic resin, the flame retardant, the toughening agent, the coupling agent and the curing agent to obtain the toughened and flame-retardant hot-melt phenolic resin.
5. The method for preparing the toughened and flame-retardant hot-melt phenolic resin according to claim 4, which is characterized by comprising the following steps:
s1, mixing the thermoplastic phenolic resin with the thermosetting phenolic resin, and stirring at 60-85 ℃ for 20-60min to obtain mixed resin;
s2, mixing the mixed resin obtained in the step S1 with the flame retardant, the toughening agent and the coupling agent, and stirring for 3-6h at 60-80 ℃ to obtain modified resin;
s3, mixing the modified resin obtained in the step S2 with the curing agent, and stirring for 1-3h at 40-90 ℃ to obtain the toughened and flame-retardant hot-melt phenolic resin.
6. A toughened and flame-retardant hot-melt phenolic resin prepreg is characterized in that the preparation raw material comprises the toughened and flame-retardant hot-melt phenolic resin according to any one of claims 1 to 3.
7. The toughened and flame-retardant hot-melt phenolic resin prepreg according to claim 6, which is characterized in that the preparation raw materials further comprise a reinforcing material, and the mass content of the toughened and flame-retardant hot-melt phenolic resin in the toughened and flame-retardant hot-melt phenolic resin prepreg is 30-50%.
8. A method of making the toughened, flame retardant, hot melt phenolic resin prepreg according to claim 6 or 7, comprising the steps of:
preparing the toughened and flame-retardant hot-melt phenolic resin into an adhesive film, and then compounding the adhesive film with the reinforcing material to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg.
9. The method for preparing the toughened and flame-retardant hot-melt phenolic resin prepreg according to claim 8, which is characterized by comprising the following steps:
A1. preparing the toughened and flame-retardant hot-melt phenolic resin into a glue film by adopting a glue film method, wherein the coating temperature is 60-90 ℃, the coating speed is 2-5m/min, and the areal weight of the glue film is controlled to be 50-150g/m2Obtaining a hot melt adhesive film;
A2. and B, compounding the hot-melt adhesive film in the step A1 with the reinforcing material to obtain the toughened and flame-retardant hot-melt phenolic resin prepreg, wherein the compounding temperature is 40-90 ℃, the compounding speed is 4-10m/min, and the compounding roller gap is 0.2-0.8 mm.
10. The toughened and flame-retardant hot-melt phenolic resin composite material is characterized by being prepared from the toughened and flame-retardant hot-melt phenolic resin prepreg according to claim 6 or 7.
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