CN117024950B - Flame-retardant modified high-fluidity nylon 6 composite material and preparation method thereof - Google Patents

Flame-retardant modified high-fluidity nylon 6 composite material and preparation method thereof Download PDF

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CN117024950B
CN117024950B CN202311178035.XA CN202311178035A CN117024950B CN 117024950 B CN117024950 B CN 117024950B CN 202311178035 A CN202311178035 A CN 202311178035A CN 117024950 B CN117024950 B CN 117024950B
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flame
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fluidity nylon
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CN117024950A (en
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陈红
陈婷
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Guangzhou Northen New Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a flame-retardant modified high-fluidity nylon 6 composite material and a preparation method thereof, and relates to the technical field of flame-retardant modification. The preparation method of the flame-retardant modified high-fluidity nylon 6 composite material comprises the following steps: (1) Dopamine, ammonium polyphosphate and Ti 3 C 2 T x Adding the nano-sheets into a buffer solution, regulating the pH to 7.5-8.5, uniformly stirring, and carrying out microencapsulation treatment for 1-10h to obtain an M-APP flame retardant; (2) And uniformly mixing the high-fluidity nylon 6, the M-APP flame retardant and the antioxidant, extruding, granulating and injection molding to obtain the flame-retardant modified high-fluidity nylon 6 composite material. The method can well solve the problems of poor interfacial binding force, reduced mechanical property and excessive addition of the flame retardant between the flame retardant and the high-fluidity nylon 6 in the prior art.

Description

Flame-retardant modified high-fluidity nylon 6 composite material and preparation method thereof
Technical Field
The invention relates to the technical field of flame retardant modification, in particular to a flame retardant modified high-fluidity nylon 6 composite material and a preparation method thereof.
Background
The high-fluidity nylon 6 (PA) resin is a novel branched PA6 resin with high Melt Flow Rate (MFR), easy molding, short time consumption, low energy consumption and cost, suitability for reinforcing with Glass Fiber (GF) and the like, accords with the development trend of energy conservation, environmental protection, miniaturization and light weight in the industries of automobiles and electronic parts, and has wide market application prospect. However, the limit oxygen index of the high-fluidity PA6 pure resin is not high, is 23-25%, the flame retardant grade is UL94V-2, and flame dripping and combustible gas are more easily generated during combustion compared with common nylon 6. The typical halogen-free flame retardants commonly used at present are ammonium polyphosphate (APP), red phosphorus and Melamine Cyanurate (MCA), but all have the problems of poor bonding property with a polymer interface, easy precipitation, easy moisture absorption and the like.
At present, few flame retardant modification reports on high-flow nylon 6 at home and abroad are provided, xie Xiang proposes that 14wt% of GO modified MCA is added into high-flow nylon in a melt blending mode in 'preparation, structure and performance of GO modified MCA/high-flow PA6 flame retardant composite material', wherein the GO content is 2%, the flame retardant property of the composite material reaches UL94V-0 level, and the Limiting Oxygen Index (LOI) value is 32. However, because the GO modified MCA still belongs to inorganic rigid particles, when the GO modified MCA has poor compatibility with a high-flow nylon matrix and large addition amount, the molecular level blending is difficult to achieve by adopting the traditional melt blending modeResulting in agglomeration and reduced mechanical properties of the composite. The impact strength of the composite material added with 14wt% of GO modified MCA is reduced by 3.2KJ/m compared with the pure high-fluidity nylon 2 The tensile strength was reduced by 2MPa.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flame-retardant modified high-fluidity nylon 6 composite material and a preparation method thereof. The method can well solve the problems of poor interfacial binding force, reduced mechanical property and excessive addition of the flame retardant between the flame retardant and the high-fluidity nylon 6 in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a preparation method of a flame-retardant modified high-fluidity nylon 6 composite material, which comprises the following steps:
(1) Mixing 0.1-20 weight parts of dopamine, 1-100 weight parts of ammonium polyphosphate and 0.1-10 weight parts of Ti 3 C 2 T x Adding the nano-sheets into a buffer solution, regulating the pH to 7.5-8.5, uniformly stirring, carrying out microencapsulation treatment for 1-10h, and drying to obtain an M-APP flame retardant;
(2) Mixing 100 parts by weight of high-fluidity nylon 6, 0.5-20 parts by weight of M-APP flame retardant and 0.2-3 parts by weight of antioxidant uniformly, extruding, granulating and injection molding to obtain the flame-retardant modified high-fluidity nylon 6 composite material.
Because dopamine is subjected to self-polymerization reaction in the buffer solution, a polydopamine film with super-strong viscosity can be rapidly formed on the surfaces of various materials, and the polydopamine is adopted for preparing the polydopamine and Ti 3 C 2 T x The nanosheets are coated by microencapsulation, ti 3 C 2 T x The surface of the nano-sheet contains a large number of-F, -O, -OH groups, and can form hydrogen bonds with ammonium polyphosphate and dopamine to form better interface binding force. At the same time Ti 3 C 2 T x When burning, the nano-sheet can form TiO on the surface of the high-fluidity nylon 6 matrix 2 Has the advantages of catalytic carbonization andthe physical barrier effect enables a more complete and compact carbon layer to be formed between the high-fluidity nylon 6 matrix and the M-APP flame retardant, not only effectively inhibits the formation of molten drops of the high-fluidity nylon 6 in the combustion process, but also is beneficial to improving the interfacial binding force between the flame retardant and the high-fluidity nylon 6, and avoids the problems of mechanical property reduction and flame retardant precipitation.
In the present invention, the ratio of dopamine to buffer is 0.1-20g:1L.
Preferably, in the step (1), the weight part of the dopamine is 5-15 parts, the weight part of the ammonium polyphosphate is 95 parts, and the Ti 3 C 2 T x The weight portion of the nano-sheet is 2.5-7.5 portions.
Preferably, the weight ratio of the high-fluidity nylon 6 to the M-APP flame retardant in the step (2) is 100: (4-14).
In the invention, the high-fluidity nylon 6 and the M-APP flame retardant are matched with each other in a specific proportion, which is favorable for further improving the compatibility between the polydopamine and the high-fluidity nylon 6 matrix as well as the flame retardant, thereby further improving the mechanical property of the composite material.
Preferably, the buffer in the step (1) is disodium hydrogen phosphate-potassium dihydrogen phosphate buffer.
Preferably, the stirring speed in the step (1) is 100-600r/min.
More preferably, the stirring speed in the step (1) is 300r/min.
Preferably, the antioxidant in the step (2) is at least one of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), n-stearyl alcohol beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate, antioxidant 168, tri (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, trisnonylphenyl phosphite, 2, 6-di-tert-butyl-4-methylphenol and triphenyl (yl) phosphorus.
More preferably, the antioxidant in the step (2) is a combination of pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and n-stearyl β - (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate.
Still further, the weight ratio of pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) to n-octadecanol β - (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate is 1:1.
preferably, the high fluidity nylon 6 in the step (2) is linear nylon 6 or dendritic nylon 6. More preferably, the high fluidity nylon 6 is dendritic nylon 6.
The high-fluidity nylon 6 is star-structure nylon 6 formed by polymerization of caprolactam monomers initiated by dendronized initiation units. The melt index is 320-360g/10min under the test condition of 2.16Kg at 230 ℃.
Preferably, ti in the step (1) 3 C 2 T x The preparation method of the nano-sheet comprises the following steps:
(1) TiH is processed by 2 Ball milling the powder, al powder and graphite powder for 1-20h to obtain a mixture;
(2) Sintering the mixture in the step (1) for 2 hours in argon atmosphere at 800-1600 ℃ to obtain Ti 3 AlC 2 Block body, then Ti 3 AlC 2 Pulverizing the block, sieving to obtain Ti with particle diameter D50 of 75-80 μm 3 AlC 2 A powder;
(3) Ti in step (2) 3 AlC 2 Adding the powder into an HF solution, wherein the mass concentration of the HF solution is 30-60%, uniformly stirring, and standing at room temperature to obtain a suspension; the Ti is 3 AlC 2 The ratio of powder to HF solution is 1-5g:100-150mL;
(4) Centrifuging the suspension in the step (3), washing with deionized water for 3-4 times until the pH value of the supernatant is neutral, and finally washing and drying the product to obtain Ti 3 C 2 T x A nano-sheet.
In the invention, ti prepared by the method 3 C 2 T x The nano-sheet not only has higher mechanical property, but also has excellent flame retardant property.
Preferably, the TiH in step (1) 2 The average particle size of the powder was 35. Mu.m, the average particle size of the Al powder was 40. Mu.m, and the average particle size of the graphite powder was 30. Mu.m.
Preferably, the TiH in step (1) 2 The molar ratio of the powder to the Al powder to the graphite powder is 3:1.1:2.
in the present invention, the TiH with the specific proportion is adopted 2 The powder, al powder and graphite powder are mutually matched to ensure that Ti 3 C 2 T x The nano-sheet forms interface binding force with ammonium polyphosphate and dopamine better, which is beneficial to further improving the mechanical property of the composite material.
In a second aspect, the invention provides a flame-retardant modified high-fluidity nylon 6 composite material prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the polydopamine is adopted to carry out microencapsulation and encapsulation treatment on the flame retardant, so that the interfacial binding force between the flame retardant and the high-flow nylon 6 is improved, and the problems of mechanical property reduction, flame retardant precipitation and the like are avoided.
(2) The invention adopts Ti 3 C 2 T x The nanometer sheet is used as a synergistic flame retardant to replace traditional inorganic synergistic flame retardants such as magnesium hydroxide, nanometer titanium oxide, expanded graphite and the like, ti 3 C 2 T x The nano-sheet has a large number of functional groups on the surface, can form hydrogen bonds with ammonium polyphosphate and dopamine to form better interface bonding force, and can form TiO on the surface of a nylon matrix during combustion 2 Has catalytic carbonization and physical barrier effects, thereby forming a more complete and compact carbon layer with the nitrogen-phosphorus flame retardant and effectively inhibiting the formation of molten drops of the high-flow nylon 6 in the combustion process.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, but the scope and embodiments of the present invention are not limited thereto.
Materials, reagents and the like used in the following examples are commercially available ones unless otherwise specified.
Preparation example 1
Ti (titanium) 3 C 2 T x The preparation method of the nano-sheet comprises the following steps:
(1) TiH is processed by 2 The powder, al powder and graphite powder were ball-milled for 8 hours at 300rpm to obtain a mixture in which TiH was contained in total of 100g 2 The molar ratio of the powder to the Al powder to the graphite powder is 3:1.1:2;
(2) Sintering the mixture in the step (1) for 2 hours at 1400 ℃ in a flowing high-purity argon atmosphere to obtain Ti 3 AlC 2 Block body, then Ti 3 AlC 2 Mechanically pulverizing the block, and sieving the obtained powder with 200 mesh sieve to obtain Ti with particle diameter D50 of 75 μm 3 AlC 2 A powder;
(3) 50g of Ti prepared in step (2) are mixed 3 AlC 2 Slowly adding the powder into HF solution in a polytetrafluoroethylene container, wherein the volume of the HF solution is 1000ml, the mass concentration is 49%, and then, standing for 24 hours at room temperature under magnetic stirring to obtain suspension;
(4) Centrifuging (8000 rpm,5 min) the suspension in step (3), washing with deionized water for 3 times until the pH of the supernatant reaches 7, washing the product with absolute ethanol for 3 times, washing the rest precipitate, and drying to obtain Ti 3 C 2 T x A nano-sheet.
Preparation example 2
Ti (titanium) 3 C 2 T x The preparation method of the nano-sheet comprises the following steps:
(1) TiH is processed by 2 The powder, al powder and graphite powder were ball-milled for 8 hours at 300rpm to obtain a mixture in which TiH was contained in total of 100g 2 The molar ratio of the powder to the Al powder to the graphite powder is 3:1.1:2;
(2) Sintering the mixture in the step (1) for 1h at 1600 ℃ in a flowing high-purity argon atmosphere to obtain Ti 3 AlC 2 Block body, then Ti 3 AlC 2 Mechanically pulverizing the block, and sieving the obtained powder with 200 mesh sieve to obtain Ti with particle diameter D50 of 80 μm 3 AlC 2 A powder;
(3) 50g of Ti prepared in step (2) are mixed 3 AlC 2 PowderSlowly adding the mixture into HF solution in a polytetrafluoroethylene container, wherein the volume of the HF solution is 1000ml, the mass concentration is 30%, and then, standing for 24 hours at room temperature under magnetic stirring to obtain suspension;
(4) Centrifuging (8000 rpm,5 min) the suspension in step (3), washing with deionized water for 3 times until the pH of the supernatant reaches 7, washing the product with absolute ethanol for 3 times, washing the rest precipitate, and drying to obtain Ti 3 C 2 T x A nano-sheet.
Example 1
The preparation method of the flame-retardant modified high-fluidity nylon 6 composite material comprises the following steps:
(1) 0.1g of dopamine, 1g of ammonium polyphosphate and 0.1g of Ti 3 C 2 T x Dissolving the nano-sheet in 1L of disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, regulating the pH to 7.5, activating and reacting for 1h at 30 ℃ with a magnetic stirrer at the rotating speed of 300r/min, and then drying in a drying oven at 75 ℃ to obtain an M-APP flame retardant; the Ti is 3 C 2 T x The nano-sheet is prepared by a preparation example 1;
(2) 100g of high-fluidity nylon 6, 0.5g of M-APP flame retardant and 0.2g of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) are uniformly mixed in a high-speed mixer, extruded and granulated by a double-screw extruder, and the prepared granules are dried in vacuum at 85 ℃ for 12 hours, and then the flame-retardant modified high-fluidity nylon 6 composite material is prepared in an injection molding machine.
Example 2
The preparation method of the flame-retardant modified high-fluidity nylon 6 composite material comprises the following steps:
(1) 20g of dopamine, 100g of ammonium polyphosphate and 10g of Ti 3 C 2 T x Dissolving the nano-sheet in 1L of disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, regulating the pH to 8.5, using a magnetic stirrer to perform an activation reaction for 5 hours at the temperature of 30 ℃ at the rotating speed of 300r/min, and then drying in a drying oven at the temperature of 75 ℃ to obtain an M-APP flame retardant; the Ti is 3 C 2 T x The nano-sheet is prepared by a preparation example 2;
(2) 100g of high-fluidity nylon 6, 20g of M-APP flame retardant and 3g of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) are uniformly mixed in a high-speed mixer, extruded and granulated by a double-screw extruder, and the produced granules are dried in vacuum at 85 ℃ for 12 hours, and then the flame-retardant modified high-fluidity nylon 6 composite material is prepared in an injection molding machine.
Example 3
The preparation method of the flame-retardant modified high-fluidity nylon 6 composite material comprises the following steps:
(1) 10g of dopamine, 95g of ammonium polyphosphate and 5g of Ti 3 C 2 T x Dissolving the nano-sheet in 1L of disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, regulating the pH to 8.5, using a magnetic stirrer to perform an activation reaction for 5 hours at the temperature of 30 ℃ at the rotating speed of 300r/min, and then drying in a drying oven at the temperature of 75 ℃ to obtain an M-APP flame retardant; the Ti is 3 C 2 T x The nano-sheet is prepared by a preparation example 1;
(2) 100g of high-fluidity nylon 6, 8g of M-APP flame retardant and 0.5g of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) are uniformly mixed in a high-speed mixer, extruded and granulated by a double-screw extruder, and the prepared granules are dried in vacuum at 85 ℃ for 12 hours, and then the flame-retardant modified high-fluidity nylon 6 composite material is prepared in an injection molding machine.
Example 4
The difference from example 3 is that only the amount of dopamine, ammonium polyphosphate and Ti in step (1) was changed 3 C 2 T x The weight of the nanoplatelets was 5g, 95g, 5g, respectively, and the other steps were the same as in example 3.
Example 5
The difference from example 3 is that only the amount of dopamine, ammonium polyphosphate and Ti in step (1) was changed 3 C 2 T x The weight of the nanoplatelets was 15g, 95g, 5g, respectively, and the other steps were the same as in example 3.
Example 6
The difference from example 3 is that only Ti in the step (1) was changed 3 C 2 T x The dosage of the nano-sheets, dopamine, ammonium polyphosphate and Ti 3 C 2 T x The weight of the nanoplatelets was 10g, 95g, 2.5g, respectively, and the other steps were the same as in example 3.
Example 7
The difference from example 3 is that only Ti in the step (1) was changed 3 C 2 T x The dosage of the nano-sheets, dopamine, ammonium polyphosphate and Ti 3 C 2 T x The weight of the nanoplatelets was 10g, 95g, 7.5g, respectively, and the other steps were the same as in example 3.
Example 8
The difference from example 3 is that only the amount of the M-APP flame retardant used in step (2) was changed, the weight of the M-APP flame retardant was 4g, and the other steps were the same as in example 3.
Example 9
The difference from example 3 is that only the amount of the M-APP flame retardant used in step (2) was changed, the weight of the M-APP flame retardant was 14g, and the other steps were the same as in example 3.
Comparative example 1
The difference from example 3 is that only Ti in the step (1) was changed 3 C 2 T x Dosage of nanosheets, ti 3 C 2 T x The weight of the nanoplatelets was 0g, and the other steps were the same as in example 3.
Comparative example 2
The composite material of comparative example 2 was prepared by the following method:
100g of high-fluidity nylon 6, 7.6g of APP flame retardant and Ti 3 C 2 T x 0.4g of nano-sheet and 1680.5g of antioxidant are evenly mixed in a high-speed mixer, extruded and granulated by a double-screw extruder, and the produced granules are dried in vacuum for 12 hours at 85 ℃ and then are prepared into the composite material in an injection molding machine.
Comparative example 3
The difference from example 3 is that only the amount of dopamine used in step (1) was changed, the weight of dopamine was 25g, and the other steps were the same as in example 3.
Comparative example 4
The difference from example 3 was that only the amount of dopamine used in step (1) was changed, the weight of dopamine was 0.06g, and the other steps were the same as in example 3.
Comparative example 5
The difference from example 3 is that only Ti in the step (1) was changed 3 C 2 T x Dosage of nanosheets, ti 3 C 2 T x The weight of the nanoplatelets was 15g, and the other steps were the same as in example 3.
Comparative example 6
The difference from example 3 is that only Ti in the step (1) was changed 3 C 2 T x Dosage of nanosheets, ti 3 C 2 T x The weight of the nanoplatelets was 0.05g, and the other steps were the same as in example 3.
Comparative example 7
The difference from example 3 is that only the amount of the M-APP flame retardant used in step (2) was changed, the weight of the M-APP flame retardant was 25g, and the other steps were the same as in example 3.
Comparative example 8
The difference from example 3 is that only the amount of the M-APP flame retardant used in step (2) was changed, the weight of the M-APP flame retardant was 0.1g, and the other steps were the same as in example 3.
Comparative example 9
The difference from example 3 is that the pH in step (1) was 9, and the other steps were the same as in example 3.
Comparative example 10
The difference from example 3 is that the reaction time in step (1) was 15h, and the other steps were the same as in example 3.
Comparative example 11
The difference from example 3 is that in step (1) the ammonium polyphosphate is replaced by an equivalent amount of melamine cyanurate, and the other steps are the same as in example 3.
Experiment
The tensile properties were tested using GB/T1040.1-2006 with a tensile rate of 5mm/min.
The notched impact strength of the simply supported beams was tested according to GB/T1043 and under constant temperature and humidity.
The flame retardant rating test standard is according to UL94 standard, and a horizontal-vertical burning test instrument is adopted for vertical burning test.
Limiting oxygen index test criteria the limiting oxygen index of the test specimens was determined by means of an oxygen index meter according to GB/T2406-2009. The experimental results are shown in table 1.
TABLE 1
From table 1, it can be seen that after the M-APP flame retardant is subjected to microencapsulation treatment of dopamine, both tensile strength and impact strength are improved, which indicates that dopamine plays a good bridging role between the flame retardant and nylon, and the interfacial binding force of the composite material is improved due to the fact that the dopamine can form hydrogen bonds with ammonium polyphosphate and high-fluidity nylon 6. With Ti 3 C 2 T x The increase in the amount of nanoplatelets, the tensile strength of the composite material increases and decreases, 5g of Ti in example 3 3 C 2 T x The nanosheets, the composite had the best tensile and impact strength, whereas example 7 had 7.5g of Ti 3 C 2 T x The nano-sheets are agglomerated, so that the stretching and impact of the composite material are reduced, which indicates Ti 3 C 2 T x The nano-sheet plays a role in synergistic flame retardance, and simultaneously, because of Ti 3 C 2 T x The surface of the nano-sheet has rich functional groups and proper amount of Ti 3 C 2 T x The nano-sheet effectively improves the interfacial binding force of the composite material and avoids agglomeration. When the addition amount of the M-APP flame retardant is 8%, the tensile strength of the composite material reaches 112MPa, the flame retardant grade reaches V-0, and the composite material has good flame retardant property and mechanical property.
In the invention, if the usage amount of the dopamine is too high, the flame retardant property of the composite material is easily influenced greatly, and if the usage amount of the dopamine is too low, the thickness of the coating is too thin, so that the mechanical property of the composite material is reduced. If the pH of the solution is not within the range defined by the present invention, the self-polymerization rate of dopamine is affected, so that the polydopamine cannot well coat the ammonium polyphosphate and Ti 3 C 2 T x The nano-sheets affect the mechanical properties and flame retardant properties of the composite material. If the reaction time is too short or too long, the self-polymerization time of dopamine is affected, and the poly-dopamine coating ammonium polyphosphate and Ti are further affected 3 C 2 T x The thickness of the nanoplatelets thus affects the mechanical properties of the composite. Thus, the invention is realized by controlling dopamine, ammonium polyphosphate and Ti 3 C 2 T x The dosage of the nano-sheets, the pH value of the solution and the reaction time are within the range limited by the invention, so that the polydopamine can better coat the ammonium polyphosphate and the Ti 3 C 2 T x The nano sheet can improve the mechanical property and flame retardant property of the composite material.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (9)

1. The preparation method of the flame-retardant modified high-fluidity nylon 6 composite material is characterized by comprising the following steps of:
(1) Mixing 0.1-20 weight parts of dopamine, 1-100 weight parts of ammonium polyphosphate and 0.1-10 weight parts of Ti 3 C 2 T x Adding the nano-sheets into a buffer solution, regulating the pH to 7.5-8.5, uniformly stirring, carrying out microencapsulation treatment for 1-10h, and drying to obtain an M-APP flame retardant;
(2) Uniformly mixing 100 parts by weight of high-fluidity nylon 6, 0.5-20 parts by weight of M-APP flame retardant and 0.2-3 parts by weight of antioxidant, extruding, granulating and injection molding to obtain a flame-retardant modified high-fluidity nylon 6 composite material;
the high-fluidity nylon 6 in the step (2) is star-structure nylon 6 formed by polymerizing caprolactam monomers initiated by a dendronization initiating unit, and the melt index is 320-360g/10min under the test condition of 2.16Kg at 230 ℃.
2. The method for preparing a flame-retardant modified high-fluidity nylon 6 composite material according to claim 1, wherein the weight part of dopamine in the step (1) is 5-15 parts, the weight part of ammonium polyphosphate is 95 parts, and the weight part of Ti is 3 C 2 T x The weight portion of the nano-sheet is 2.5-7.5 portions.
3. The method for preparing the flame-retardant modified high-fluidity nylon 6 composite material according to claim 1, wherein the weight ratio of the high-fluidity nylon 6 to the M-APP flame retardant in the step (2) is 100: (4-14).
4. The method for preparing a flame-retardant modified high-fluidity nylon 6 composite material according to claim 1, wherein the buffer solution in the step (1) is disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution.
5. The method for preparing the flame-retardant modified high-fluidity nylon 6 composite material according to claim 1, wherein the antioxidant in the step (2) is at least one of pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), n-octadecanol beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate, antioxidant 168, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, trisnonylphenyl phosphite, 2, 6-di-tert-butyl-4-methylphenol and triphenyl (yl) phosphorus.
6. The method for preparing a flame retardant modified high fluidity nylon 6 composite material according to claim 5, wherein the antioxidant in the step (2) is a combination of pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and n-octadecanol β - (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate.
7. The method for preparing the flame-retardant modified high-fluidity nylon 6 composite material according to claim 6, wherein the weight ratio of pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) to n-stearyl alcohol beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate is 1:1.
8. the method for preparing a flame retardant modified high fluidity nylon 6 composite material according to claim 1, wherein in the step (1), ti is as follows 3 C 2 T x The preparation method of the nano-sheet comprises the following steps:
(1) TiH is processed by 2 Ball milling the powder, al powder and graphite powder for 1-20h to obtain a mixture;
(2) Sintering the mixture in the step (1) for 1-2h in argon atmosphere at 800-1600 ℃ to obtain Ti 3 AlC 2 Block body, then Ti 3 AlC 2 Pulverizing the block, sieving to obtain Ti with particle diameter D50 of 75-80 μm 3 AlC 2 A powder;
(3) Ti in step (2) 3 AlC 2 Adding the powder into HF solution with mass concentration of 30-60%, stirring, standing at room temperature to obtain suspension, and collecting Ti 3 AlC 2 The ratio of powder to HF solution is 1-5g:100-150mL;
(4) Centrifuging the suspension in the step (3), washing with deionized water for 3-4 times until the pH value of the supernatant is neutral, and finally washing and drying the product to obtain Ti 3 C 2 T x A nano-sheet.
9. The flame-retardant modified high-fluidity nylon 6 composite material is characterized by being prepared by the preparation method of the flame-retardant modified high-fluidity nylon 6 composite material according to any one of claims 1-8.
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CN101148506A (en) * 2007-11-02 2008-03-26 湖南大学 Method for producing high-fluidity nylon 6
CN103044901A (en) * 2012-12-17 2013-04-17 株洲时代新材料科技股份有限公司 High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof
CN109096754A (en) * 2018-07-12 2018-12-28 大连理工大学 A kind of MXene- poly-dopamine composite material and preparation method
CN114855298A (en) * 2022-04-14 2022-08-05 东华大学 Flame-retardant smoke-inhibiting polylactic acid fiber and preparation method thereof

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US9688867B2 (en) * 2013-09-09 2017-06-27 American University Flame retardant coatings

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Publication number Priority date Publication date Assignee Title
CN101148506A (en) * 2007-11-02 2008-03-26 湖南大学 Method for producing high-fluidity nylon 6
CN103044901A (en) * 2012-12-17 2013-04-17 株洲时代新材料科技股份有限公司 High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof
CN109096754A (en) * 2018-07-12 2018-12-28 大连理工大学 A kind of MXene- poly-dopamine composite material and preparation method
CN114855298A (en) * 2022-04-14 2022-08-05 东华大学 Flame-retardant smoke-inhibiting polylactic acid fiber and preparation method thereof

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