CN111534092B - High-toughness halogen-free cyanate ester resin composite material and preparation method thereof - Google Patents
High-toughness halogen-free cyanate ester resin composite material and preparation method thereof Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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Abstract
The invention discloses a high-toughness halogen-free cyanate ester resin composite material and a preparation method thereof, the composite material is prepared by mixing modified cyanate ester resin with carbon nano tubes, a surfactant and deionized water, stirring uniformly at a high speed, and combining a layer of surfactant on the surfaces of single-wall carbon nano tubes and multi-wall carbon nano tubes in an ultrasonic dispersion process, so that the dispersion state of the carbon nano tubes is favorably kept; the side phosphorus group in the DOPO structure is dehydrated and carbonized at high temperature, so that oxygen is isolated, and no smoke is generated and toxic and harmful substances such as hydrogen halide are generated.
Description
Technical Field
The invention relates to the technical field of halogen-free cyanate ester resin, in particular to a high-toughness halogen-free cyanate ester resin composite material and a preparation method thereof.
Background
At present, in order to realize the flame retardant performance of the resin, the commonly used bisphenol a type cyanate ester resin is usually added with halogen, but the halogen-containing flame retardant material can generate a large amount of smoke and toxic corrosive hydrogen halide gas in the flame retardant process to cause pollution and harm, and the toughness of the existing bisphenol a type cyanate ester resin material is not enough, the toughening method is usually to add a toughening agent into the material, and the carbon nano tube has higher toughness and is widely applied to the toughening additive of the cyanate ester resin. In the prior art, carbon nanotubes and cyanate ester resin are usually directly mixed, although the toughness can be enhanced, the carbon nanotubes are not uniformly dispersed and the toughening effect is not obvious because the carbon nanotubes and the cyanate ester resin can not be polymerized, and the toughness of the toughened material can not meet the requirement because the bisphenol A type cyanate ester resin has low toughness.
The invention patent with the application number of CN201810869549.2 discloses a conductive carbon nanotube/cyanate composite material and a preparation method thereof, wherein the carbon nanotube is directly mixed with cyanate resin in the method, the toughness of the prepared composite material is improved to a certain extent, but the bending strength of the composite material is only 139.6MPa at most, and the requirement cannot be met. The patent publication No. CN110218445A discloses a high-toughness halogen-free cyanate ester composite material, which is obtained by adding a phosphorus-containing cyanate ester resin and a modified carbon nanotube into a reaction vessel at the same time, mixing and dissolving the materials at a high temperature, pouring the mixture into a preheated mold, and performing vacuum defoaming and curing on the mixture, so that the crosslinking degree of the composite material is improved, and the toughness and the strength of the material are greatly enhanced. However, the mechanical properties and the processability of the conventional halogen-free cyanate ester resin composite material still need to be improved, and the thermal stability, the chemical stability and the flame retardant property need to be further improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a high-toughness halogen-free cyanate ester resin composite material and a preparation method thereof.
The modified cyanate resin is mixed with the carbon nano tube, the surfactant and the deionized water, then the mixture is uniformly stirred at a high speed, a layer of surfactant is combined on the surfaces of the single-walled carbon nano tube and the multi-walled carbon nano tube in the ultrasonic dispersion process, so that the dispersion state of the carbon nano tube is favorably kept, the surfactants are all nonionic, the composite material is enabled to keep good solubility in water or an organic solvent, the stability is good, the composite material is not easily influenced by strong electrolyte inorganic salt, acid and alkali, the foaming is not easily generated in the curing process, the compatibility of the carbon nano tube and the modified cyanate resin is improved, and the mechanical property and the processing property of the composite material are improved.
The compound I is obtained by Mannich reaction under the condition that raw materials including 5-amino-m-benzaldehyde, DOPO, paraformaldehyde and N, N-dimethylformamide are selected as solvents; the DOPO structure contains a P-H bond, has high activity on olefin, epoxy bond and carbonyl, can react to generate a plurality of derivatives, and lateral phosphorus groups are introduced in a mode of cyclic O-P-O bond, so that the thermal stability and the chemical stability are higher than those of common acyclic organic phosphate, the flame retardant property is better, and a derivative compound with good and durable flame retardant property is obtained after the reaction; the compound I and p-hydroxyamine are subjected to condensation reaction under the conditions of ethanol serving as a solvent and acetic acid catalysis to obtain a compound II with active imino, the toughness of a polymer is improved by a conjugated structure of imino and a benzene ring, modified cyanate resin with good toughness and flame retardant property is obtained after cyanation reaction, the modified cyanate resin is more easily compatible and crosslinked with a carbon nano tube, a side phosphorus group in a DOPO structure is dehydrated and carbonized at high temperature, oxygen is isolated, and smoke is avoided and toxic and harmful substances such as hydrogen halide are not generated.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a high-toughness halogen-free cyanate ester resin composite material, which is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.2-99.5%, and the mass ratio of the surfactant to the carbon nano tubes is 0.3-0.6: 1;
the reaction formula of the modified cyanate ester resin is as follows:
the preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 5-amino-m-benzaldehyde, DOPO, paraformaldehyde and N, N-dimethylformamide into a three-neck flask, heating to 155-160 ℃, carrying out reflux stirring reaction for 10-12 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 2-3 times by using ethyl acetate, carrying out recrystallization on a concentrate after reduced pressure concentration by using petroleum ether, and drying crystals for 16-20 hours at 45-55 ℃ to obtain a compound I;
s2, dissolving p-hydroxyaniline in ethanol, adding the compound I and a proper amount of acetic acid, heating to 80-85 ℃, refluxing and stirring for reaction for 3-5 hours, standing until a solid is separated out, filtering under reduced pressure, washing a filter cake for 2-3 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding the compound II, toluene and triethylamine into a three-neck flask, cooling to-5 ℃, slowly adding cyanogen chloride, heating to 70-80 ℃ after the addition is finished, stirring for reacting for 6-8 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate ester III.
As a further embodiment of the present invention, the molar ratio of 5-amino-m-diphenylaldehyde, DOPO and paraformaldehyde in step S1 is 1: 2.2-2.5: 2.6 to 3.2, the addition amount of the N, N-dimethylformamide is 10 to 20 times of the mass of the 5-amino-m-diphenylformaldehyde, the addition amount of the petroleum ether during recrystallization is 10 to 15 times of the mass of the concentrate, the recrystallization temperature is 5 to 10 ℃, and the recrystallization time is 10 to 15 hours.
As a further scheme of the invention, the molar ratio of the p-hydroxyaniline, the ethanol, the compound I and the acetic acid in the step S2 is 2.1-2.5: 8-15: 1: 0.03 to 0.06.
As a further scheme of the invention, the molar ratio of the compound II, triethylamine and cyanogen chloride in the step S3 is 1: 2.5-3.2: 2.1-2.3, and the addition amount of the toluene is 10-20 times of the mass of the compound II.
According to a further scheme of the invention, the carbon nano-tube comprises a single-wall carbon nano-tube with the diameter of 0.8-1.5 nm and a multi-wall carbon nano-tube with the diameter of 30-50 nm according to the mass ratio of 1.2-1.5: 1 are mixed.
As a further scheme of the invention, the surfactant is one or a mixture of more of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether and high-carbon fatty alcohol polyoxyethylene ether.
The invention also provides a preparation method of the high-toughness halogen-free cyanate ester resin composite material, which comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and the deionized water, uniformly stirring at the rotating speed of 2000-3000rpm, and performing ultrasonic dispersion for 40-60min to obtain a mixture;
(2) and (3) carrying out vacuum freeze drying on the mixture for 10-20 min, heating to 120-130 ℃, and curing and forming by stages to obtain the composite material.
As a further scheme of the invention, the addition amount of the deionized water is 0.2-0.4 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 400-600W.
As a further scheme of the invention, the staged curing molding specifically comprises the following steps: heating to 170-180 ℃ for curing for 1-2 hours, heating to 190-200 ℃ for curing for 1-2 hours, and heating to 230-240 ℃ for curing for 2-3 hours.
The invention has the beneficial effects that:
1. according to the high-toughness halogen-free cyanate ester resin composite material, after the modified cyanate ester resin is mixed with the carbon nano tubes, the surfactant and deionized water, the mixture is uniformly stirred at a high speed, a layer of surfactant is combined on the surfaces of the single-walled carbon nano tubes and the multi-walled carbon nano tubes in the ultrasonic dispersion process, so that the dispersion state of the carbon nano tubes is favorably kept, and the surfactants are all nonionic, so that the composite material keeps good solubility in water or an organic solvent, is good in stability, is not easily influenced by strong electrolyte inorganic salt, acid and alkali, is not easily foamed in the curing process, improves the compatibility of the carbon nano tubes and the modified cyanate ester resin, and improves the mechanical property and the processing property of the composite material.
2. The modified cyanate ester resin is prepared by performing a Mannich reaction on raw materials including 5-amino-m-benzaldehyde, DOPO and paraformaldehyde under the condition that N, N-dimethylformamide is taken as a solvent to obtain a compound I; the DOPO structure contains a P-H bond, has high activity on olefin, epoxy bond and carbonyl, can react to generate a plurality of derivatives, and lateral phosphorus groups are introduced in a mode of cyclic O-P-O bond, so that the thermal stability and the chemical stability are higher than those of common acyclic organic phosphate, the flame retardant property is better, and a derivative compound with good and durable flame retardant property is obtained after the reaction; the compound I and p-hydroxyamine are subjected to condensation reaction under the conditions of ethanol serving as a solvent and acetic acid catalysis to obtain a compound II with active imino, the toughness of a polymer is improved by a conjugated structure of imino and a benzene ring, modified cyanate resin with good toughness and flame retardant property is obtained after cyanation reaction, the modified cyanate resin is more easily compatible and crosslinked with a carbon nano tube, a side phosphorus group in a DOPO structure is dehydrated and carbonized at high temperature, oxygen is isolated, and smoke is avoided and toxic and harmful substances such as hydrogen halide are not generated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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 high-toughness halogen-free cyanate ester resin composite material is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.4%, and the mass ratio of the surfactant to the carbon nano tubes is 0.5: 1; the carbon nano tube is prepared by mixing a single-walled carbon nano tube with the diameter of 0.8-1.5 nm and a multi-walled carbon nano tube with the diameter of 30-50 nm according to the mass ratio of 1.4: 1 are mixed. The surfactant is composed of octyl phenol polyoxyethylene ether and high-carbon fatty alcohol polyoxyethylene ether according to the mass ratio of 1: 1 are mixed.
The preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 149g (1mol) of 5-amino-m-benzaldehyde, 518.4g (2.4mol) of DOPO, 84g (2.8mol) of paraformaldehyde and 2384g of N, N-dimethylformamide into a three-neck flask, heating to 157 ℃, refluxing and stirring for reaction for 11 hours, standing until a solid is separated out, filtering under reduced pressure, washing a filter cake for 2 times by using ethyl acetate, recrystallizing a concentrate after concentration under reduced pressure by using petroleum ether, and drying crystals for 18 hours at 52 ℃ to obtain a compound I; the addition amount of petroleum ether during recrystallization is 15 times of the mass of the concentrate, the recrystallization temperature is 9 ℃, and the recrystallization time is 14 hours.
S2, dissolving 26.16g (0.24mol) of p-hydroxyaniline in 55.2g (1.2mol) of ethanol, adding 60.5g (0.1mol) of compound I and 3g (0.05mol) of acetic acid, heating to 83 ℃, refluxing and stirring for reaction for 4.5 hours, standing until a solid is separated out, filtering under reduced pressure, washing a filter cake for 3 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding 78.72g (0.1mol) of compound II, 1180.8g of toluene and 29.29g (0.29mol) of triethylamine into a three-neck flask, cooling to 3 ℃, slowly adding 13.53g (0.22mol) of cyanogen chloride, heating to 78 ℃ after the addition is finished, stirring for reaction for 7 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate III.
The preparation method of the high-toughness halogen-free cyanate ester resin composite material comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and deionized water, uniformly stirring at the rotating speed of 2500rpm, and performing ultrasonic dispersion for 50min to obtain a mixture; the addition amount of the deionized water is 0.35 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 500W.
(2) And (3) carrying out vacuum freeze drying on the mixture for 15min, heating to 128 ℃, and curing and forming in stages to obtain the composite material. The staged curing molding specifically comprises the following steps: heating to 178 ℃ for curing for 1.5 hours, heating to 196 ℃ for curing for 1.5 hours, and heating to 236 ℃ for curing for 2.6 hours.
Example 2
The high-toughness halogen-free cyanate ester resin composite material is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.4%, and the mass ratio of the surfactant to the carbon nano tubes is 0.52: 1; the carbon nano tube is prepared by mixing a single-walled carbon nano tube with the diameter of 0.8-1.5 nm and a multi-walled carbon nano tube with the diameter of 30-50 nm according to the mass ratio of 1.5: 1 are mixed. The surfactant is octyl phenol polyethenoxy ether.
The preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 149g (1mol) of 5-amino-m-benzaldehyde, 496.8g (2.3mol) of DOPO, 93g (3.1mol) of paraformaldehyde and 2682g of N, N-dimethylformamide into a three-neck flask, heating to 158 ℃, carrying out reflux stirring reaction for 11.5 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 3 times by using ethyl acetate, carrying out reduced pressure concentration, recrystallizing a concentrate by using petroleum ether, and drying crystals for 18 hours at 53 ℃ to obtain a compound I; the addition amount of petroleum ether during recrystallization was 13 times the mass of the concentrate, the recrystallization temperature was 6 ℃, and the recrystallization time was 14 hours.
S2, dissolving 25g (0.23mol) of p-hydroxyaniline in 46g (1mol) of ethanol, adding 60.5g (0.1mol) of compound I and 2.4g (0.04mol) of acetic acid, heating to 84 ℃, refluxing and stirring for reaction for 4.5 hours, standing until a solid is separated out, filtering under reduced pressure, washing a filter cake for 2 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding 78.72g (0.1mol) of compound II, 1023g of toluene and 27.3g (0.27mol) of triethylamine into a three-neck flask, cooling to 4 ℃, slowly adding 13.9g (0.226mol) of cyanogen chloride, heating to 76 ℃ after the addition is finished, stirring for reaction for 7.5 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate III.
The preparation method of the high-toughness halogen-free cyanate ester resin composite material comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and deionized water, uniformly stirring at the rotating speed of 2800rpm, and performing ultrasonic dispersion for 55min to obtain a mixture; the addition amount of the deionized water is 0.36 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 500W.
(2) And (3) carrying out vacuum freeze drying on the mixture for 16min, heating to 128 ℃, and curing and molding in stages to obtain the composite material. The staged curing molding specifically comprises the following steps: heating to 180 deg.C for 1.6 hr, heating to 198 deg.C for 1.8 hr, and heating to 238 deg.C for 2.4 hr.
Example 3
The high-toughness halogen-free cyanate ester resin composite material is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.2%, and the mass ratio of the surfactant to the carbon nano tubes is 0.6: 1; the carbon nano tube is prepared by mixing a single-walled carbon nano tube with the diameter of 0.8-1.5 nm and a multi-walled carbon nano tube with the diameter of 30-50 nm according to the mass ratio of 1.5: 1 are mixed. The surfactant is higher fatty alcohol polyoxyethylene ether.
The preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 149g (1mol) of 5-amino-m-benzaldehyde, 518.4g (2.4mol) of DOPO, 81g (2.7mol) of paraformaldehyde and 2086g of N, N-dimethylformamide into a three-neck flask, heating to 160 ℃, carrying out reflux stirring reaction for 12 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 3 times by using ethyl acetate, carrying out reduced pressure concentration, recrystallizing a concentrate by using petroleum ether, and drying crystals for 19 hours at 53 ℃ to obtain a compound I; the addition amount of petroleum ether during recrystallization was 14 times the mass of the concentrate, the recrystallization temperature was 8 ℃, and the recrystallization time was 13 hours.
S2, dissolving 25.62g (0.235mol) of p-hydroxyaniline in 64.4(1.4mol) of ethanol, adding 60.5g (0.1mol) of compound I and 2.4g (0.04mol) of acetic acid, heating to 85 ℃, refluxing and stirring for reaction for 4.5 hours, standing until a solid is precipitated, filtering under reduced pressure, washing a filter cake for 3 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding 78.72g (0.1mol) of compound II, 1574g of toluene and 31.31g (0.31mol) of triethylamine into a three-neck flask, cooling to-3 ℃, slowly adding 13.84g (0.225mol) of cyanogen chloride, heating to 80 ℃ after the addition is finished, stirring for reacting for 8 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate III.
The preparation method of the high-toughness halogen-free cyanate ester resin composite material comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and deionized water, uniformly stirring at the rotating speed of 2500rpm, and performing ultrasonic dispersion for 58min to obtain a mixture; the addition amount of the deionized water is 0.36 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 580W.
(2) And (3) carrying out vacuum freeze drying on the mixture for 18min, heating to 130 ℃, and curing and forming in stages to obtain the composite material. The staged curing molding specifically comprises the following steps: heating to 178 ℃ for curing for 2 hours, heating to 198 ℃ for curing for 2 hours, and heating to 235 ℃ for curing for 2.5 hours.
Example 4
The high-toughness halogen-free cyanate ester resin composite material is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.3%, and the mass ratio of the surfactant to the carbon nano tubes is 0.45: 1; the carbon nano tube is prepared by mixing a single-walled carbon nano tube with the diameter of 0.8-1.5 nm and a multi-walled carbon nano tube with the diameter of 30-50 nm according to the mass ratio of 1.38: 1 are mixed. The surfactant is higher fatty alcohol polyoxyethylene ether.
The preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 149g (1mol) of 5-amino-m-benzaldehyde, 475.2g (2.2mol) of DOPO, 87g (2.9mol) of paraformaldehyde and 1937g of N, N-dimethylformamide into a three-neck flask, heating to 159 ℃, carrying out reflux stirring reaction for 12 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 3 times by using ethyl acetate, carrying out reduced pressure concentration, recrystallizing a concentrate by using petroleum ether, and drying crystals for 18 hours at 53 ℃ to obtain a compound I; the addition amount of petroleum ether during recrystallization was 14 times the mass of the concentrate, the recrystallization temperature was 7 ℃, and the recrystallization time was 14 hours.
S2, dissolving 26.38g (0.242mol) of p-hydroxyaniline in 50.6g (1.1mol) of ethanol, adding 60.5g (0.1mol) of compound I and 2.22g (0.037mol) of acetic acid, heating to 81 ℃, refluxing and stirring for reaction for 5 hours, standing until a solid is precipitated, filtering under reduced pressure, washing a filter cake for 2 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding 78.72g (0.1mol) of compound II, 1496g of toluene and 30.3g (0.3mol) of triethylamine into a three-neck flask, cooling to 0 ℃, slowly adding 13.53g (0.22mol) of cyanogen chloride, heating to 77 ℃ after the addition is finished, stirring for reaction for 7.5 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate ester III.
The preparation method of the high-toughness halogen-free cyanate ester resin composite material comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and deionized water, uniformly stirring at the rotating speed of 3000rpm, and performing ultrasonic dispersion for 58min to obtain a mixture; the addition amount of the deionized water is 0.4 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 580W.
(2) And (3) carrying out vacuum freeze drying on the mixture for 20min, heating to 129 ℃, and carrying out staged curing and forming to obtain the composite material. The staged curing molding specifically comprises the following steps: heating to 178 ℃ for curing for 1.8 hours, heating to 196 ℃ for curing for 1.5 hours, and heating to 238 ℃ for curing for 2.5 hours.
Example 5
The high-toughness halogen-free cyanate ester resin composite material is prepared from modified cyanate ester resin, carbon nano tubes and a surfactant, wherein the carbon nano tubes are uniformly dispersed in the cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.3%, and the mass ratio of the surfactant to the carbon nano tubes is 0.55: 1; the carbon nano tube is prepared by mixing a single-walled carbon nano tube with the diameter of 0.8-1.5 nm and a multi-walled carbon nano tube with the diameter of 30-50 nm according to the mass ratio of 1.45: 1 are mixed. The surfactant is prepared by mixing octyl phenol polyoxyethylene ether and nonyl phenol polyoxyethylene ether according to the mass ratio of 2: 1.
The preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 149g (1mol) of 5-amino-m-benzaldehyde, 540g (2.5mol) of DOPO, 90g (3mol) of paraformaldehyde and 2831g of N, N-dimethylformamide into a three-neck flask, heating to 160 ℃, carrying out reflux stirring reaction for 12 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 3 times by using ethyl acetate, carrying out reduced pressure concentration, recrystallizing a concentrate by using petroleum ether, and drying crystals for 19 hours at 54 ℃ to obtain a compound I;
s2, dissolving 26.71g (0.24mol) of p-hydroxyaniline in 64.4g (1.4mol) of ethanol, adding 60.5g (0.1mol) of the compound I and 2.88g (0.048mol) of acetic acid, heating to 85 ℃, refluxing and stirring for reaction for 4 hours, standing until a solid is precipitated, filtering under reduced pressure, washing a filter cake for 3 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding 78.72g (0.1mol) of compound II, 1417g of toluene and 27.3g (0.27mol) of triethylamine into a three-neck flask, cooling to-2 ℃, slowly adding 13.4g (0.22mol) of cyanogen chloride, heating to 76 ℃ after the addition is finished, stirring for reaction for 7.6 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate ester III.
The preparation method of the high-toughness halogen-free cyanate ester resin composite material comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and deionized water, uniformly stirring at the rotating speed of 2900rpm, and performing ultrasonic dispersion for 58min to obtain a mixture; the addition amount of the deionized water is 0.4 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 580W.
(2) And (3) carrying out vacuum freeze drying on the mixture for 18min, heating to 130 ℃, and curing and forming in stages to obtain the composite material. The staged curing molding specifically comprises the following steps: heating to 178 ℃ for curing for 1.8 hours, heating to 198 ℃ for curing for 1.5 hours, and heating to 240 ℃ for curing for 3 hours.
Comparative example 1
This comparative example differs from example 1 in that the modified cyanate ester resin was replaced with a commercially available bisphenol a type cyanate ester.
Comparative example 2
This comparative example differs from example 1 in that no carbon nanotubes are added.
Performance testing
The high-toughness halogen-free cyanate ester resin composite materials prepared in the examples 1-5 and the comparative examples 1-2 are tested for tensile strength, tensile elongation at break, bending strength and oxygen index, the standard of the oxygen index test is GB/T2406-2009, and the specific test results are shown in the following table:
as can be seen from the above table, the halogen-free cyanate ester resin composite material prepared by the invention has good tensile strength, tensile elongation at break, bending strength and oxygen index, which indicates that the material has high toughness and good heat-resistant and flame-retardant properties, because the DOPO structure contains P-H bonds, the DOPO structure has activity on olefin, epoxy bonds and carbonyl groups, and can react to generate a plurality of derivatives, lateral phosphorus groups are introduced in a mode of cyclic O ═ P-O bonds, and a derivative compound with good and durable flame-retardant properties is obtained after the reaction; the toughness of the polymer is improved by the conjugated structure of the imino group and the benzene ring, the modified cyanate resin with good toughness and flame retardant property is obtained after cyanation reaction, the modified cyanate resin is more easily compatible and crosslinked with the carbon nano tube, and the side phosphorus group in the DOPO structure is dehydrated and carbonized at high temperature to isolate oxygen, so that smoke is not generated and toxic and harmful substances such as hydrogen halide are not generated.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. The high-toughness halogen-free cyanate ester resin composite material is characterized by being prepared from modified cyanate ester resin, carbon nanotubes and a surfactant, wherein the carbon nanotubes are uniformly dispersed in the modified cyanate ester resin, the mass ratio of the modified cyanate ester resin in the composite material is 99.2-99.5%, and the mass ratio of the surfactant to the carbon nanotubes is 0.3-0.6: 1;
the reaction formula of the modified cyanate ester resin is as follows:
the preparation method of the modified cyanate ester resin comprises the following steps:
s1, adding 5-amino-m-benzaldehyde, DOPO, paraformaldehyde and N, N-dimethylformamide into a three-neck flask, heating to 155-160 ℃, carrying out reflux stirring reaction for 10-12 hours, standing until a solid is separated out, carrying out reduced pressure filtration, washing a filter cake for 2-3 times by using ethyl acetate, carrying out recrystallization on a concentrate after reduced pressure concentration by using petroleum ether, and drying crystals for 16-20 hours at 45-55 ℃ to obtain a compound I;
s2, dissolving p-hydroxyaniline in ethanol, adding the compound I and a proper amount of acetic acid, heating to 80-85 ℃, refluxing and stirring for reaction for 3-5 hours, standing until a solid is separated out, filtering under reduced pressure, washing a filter cake for 2-3 times by using ethyl acetate, and concentrating under reduced pressure to obtain a compound II;
s3, adding the compound II, toluene and triethylamine into a three-neck flask, cooling to-5 ℃, slowly adding cyanogen chloride, heating to 70-80 ℃ after the addition is finished, stirring for reacting for 6-8 hours, filtering, distilling the filtrate under reduced pressure, and recrystallizing petroleum ether to obtain the modified cyanate ester III.
2. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein the molar ratio of 5-amino-m-diphenylformaldehyde, DOPO, paraformaldehyde in step S1 is 1: 2.2-2.5: 2.6 to 3.2, the addition amount of the N, N-dimethylformamide is 10 to 20 times of the mass of the 5-amino-m-diphenylformaldehyde, the addition amount of the petroleum ether during recrystallization is 10 to 15 times of the mass of the concentrate, the recrystallization temperature is 5 to 10 ℃, and the recrystallization time is 10 to 15 hours.
3. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein the molar ratio of the p-hydroxyphenylamine, the ethanol, the compound I and the acetic acid in the step S2 is 2.1-2.5: 8-15: 1: 0.03 to 0.06.
4. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein the molar ratio of the compound ii in the step S3, triethylamine and cyanogen chloride is 1: 2.5-3.2: 2.1-2.3, and the addition amount of the toluene is 10-20 times of the mass of the compound II.
5. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein the carbon nanotubes are prepared by mixing single-walled carbon nanotubes with a diameter of 0.8-1.5 nm and multi-walled carbon nanotubes with a diameter of 30-50 nm according to a mass ratio of 1.2-1.5: 1 are mixed.
6. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein said surfactant is one or a mixture of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether.
7. The high-toughness halogen-free cyanate ester resin composite material according to claim 1, wherein the preparation method comprises the following steps:
(1) mixing the carbon nano tube, the surfactant, the modified cyanate ester resin and the deionized water, uniformly stirring at the rotating speed of 2000-3000rpm, and performing ultrasonic dispersion for 40-60min to obtain a mixture;
(2) and (3) carrying out vacuum freeze drying on the mixture for 10-20 min, heating to 120-130 ℃, and curing and forming by stages to obtain the composite material.
8. The preparation method of the high-toughness halogen-free cyanate ester resin composite material according to claim 7, wherein the addition amount of the deionized water is 0.2-0.4 times of the mass of the modified cyanate ester resin, and the power of ultrasonic dispersion is 400-600W.
9. The preparation method of the high-toughness halogen-free cyanate ester resin composite material according to claim 7, wherein the staged curing molding specifically comprises: heating to 170-180 ℃ for curing for 1-2 hours, heating to 190-200 ℃ for curing for 1-2 hours, and heating to 230-240 ℃ for curing for 2-3 hours.
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| CN104231624A (en) * | 2014-08-22 | 2014-12-24 | 南京信息职业技术学院 | Modified cyanate resin heat-conducting composite material and preparation method thereof |
| CN109161195A (en) * | 2018-08-02 | 2019-01-08 | 北京空间飞行器总体设计部 | A kind of conductivity type carbon nanotube/cyanate composite material and preparation method thereof |
| CN110218445A (en) * | 2019-06-04 | 2019-09-10 | 扬州天启新材料股份有限公司 | A kind of high-toughness halogen-free cyanate composite material and preparation method thereof |
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| CN104231624A (en) * | 2014-08-22 | 2014-12-24 | 南京信息职业技术学院 | Modified cyanate resin heat-conducting composite material and preparation method thereof |
| CN109161195A (en) * | 2018-08-02 | 2019-01-08 | 北京空间飞行器总体设计部 | A kind of conductivity type carbon nanotube/cyanate composite material and preparation method thereof |
| CN110218445A (en) * | 2019-06-04 | 2019-09-10 | 扬州天启新材料股份有限公司 | A kind of high-toughness halogen-free cyanate composite material and preparation method thereof |
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