CN112341804A - Preparation method of flame-retardant polyamide composite material - Google Patents
Preparation method of flame-retardant polyamide composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a flame-retardant polyamide composite material, which relates to the field of high polymer materials and comprises the following steps: (1) dispersing in a graphene oxide solvent; (2) preparing surface aminated graphene; (3) preparing divinylbenzene-maleic anhydride copolymerized microsphere solid particles; (4) preparing modified graphene flame-retardant particles; (5) preparing a flame-retardant polyamide composite material; according to the method, the organic group is introduced to the surface of the graphene oxide, so that the polarity of the surface of the graphene is improved, the modified graphene flame-retardant particles are matched with the phosphorus flame retardant, the modified graphene flame-retardant particles have good flame retardancy, and meanwhile, the modification of the surface of the graphene improves the compatibility of the flame retardant and a polyamide material, and the influence of the flame retardant on the mechanical property of the polyamide is reduced.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a flame-retardant polyamide composite material.
Background
The demand of polyamide is always the first of five general purpose engineering plastics, and the annual demand increase rate is as high as 10%. The composite material has good mechanical property, durability, corrosion resistance, heat resistance and other properties, and is widely applied to the industries of electronics, electrics, automobiles, buildings, office equipment, machinery, aerospace and the like. However, the polyamide material without flame retardant treatment has low flame retardant rating, the fire retardant rating can only reach V-2 rating, a fire disaster is easily generated during combustion, the polyamide material is very easy to drip during combustion, and a fire accident is easily caused, so that the application field of the polyamide material can be greatly expanded by improving the flame retardant of the polyamide.
Chinese patent CN102492290B discloses a preparation method of high-strength high-toughness flame-retardant polyamide, based on 100 parts by weight of polyamide with relative viscosity of 2.4-3.3, adding a mixture consisting of 15-30 parts by weight of decabromodiphenylethane flame retardant, 3-10 parts by weight of antimony trioxide flame retardant, 0-5 parts by weight of light stabilizer, 0.2-1 part by weight of heat stabilizer and 0.5-1 part by weight of antioxidant, and carrying out melt mixing, extrusion, cooling, drying and grain cutting by a double-screw extruder to obtain the high-strength high-toughness flame-retardant polyamide. The invention adopts decabromodiphenylethane and antimony trioxide and uses a method of modifying polyamide, which can properly improve the flame retardance of the polyamide material, but uses halogen flame retardant to have certain influence on the environment, and simultaneously uses antimony trioxide flame retardant without any treatment on the surface to influence the combination with the polyamide material.
Chinese patent CN102796366B discloses a non-antimony flame-retardant polyamide composite material, which comprises the following components in percentage by weight: 20 to 90 percent of polyamide, 5 to 25 percent of halogen flame retardant, 2 to 10 percent of non-antimony flame retardant synergist, 0.1 to 3 percent of lubricant, 0.1 to 1 percent of antioxidant, 0.3 to 3 percent of surface modifier and 1 to 40 percent of reinforcing modifier, wherein the percentages are the weight percentages of the components relative to the raw materials; wherein the non-antimony flame-retardant synergist comprises magnesium oxide, silicon dioxide and tin dioxide, and the molar ratio is 2-3: 1-2: 1. The invention also provides a preparation method and application of the composite material. The non-antimony flame-retardant polyamide composite material disclosed by the invention has the advantages that the CTI is improved to more than 400V under the condition that antimony trioxide and zinc borate are not contained, the flow mark problem is avoided, and the production cost can be reduced, but 5% -25% of halogen flame retardant is also added, so that smoke is easily generated during combustion, and the influence on the environment is caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a flame-retardant polyamide composite material, which improves the polarity of the graphene surface by introducing organic groups to the graphene oxide surface, and the modified graphene flame-retardant particles are matched with a phosphorus flame retardant to have good flame retardance, and meanwhile, the modification of the graphene surface improves the compatibility of the flame retardant and a polyamide material, and reduces the influence of the flame retardant on the mechanical property of polyamide.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a flame-retardant polyamide composite material comprises the following steps:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 0.5-2 ml, and carrying out ultrasonic treatment for 30-60 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 60-80 ℃, and magnetically stirring for 100-150 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to be 80-95 ℃, slowly dropping an initiator into the maleic anhydride solution at the stirring speed of 300-500 revolutions per minute for 30-60 minutes, and continuing to react for 4-6 hours after dropping; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to be dried for 4 hours at the temperature of 80-90 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 1-2 hours, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the surface aminated graphene solution prepared in the step (2), controlling the temperature of an oil bath to 140 ℃, stirring for reacting for 4-6 hours, continuously adding phenyl phosphoryl dichloride into the mixed solution, stirring for reacting at normal temperature for 20-26 hours, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, putting the viscous liquid into an oven for drying to obtain solid particles, and grinding and crushing to obtain modified graphene flame-retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the temperature of the extruder in three stages is set to 200-205 ℃, 210-220 ℃ and 225-230 ℃ in sequence.
Preferably, the mass ratio of the amine molecules to the graphene oxide in the step (2) is 180-220: 1.
Preferably, the amine molecule is one or more of 1, 6-diaminohexane, diethylenetriamine, triethylenetetramine and tetraethylenepentamine in combination.
Preferably, the solvent in step (3) is one or a combination of acetone, butanone, cyclohexanone or methyl isobutyl ketone.
Preferably, in the step (3), the maleic anhydride, the divinylbenzene and the initiator are formulated in a mass ratio of 10-18:25-40: 0.2-0.6.
Preferably, the initiator is an organic peroxide or an azo compound.
Preferably, the amount of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles used in the step (4) is 8 to 15 times of the amount of the graphene oxide, and the amount of the phenylphosphoryl dichloride is 35 to 45 times of the amount of the graphene oxide.
Preferably, the amount mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 80-100:3-10: 7-15.
Preferably, the amount mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 85:5: 10.
Preferably, the phosphorus flame retardant is formed by mixing aluminum diethylphosphinate and melamine polyphosphate according to the mass ratio of 3: 1.
The invention has the following beneficial effects:
(1) according to the method, the organic group is introduced to the surface of the graphene oxide, so that the polarity of the surface of the graphene is improved, the modified graphene flame-retardant particles are matched with the phosphorus flame retardant, the modified graphene flame-retardant particles have good flame retardancy, and meanwhile, the modification of the surface of the graphene improves the compatibility of the flame retardant and a polyamide material, and the influence of the flame retardant on the mechanical property of the polyamide is reduced.
(2) According to the invention, the modified graphene flame-retardant particles and the phosphorus flame retardant are cooperatively matched, and the graphene sheet layer dispersed in the polyamide material is effectively blocked before a complete and continuous chemical carbon layer is formed under catalysis of phosphorus during combustion, so that the flame-retardant effect at the initial stage of combustion is improved.
(3) According to the invention, the divinylbenzene-maleic anhydride copolymer microspheres are grafted on the surface of graphene, meanwhile, phosphorus is introduced to the surface of graphene through phenylphosphoryl dichloride, the divinylbenzene-maleic anhydride copolymer contains maleic anhydride groups with a content, the interfacial bonding force between the equine graphene and a polyamide material is improved, the stability and the mechanical property of the composite material are improved, meanwhile, the divinylbenzene-maleic anhydride has a good char forming effect on the surface of the graphene, the flame retardance of the material is improved, meanwhile, the phosphorus-containing flame retardant is introduced to the surface of the graphene, the combination of physical flame retardance and chemical flame retardance is realized, the flame retardant efficiency is obviously improved, and in the initial combustion stage and the later combustion stage, phosphoric acid substances produced by the phosphorus on the surface of the divinylbenzene-maleic anhydride catalyze resin to form a chemical carbon layer to wrap a physical layer, so that a continuous and compact.
(4) The flame-retardant polyamide composite material prepared by the method does not contain any halogen flame-retardant element, is green and environment-friendly when used, and does not pollute the environment.
Detailed Description
Reference will now be made in detail to the present embodiments of the invention, with the understanding that the scope of the invention is not limited to the specific embodiments. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
A preparation method of a flame-retardant polyamide composite material comprises the following steps:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 0.5 ml, and performing ultrasonic treatment for 30 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 60 ℃, and magnetically stirring for 100 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to 80 ℃, slowly dripping an initiator into the maleic anhydride solution at the stirring speed of 300 revolutions per minute for 30 minutes, and continuing to react for 4 hours after dripping is finished; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to dry for 4 hours at the temperature of 80 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 1 hour, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the graphene solution with aminated surface prepared in the step (2), controlling the temperature of an oil bath to 130 ℃, stirring for reacting for 4 hours, continuously adding phenylphosphoryl dichloride into the mixed solution, stirring for reacting for 20 hours at normal temperature, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, drying in an oven to obtain solid particles, and grinding and crushing to obtain modified graphene flame retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the three stage temperatures of the extruder were set to 200 degrees celsius, 210 degrees celsius, and 225 degrees celsius in this order.
In the step (2), the mass ratio of the amine molecules to the graphene oxide is 180: 1.
The amine molecule is 1, 6-diaminohexane.
The solvent in the step (3) is acetone.
In the step (3), maleic anhydride, divinyl benzene and an initiator are prepared according to the mass ratio of 10:25: 0.2.
The initiator is an organic peroxide.
In the step (4), the dosage of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles is 8 times of that of the graphene oxide, and the dosage of the phenylphosphoryl dichloride is 35 times of that of the graphene oxide.
The mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 80:3: 7.
The phosphorus flame retardant is formed by mixing aluminum diethylphosphinate and melamine polyphosphate according to the mass ratio of 3: 1.
Example 2
A preparation method of a flame-retardant polyamide composite material comprises the following steps:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 1.5 ml, and performing ultrasonic treatment for 45 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 70 ℃, and magnetically stirring for 130 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to 88 ℃, slowly dripping an initiator into the maleic anhydride solution at the stirring speed of 400 revolutions per minute for 45 minutes, and continuing to react for 5 hours after dripping is finished; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to dry for 4 hours at 88 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 1.6 hours, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the surface aminated graphene solution prepared in the step (2), controlling the temperature of an oil bath to 134 ℃, stirring for reacting for 4.6 hours, continuously adding phenylphosphoryl dichloride into the mixed solution, stirring for reacting for 23 hours at normal temperature, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, putting the viscous liquid into an oven for drying to obtain solid particles, and grinding and crushing to obtain modified graphene flame-retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the three stage temperatures of the extruder were set to 203 degrees celsius, 216 degrees celsius, and 228 degrees celsius in this order.
In the step (2), the mass ratio of the amine molecules to the graphene oxide is 203: 1.
The amine molecule is diethylenetriamine.
The solvent in step (3) is cyclohexanone.
In the step (3), maleic anhydride, divinyl benzene and an initiator are prepared according to a mass ratio of 17:36: 0.4.
The initiator is an azo compound.
In the step (4), the dosage of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles is 10 times of that of the graphene oxide, and the dosage of the phenylphosphoryl dichloride is 38 times of that of the graphene oxide.
The mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 94:7: 12.
The phosphorus flame retardant is formed by mixing aluminum diethylphosphinate and melamine polyphosphate according to the mass ratio of 3: 1.
Example 3
A preparation method of a flame-retardant polyamide composite material comprises the following steps:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 2 ml, and performing ultrasonic treatment for 60 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 60-80 ℃, and magnetically stirring for 150 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to 95 ℃, slowly dripping an initiator into the maleic anhydride solution at the stirring speed of 500 revolutions per minute for 60 minutes, and continuing to react for 6 hours after dripping is finished; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to dry for 4 hours at 90 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 2 hours, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the graphene solution with aminated surface prepared in the step (2), controlling the temperature of an oil bath to 140 ℃, stirring and reacting for 6 hours, continuously adding phenylphosphoryl dichloride into the mixed solution, stirring and reacting at normal temperature for 26 hours, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, drying the viscous liquid in a drying oven to obtain solid particles, and grinding and crushing the solid particles to obtain modified graphene flame-retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the three stage temperatures of the extruder were set to 205 degrees celsius, 220 degrees celsius, and 230 degrees celsius in this order.
In the step (2), the mass ratio of the amine molecules to the graphene oxide is 220: 1.
The amine molecule is formed by mixing diethylenetriamine and triethylene tetramine according to the ratio of 1: 1.
The solvent in the step (3) is butanone.
In the step (3), maleic anhydride, divinyl benzene and an initiator are prepared according to the mass ratio of 18:40: 0.6.
The initiator is an azo compound.
In the step (4), the dosage of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles is 15 times of that of the graphene oxide, and the dosage of the phenylphosphoryl dichloride is 45 times of that of the graphene oxide.
The mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 100:10: 15.
Example 4
A preparation method of a flame-retardant polyamide composite material comprises the following steps:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 1.8 ml, and performing ultrasonic treatment for 50 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 76 ℃, and magnetically stirring for 135 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to 88 ℃, slowly dripping an initiator into the maleic anhydride solution at the stirring speed of 480 revolutions per minute for 52 minutes, and continuing to react for 5.2 hours after dripping is finished; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to dry for 4 hours at 86 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 1.8 hours, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the surface aminated graphene solution prepared in the step (2), controlling the temperature of an oil bath to 138 ℃, stirring for reacting for 4.6 hours, continuously adding phenylphosphoryl dichloride into the mixed solution, stirring for reacting for 24 hours at normal temperature, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, putting the viscous liquid into an oven for drying to obtain solid particles, and grinding and crushing to obtain modified graphene flame-retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the three stage temperatures of the extruder were set to 203 degrees celsius, 218 degrees celsius, and 228 degrees celsius, in that order.
In the step (2), the mass ratio of the amine molecules to the graphene oxide is 207: 1.
The amine molecule is tetraethylenepentamine.
The solvent in the step (3) is methyl isobutyl ketone.
In the step (3), maleic anhydride, divinyl benzene and an initiator are prepared according to a mass ratio of 17:33: 0.4.
The initiator is an azo compound.
In the step (4), the dosage of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles is 13 times of that of the graphene oxide, and the dosage of the phenylphosphoryl dichloride is 42 times of that of the graphene oxide.
The mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus flame retardant in the step (5) is 85:5: 10.
The phosphorus flame retardant is formed by mixing aluminum diethylphosphinate and melamine polyphosphate according to the mass ratio of 3: 1.
Comparative example 1: polyamide materials without any treatment;
comparative example 2: carrying out co-melting extrusion granulation on polyamide and modified graphene flame retardant particles according to the proportion of 80:10, (the modified graphene flame retardant particles are completely the same as those in the embodiment 1);
comparative example 3: the polyamide and the phosphorus flame retardant were subjected to co-melting extrusion granulation at a ratio of 80:10 (the phosphorus flame retardant was the same as the phosphorus flame retardant in example 1)
The flame retardant properties of the polyamide materials of comparative examples 1 to 3 and the flame retardant properties of the flame retardant polyamide composite materials prepared in examples 1 to 4 were subjected to a performance test. The test results are shown in table 1 below;
table 1:
testing of Limiting Oxygen Index (LOI) tests were performed on a limiting oxygen index instrument in accordance with ISO 4589-2-2016;
fire rating (UL-94) test: testing on a horizontal vertical combustion tester according to ISO 4589-2-2016;
by analyzing the data in table 1 above and performing performance tests on the data in examples 1-4 and the data in comparative example 1, it can be seen that the limited oxygen index and the flame retardant rating of the flame retardant polyamide composite materials of examples 1-4 are significantly higher than the polyamide material of comparative example 1 without any treatment.
By analyzing and comparing the measured data of example 1 with those of comparative example 2 and comparative example 3, the limit oxygen index value of the material of example 1 is increased by 40.7% relative to that of comparative example 2, the fire rating is increased from V-2 to V-1, the limit oxygen index of the material of example 1 is increased by 18.6% relative to that of comparative example 3, and the fire rating is increased from V-2 to V-1, and from the above analysis, it can be seen that the composite flame retardance of example 1 using the modified graphene flame retardant particles and the phosphorus-based flame retardant is superior to that of comparative example 2 using the modified graphene flame retardant particles alone and that of comparative example 3 using the phosphorus-based flame retardant alone.
Comparing the respective flame retardant properties of the flame retardant polyamide composite materials of examples 1-4, it can be seen from Table 1 that the flame retardant polyamide composite material of example 4 has the highest limiting oxygen index value and the fire rating as high as V-0.
The mechanical properties of the polyamide materials of comparative examples 1 to 3 and the mechanical properties of the flame-retardant polyamide composite materials prepared in examples 1 to 4 were subjected to a performance test, and the test results are shown in Table 2 below;
table 2:
| test set | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 1 | 42.6 | 34.7 |
| Example 2 | 43.1 | 40.2 |
| Example 3 | 38.4 | 36.7 |
| Example 4 | 40.6 | 38.5 |
| Comparative example 1 | 58.7 | 63.2 |
| Comparative example 2 | 48.3 | 42.3 |
| Comparative example 3 | 34.8 | 21.6 |
And (3) testing tensile property: the tensile rate was 10 mm/min as tested in ISO-527-;
as can be seen from the above Table 2, the polyamide material of comparative example 1 without any treatment has the highest tensile strength and elongation at break, and after the flame retardant is added, the tensile resistance of the composite material is reduced, mainly because the polyamide and the flame retardant in the composite material have compatibility problem when being melt blended and extruded, so that the comprehensive mechanical properties of the material are reduced.
Comparing comparative example 2 and comparative example 3, only the modified graphene flame-retardant particles are added as the flame retardant in comparative example 2, only the phosphorus flame retardant is added as the flame retardant in comparative example 3, the tensile strength in comparative example 2 is 38.8% higher than that in comparative example 3, and the elongation at break is 95.8% higher, mainly because the modified graphene flame-retardant particles contain a large amount of anhydride groups, the compatibility between the flame retardant and the polyamide material is increased, and the influence of the flame retardant on the mechanical property of the polyamide material is reduced.
Based on the data particles in tables 1 and 2, it can be seen that the mechanical properties and flame retardant properties of the composite are combined, and the overall combination of properties of the flame retardant polyamide composite of example 4 is better.
In summary, the invention has the following advantages:
(1) according to the method, the organic group is introduced to the surface of the graphene oxide, so that the polarity of the surface of the graphene is improved, the modified graphene flame-retardant particles are matched with the phosphorus flame retardant, the modified graphene flame-retardant particles have good flame retardancy, and meanwhile, the modification of the surface of the graphene improves the compatibility of the flame retardant and a polyamide material, and the influence of the flame retardant on the mechanical property of the polyamide is reduced.
(2) According to the invention, the modified graphene flame-retardant particles and the phosphorus flame retardant are cooperatively matched, and the graphene sheet layer dispersed in the polyamide material is effectively blocked before a complete and continuous chemical carbon layer is formed under catalysis of phosphorus during combustion, so that the flame-retardant effect at the initial stage of combustion is improved.
(3) According to the invention, the divinylbenzene-maleic anhydride copolymer microspheres are grafted on the surface of graphene, meanwhile, phosphorus is introduced to the surface of graphene through phenylphosphoryl dichloride, the divinylbenzene-maleic anhydride copolymer contains maleic anhydride groups with a content, the interfacial bonding force between the equine graphene and a polyamide material is improved, the stability and the mechanical property of the composite material are improved, meanwhile, the divinylbenzene-maleic anhydride has a good char forming effect on the surface of the graphene, the flame retardance of the material is improved, meanwhile, the phosphorus-containing flame retardant is introduced to the surface of the graphene, the combination of physical flame retardance and chemical flame retardance is realized, the flame retardant efficiency is obviously improved, and in the initial combustion stage and the later combustion stage, phosphoric acid substances produced by the phosphorus on the surface of the divinylbenzene-maleic anhydride catalyze resin to form a chemical carbon layer to wrap a physical layer, so that a continuous and compact.
(4) The flame-retardant polyamide composite material prepared by the method does not contain any halogen flame-retardant element, is green and environment-friendly when used, and does not pollute the environment.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant polyamide composite material is characterized by comprising the following steps of:
(1) dispersing graphene oxide in N, N-dimethylformamide according to the solid-liquid mass volume ratio of 1 g: 0.5-2 ml, and carrying out ultrasonic treatment for 30-60 minutes to obtain a graphene oxide dispersion liquid;
(2) adding amine molecules into the graphene oxide dispersion liquid prepared in the step (1), heating to 60-80 ℃, and magnetically stirring for 100-150 minutes to obtain a graphene solution with aminated surface;
(3) adding maleic anhydride into a solvent, stirring, mixing and dissolving uniformly to form a maleic anhydride solution, introducing nitrogen into the maleic anhydride solution to drive away redundant oxygen in the solution, adding divinylbenzene under the protection of the nitrogen, stirring uniformly, controlling the temperature to be 80-95 ℃, slowly dropping an initiator into the maleic anhydride solution at the stirring speed of 300-500 revolutions per minute for 30-60 minutes, and continuing to react for 4-6 hours after dropping; obtaining a divinylbenzene-maleic anhydride copolymer microsphere dispersion system, then obtaining divinylbenzene-maleic anhydride copolymer microsphere solid particles through centrifugal dispersion, and placing the divinylbenzene-maleic anhydride copolymer microsphere solid particles in an oven to be dried for 4 hours at the temperature of 80-90 ℃;
(4) grinding the divinylbenzene-maleic anhydride copolymerized microsphere solid particles in the step (3) in a ball mill for 1-2 hours, adding the ground divinylbenzene-maleic anhydride copolymerized microsphere solid particles into the surface aminated graphene solution prepared in the step (2), controlling the temperature of an oil bath to 140 ℃, stirring for reacting for 4-6 hours, continuously adding phenyl phosphoryl dichloride into the mixed solution, stirring for reacting at normal temperature for 20-26 hours, performing suction filtration, performing rotary evaporation on the filtrate to obtain viscous liquid, putting the viscous liquid into an oven for drying to obtain solid particles, and grinding and crushing to obtain modified graphene flame-retardant particles;
(5) respectively placing polyamide, modified graphene flame-retardant particles and a phosphorus flame retardant into an oven for drying and removing surface moisture, adding the materials into a high-speed mixer for uniform mixing, and adding the materials into an extruder for extrusion granulation to obtain a flame-retardant polyamide composite material;
the temperature of the extruder in three stages is set to 200-205 ℃, 210-220 ℃ and 225-230 ℃ in sequence.
2. The method for preparing the flame-retardant polyamide composite material as claimed in claim 1, wherein the mass ratio of the amine molecules to the graphene oxide in the step (2) is 180-220: 1.
3. The method of claim 2, wherein the amine molecule is one or more selected from the group consisting of 1, 6-diaminohexane, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
4. The method for preparing flame retardant polyamide composite material according to claim 1, wherein the solvent in step (3) is one or more of acetone, butanone, cyclohexanone or methyl isobutyl ketone.
5. The method for preparing a flame-retardant polyamide composite material according to claim 1, wherein in the step (3), maleic anhydride, divinylbenzene and an initiator are formulated in a mass ratio of 10-18:25-40: 0.2-0.6.
6. The method for preparing a flame retardant polyamide composite material according to claim 5, wherein the initiator is an organic peroxide or an azo compound.
7. The method for preparing a flame-retardant polyamide composite material according to claim 1, wherein the amount of the divinylbenzene-maleic anhydride copolymerized microsphere solid particles used in the step (4) is 8 to 15 times the amount of the graphene oxide, and the amount of the phenylphosphoryl dichloride is 35 to 45 times the amount of the graphene oxide.
8. The preparation method of the flame-retardant polyamide composite material as claimed in claim 1, wherein the amount by mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus-based flame retardant in the step (5) is 80-100:3-10: 7-15.
9. The preparation method of the flame-retardant polyamide composite material as claimed in claim 8, wherein the amount by mass ratio of the polyamide, the modified graphene flame-retardant particles and the phosphorus-based flame retardant in the step (5) is 85:5: 10.
10. The preparation method of the flame-retardant polyamide composite material as claimed in claim 8, wherein the phosphorus-based flame retardant is formed by mixing aluminum diethylphosphinate and melamine polyphosphate according to a mass ratio of 3: 1.
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| CN113773513A (en) * | 2021-08-30 | 2021-12-10 | 嘉兴学院 | Graphite alkyne-hyaluronic acid composite flame retardant and preparation method and application thereof |
| CN114835556A (en) * | 2022-05-11 | 2022-08-02 | 常州巨德新材料有限公司 | Bromine-containing norbornene derivative, preparation method thereof and flame-retardant polydicyclopentadiene material |
| CN115182068A (en) * | 2022-08-11 | 2022-10-14 | 东莞信鸿工程塑料有限公司 | High-flame-retardancy polyamide fiber and preparation method thereof |
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| CN116925375A (en) * | 2023-07-18 | 2023-10-24 | 东莞市普万光电散热科技有限公司 | Graphene oxide grafted modified polyamide composite material, fabric and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113773513A (en) * | 2021-08-30 | 2021-12-10 | 嘉兴学院 | Graphite alkyne-hyaluronic acid composite flame retardant and preparation method and application thereof |
| CN114835556A (en) * | 2022-05-11 | 2022-08-02 | 常州巨德新材料有限公司 | Bromine-containing norbornene derivative, preparation method thereof and flame-retardant polydicyclopentadiene material |
| CN115182068A (en) * | 2022-08-11 | 2022-10-14 | 东莞信鸿工程塑料有限公司 | High-flame-retardancy polyamide fiber and preparation method thereof |
| CN115368757A (en) * | 2022-09-01 | 2022-11-22 | 安徽嘉阳新材料科技有限公司 | Preparation process of high-strength high-barrier high-thermal-stability modified graphene powder |
| CN116925375A (en) * | 2023-07-18 | 2023-10-24 | 东莞市普万光电散热科技有限公司 | Graphene oxide grafted modified polyamide composite material, fabric and preparation method thereof |
| CN116925375B (en) * | 2023-07-18 | 2024-03-26 | 东莞市普万光电散热科技有限公司 | Graphene oxide grafted modified polyamide composite material, fabric and preparation method thereof |
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