CN113980337B - Flame-retardant composite foam board for vehicle and preparation process thereof - Google Patents
Flame-retardant composite foam board for vehicle and preparation process thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
Abstract
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant composite foam board for a vehicle and a preparation process thereof; the composite foam board is composed of the following raw materials in parts by weight: 80 to 90 parts of polypropylene resin, 20 to 30 parts of modified polytetrafluoroethylene, 3 to 7 parts of plasticizer, 0.4 to 1.2 parts of ethylene bis stearamide, 8 to 20 parts of calcium carbonate, 0.5 to 1.0 part of dilauryl thiodipropionate, 1.2 to 2.0 parts of methyl tin mercaptide, 0.6 to 1.8 parts of 2-hydroxy-4-methoxybenzophenone, 0.8 to 1.6 parts of 8-hydroxyquinoline copper, 20 to 32 parts of organic flame retardant and 8 to 15 parts of synergistic flame retardant; in the invention, the polypropylene resin, the modified polytetrafluoroethylene and the like are used as raw materials, so that the prepared composite foam board has excellent mechanical properties; in addition, the synergistic cooperation of the organic flame retardant and the synergistic flame retardant enables the composite foam board to have good flame retardant performance, and the safety performance and the quality of the composite foam board are effectively guaranteed.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant composite foam board for a vehicle and a preparation process thereof.
Background
The foamed plastic has the advantages of light weight, heat insulation, sound insulation, buffering, high specific strength, low cost and the like, and is widely applied to the fields of packaging industry, agriculture, transportation industry, military industry, aerospace industry, daily necessities and the like. At present, the development of the foam plastics is very rapid, and the main varieties are three main categories of polyurethane soft and hard foam plastics, polystyrene and polyethylene extrusion foaming.
However, the chlorofluorocarbon used in the molding process of the expanded polystyrene product can damage the atmospheric ozone layer and cause great pollution to the environment. And the product waste is large in volume, does not decay and is difficult to recycle, so that white pollution is caused to the surrounding environment. Therefore, a fluorine-free, lightweight environmentally friendly foam material capable of replacing expanded polystyrene has been actively sought.
Compared with the traditional expanded polystyrene and polyethylene products, the polypropylene expanded product is favored by people due to the advantages of excellent heat resistance, mechanical property, good environmental adaptability and the like, and the total processing cost from extrusion expansion to thermoforming is lower than that of the expanded polystyrene product. Therefore, it is widely used in the fields of automobile interior, food, cosmetics, and electronic product packaging.
Although the polypropylene foam materials have the advantages mentioned above, the flame retardant property is relatively poor, and the mechanical properties are relatively insufficient, and further improvement is still needed. Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a flame retardant composite foam board for vehicles and a preparation process thereof.
Disclosure of Invention
The invention aims to provide a flame-retardant composite foam board for a vehicle and a preparation process thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the flame-retardant composite foam board for the vehicle comprises the following raw materials in parts by weight: 80 to 90 parts of polypropylene resin, 20 to 30 parts of modified polytetrafluoroethylene, 3 to 7 parts of plasticizer, 0.4 to 1.2 parts of ethylene bis stearamide, 8 to 20 parts of calcium carbonate, 0.5 to 1.0 part of dilauryl thiodipropionate, 1.2 to 2.0 parts of methyl tin mercaptide, 0.6 to 1.8 parts of 2-hydroxy-4-methoxybenzophenone, 0.8 to 1.6 parts of 8-hydroxyquinoline copper, 20 to 32 parts of organic flame retardant and 8 to 15 parts of synergistic flame retardant.
Further, the preparation method of the modified polytetrafluoroethylene comprises the following steps: soaking the polytetrafluoroethylene granules in coupling agent hydrolysate with the mass 5-8 times of that of the polytetrafluoroethylene granules, soaking for 2-4 h in a water bath/oil bath environment at the temperature of 50-60 ℃, filtering out the polytetrafluoroethylene granules, and drying the polytetrafluoroethylene granules to finish the modification of the polytetrafluoroethylene.
Furthermore, the preparation method of the coupling agent hydrolysate comprises the following steps: respectively weighing 15-25 parts of coupling agent, 70-100 parts of ethanol and 12-20 parts of deionized water according to parts by weight, uniformly mixing the raw materials, and adjusting the pH value to 2.5-3.2; then mechanically stirring the obtained coupling agent mixed solution for 40-60 min at the temperature of 45-55 ℃, thus obtaining the coupling agent hydrolysate finished product.
Furthermore, the coupling agent is selected from silane coupling agents, and the silane coupling agent is selected from any one of KH792, KH550, KH560 and KH 570.
Further, the preparation method of the synergistic flame retardant comprises the following steps:
i, adding modified graphene oxide into a proper amount of ethanol according to a solid-liquid ratio of 0.1-0.15 g/mL, uniformly dispersing by ultrasonic, adjusting the pH value of a mixed component to 9.5-11.5 by dropwise adding ammonia water, slowly dropwise adding a zinc nitrate aqueous solution with the volume of 0.4-0.8 time that of the ethanol and the concentration of 0.5-1.0 g/mL into the mixed component, and stirring and reacting the obtained mixed phase at the temperature of 20-50 ℃ for 2-6 h; after the reaction is finished, sequentially carrying out centrifugal filtration, distilled water washing and drying treatment on the obtained product components; storing the obtained material for later use;
and II, putting the dried material into ethanol according to a solid-liquid ratio of 0.08-0.12 g/mL, uniformly mixing and stirring, adding boric acid with the mass being 1.5-2.5 times that of the modified graphene oxide, mixing and stirring for 3-7 h, adding laurylamine with the mass being 0.7-1.0 time that of the boric acid, mechanically stirring for 3-8 h, sequentially centrifuging the obtained reaction product while hot and washing with ethanol for 2-3 times, and then drying the reaction product to finally obtain solid powder, namely the high-efficiency flame retardant finished product.
Further, the preparation method of the modified graphene oxide comprises the following steps: firstly, carrying out ultrasonic dispersion treatment on a graphene oxide aqueous solution with the concentration of 6-15 mg/mL, and then injecting a refrigerant into the obtained graphene oxide dispersion liquid until the obtained mixed liquid is solidified by condensation; and then, carrying out freeze drying treatment on the obtained solid material at the temperature of-40 to-60 ℃ for 15 to 50 hours to finally obtain a modified graphene oxide finished product.
Furthermore, the frequency of ultrasonic dispersion is 20-25 kHz during ultrasonic dispersion, and the time of ultrasonic dispersion is 2-3 h.
Furthermore, the refrigerant is liquid nitrogen, and the injection rate of the refrigerant is 40-60 mL/min.
Furthermore, the organic flame retardant is any one of melamine, ammonium polyphosphate and tributyl phosphate.
The preparation process of the flame-retardant composite foam board for the vehicle comprises the following steps:
s1, weighing the raw materials according to the formula amount, respectively placing the weighed raw materials in a drying box for drying treatment, and respectively storing the raw materials for later use;
s2, transferring the dried raw materials into a multi-screw extruder together, and extruding and granulating the raw materials under the conditions that the temperature of the extruder is 150-250 ℃ and the rotating speed of a screw is 80-150 rpm, and storing the obtained polypropylene/polytetrafluoroethylene beads for later use;
s3, transferring the obtained polypropylene/polytetrafluoroethylene beads into a supercritical die-pressing foaming machine, ensuring that the total volume of the added materials is not more than one third of the volume of the container, and then soaking for 2-5 hours under the conditions that the pressure is 10-25 MPa, the intermittent foaming temperature is 150-250 ℃ and supercritical CO2 is used as a foaming agent; finally, carrying out pressure relief at the speed of 12-20 MPa/s; the obtained foaming material is processed to prepare a foam board product, namely a finished product of the flame-retardant composite foam board for the vehicle.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, graphene oxide is used as a raw material, and is treated by a special process to obtain modified graphene oxide with a porous structure and a richer specific surface area, the obtained modified graphene oxide has a larger specific surface area and a porous structure, so that more hydroxide precipitates of zinc salt can be adsorbed, and then the modified graphene oxide and boric acid have a chemical action, and finally quite abundant zinc borate is deposited on the surface of the modified graphene oxide. Because zinc borate can be vitrified due to a large amount of heat absorption at high temperature, the prepared synergistic flame retardant has excellent flame retardant property. Moreover, a synergistic effect exists between the synergistic flame retardant and the organic flame retardant, and the synergistic effect and the organic flame retardant are matched with each other, so that the prepared composite foam board has excellent flame retardant performance, and the safety performance and the quality of the composite foam board are effectively improved.
In addition, the laurylamine is used, so that the surface performance of the synergistic flame retardant can be effectively changed, the surface performance of the synergistic flame retardant is changed from hydrophilic to hydrophobic, the dispersing performance of the synergistic flame retardant is effectively improved, the synergistic flame retardant can be better fused with an organic phase formed by polypropylene and polytetrafluoroethylene, and the flame retardant performance and the quality of the prepared composite foam material are ensured.
2. According to the invention, polytetrafluoroethylene is soaked in the home-made coupling agent hydrolysate for modification treatment, and the silane coupling agent acts on the surface of the polytetrafluoroethylene, so that the polytetrafluoroethylene can be better fused with polypropylene in the extruded and granulated melt, and a polypropylene/polytetrafluoroethylene system formed by the polytetrafluoroethylene and the silane coupling agent has excellent mechanical properties, so that the tensile strength, bending strength and impact strength of the prepared composite foam board are greatly improved; effectively ensuring the quality of the prepared composite foam board.
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 flame-retardant composite foam board for the vehicle comprises the following raw materials in parts by weight: 80 parts of polypropylene resin, 20 parts of modified polytetrafluoroethylene, 3 parts of plasticizer, 0.4 part of ethylene bis stearamide, 8 parts of calcium carbonate, 0.5 part of dilauryl thiodipropionate, 1.2 parts of methyl tin mercaptide, 0.6 part of 2-hydroxy-4-methoxybenzophenone, 0.8 part of 8-hydroxyquinoline copper, 20 parts of organic flame retardant and 8 parts of synergistic flame retardant.
The preparation method of the modified polytetrafluoroethylene comprises the following steps: soaking the polytetrafluoroethylene granules in coupling agent hydrolysate with the mass 5 times of that of the polytetrafluoroethylene granules, soaking for 2 hours in a water bath/oil bath environment at the temperature of 50 ℃, filtering out the polytetrafluoroethylene granules, and drying the polytetrafluoroethylene granules to finish the modification of the polytetrafluoroethylene.
The preparation method of the coupling agent hydrolysate comprises the following steps: respectively weighing 15 parts of coupling agent, 70 parts of ethanol and 12 parts of deionized water according to parts by weight, uniformly mixing all the raw materials, and adjusting the pH value to 2.5; and mechanically stirring the obtained coupling agent mixed solution at the temperature of 45 ℃ for 40min to obtain the coupling agent hydrolysate finished product.
The coupling agent is silane coupling agent, and the silane coupling agent is KH792 silane coupling agent.
The preparation method of the synergistic flame retardant comprises the following steps:
i, adding modified graphene oxide into a proper amount of ethanol according to a solid-to-liquid ratio of 0.1g/mL, uniformly dispersing by ultrasonic waves, adjusting the pH value of a mixed component to 9.5 by dropwise adding ammonia water, slowly dropwise adding a zinc nitrate aqueous solution with the volume being 0.4 time of that of the ethanol and the concentration being 0.5g/mL into the mixed component, and stirring and reacting the obtained mixed phase at the temperature of 20 ℃ for 2 hours; after the reaction is finished, sequentially carrying out centrifugal filtration, distilled water washing and drying treatment on the obtained product components; storing the obtained material for later use;
and II, putting the dried material into ethanol according to a solid-liquid ratio of 0.08g/mL, uniformly mixing and stirring, adding boric acid with the mass being 1.5 times that of the modified graphene oxide, mixing and stirring for 3 hours, adding laurylamine with the mass being 0.7 time that of the boric acid, mechanically stirring for 3 hours, sequentially centrifuging the obtained reaction product while hot and washing the reaction product with ethanol for 2 times, and drying the reaction product to finally obtain solid powder, namely the finished product of the efficient flame retardant.
The preparation method of the modified graphene oxide comprises the following steps: firstly, carrying out ultrasonic dispersion treatment on a graphene oxide aqueous solution with the concentration of 6mg/mL, and then injecting a refrigerant into the obtained graphene oxide dispersion liquid until the obtained mixed liquid is solidified when meeting condensation; and then, carrying out freeze drying treatment on the obtained solid material at the temperature of-40 ℃ for 15h to finally obtain the modified graphene oxide finished product.
The ultrasonic dispersion frequency is 20kHz during ultrasonic dispersion, and the ultrasonic dispersion time is 2h.
The refrigerant is liquid nitrogen, and the injection rate of the refrigerant is 40mL/min.
The organic flame retardant is melamine.
The preparation process of the flame-retardant composite foam board for the vehicle comprises the following steps:
s1, weighing the raw materials according to the formula amount, respectively placing the weighed raw materials in a drying box for drying treatment, and respectively storing the raw materials for later use;
s2, transferring the dried raw materials into a multi-screw extruder together, extruding and granulating the raw materials under the conditions that the temperature of the extruder is 150 ℃ and the rotating speed of a screw is 80rpm, and storing the obtained polypropylene/polytetrafluoroethylene beads for later use;
s3, transferring the obtained polypropylene/polytetrafluoroethylene beads into a supercritical die-pressing foaming machine, ensuring that the total volume of the added materials is not more than one third of the volume of the container, and then performing supercritical CO at the pressure of 10MPa and the intermittent foaming temperature of 150 DEG C 2 Soaking for 2 hours under the condition of foaming agent; finally, carrying out pressure relief at the speed of 12 MPa/s; the obtained foaming material is processed to prepare a foam board product, namely a finished product of the flame-retardant composite foam board for the vehicle.
Example 2
The preparation process of the flame-retardant composite foam board for the vehicle provided by the embodiment is substantially the same as that of the embodiment 1, and the main difference is that the specific mixture ratio of the used raw materials is different, specifically:
85 parts of polypropylene resin, 25 parts of modified polytetrafluoroethylene, 5 parts of plasticizer, 0.8 part of ethylene bis stearamide, 15 parts of calcium carbonate, 0.8 part of dilauryl thiodipropionate, 1.6 parts of methyl tin mercaptide, 1.2 parts of 2-hydroxy-4-methoxybenzophenone, 1.4 parts of 8-hydroxyquinoline copper, 25 parts of organic flame retardant and 12 parts of synergistic flame retardant.
Example 3
The preparation process of the flame-retardant composite foam board for the vehicle provided by the embodiment is substantially the same as that of the embodiment 1, and the main difference is that the specific mixture ratio of the used raw materials is different, specifically:
90 parts of polypropylene resin, 30 parts of modified polytetrafluoroethylene, 7 parts of plasticizer, 1.2 parts of ethylene bis stearamide, 20 parts of calcium carbonate, 1.0 part of dilauryl thiodipropionate, 2.0 parts of methyl tin mercaptide, 1.8 parts of 2-hydroxy-4-methoxybenzophenone, 1.6 parts of 8-hydroxyquinoline copper, 32 parts of organic flame retardant and 15 parts of synergistic flame retardant.
Comparative example 1: the preparation process of the flame retardant composite foam board for the vehicle provided by the embodiment is substantially the same as that of the embodiment 1, and the main differences are as follows: replacing modified polytetrafluoroethylene with common polytetrafluoroethylene with similar and equal specifications;
comparative example 2: the preparation process of the flame retardant composite foam board for the vehicle provided by the embodiment is substantially the same as that of the embodiment 1, and the main differences are as follows: equivalent zinc borate is adopted to replace the synergistic flame retardant;
performance testing
The composite foam boards prepared by examples 1 to 3 of the present invention were respectively referred to as experimental examples 1 to 3; the composite foam sheets prepared by comparative examples 1 to 2 were designated comparative examples 1 to 2; the composite foam boards provided in examples 1-3 and comparative examples 1-2 were then tested for their relevant properties, and the results are reported in the following table:
note: 1. the closed cell rate is tested according to the GB10799 test standard;
2. the melt flow rate is tested according to the ISO1133 detection standard;
3. the tensile strength is tested according to ISO527 test standard;
4. the bending strength is tested according to ISO178 detection standard;
5. testing the notch impact strength of the cantilever beam according to an ISO180 detection standard;
6. the oxygen index is tested according to ISO 4589 detection standard;
7. the vertical combustion test is tested according to UL 94 detection standard;
the relevant data in the comparison and analysis table show that the composite foam board prepared according to the invention not only has excellent mechanical properties, but also has good flame retardant property, and the safety performance and the quality of the composite foam board are effectively ensured. Therefore, the fiber fabric prepared by the method has wider market prospect and is more suitable for popularization.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., 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 preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. The flame-retardant composite foam board for the vehicle is characterized by comprising the following raw materials in parts by weight: 80 to 90 parts of polypropylene resin, 20 to 30 parts of modified polytetrafluoroethylene, 3 to 7 parts of plasticizer, 0.4 to 1.2 parts of ethylene bis stearamide, 8 to 20 parts of calcium carbonate, 0.5 to 1.0 part of dilauryl thiodipropionate, 1.2 to 2.0 parts of methyl tin mercaptide, 0.6 to 1.8 parts of 2-hydroxy-4-methoxybenzophenone, 0.8 to 1.6 parts of 8-hydroxyquinoline copper, 20 to 32 parts of organic flame retardant and 8 to 15 parts of synergistic flame retardant;
the preparation method of the synergistic flame retardant comprises the following steps:
i, adding modified graphene oxide into a proper amount of ethanol according to a solid-to-liquid ratio of 0.1-0.15 g/mL, uniformly dispersing by ultrasonic, adjusting the pH value of a mixed component to 9.5-11.5 by dropwise adding ammonia water, slowly dropwise adding a zinc nitrate aqueous solution with the volume of 0.4-0.8 time that of the ethanol and the concentration of 0.5-1.0 g/mL into the mixed component, and stirring and reacting the obtained mixed phase at the temperature of 20-50 ℃ for 2-6 h; after the reaction is finished, sequentially carrying out centrifugal filtration, distilled water washing and drying treatment on the obtained product components; storing the obtained material for later use;
II, putting the dried material into ethanol according to a solid-liquid ratio of 0.08-0.12 g/mL, mixing and stirring uniformly, adding boric acid with the mass being 1.5-2.5 times that of the modified graphene oxide, mixing and stirring for 3-7 h, adding laurylamine with the mass being 0.7-1.0 time that of the boric acid, mechanically stirring for 3-8 h, sequentially carrying out hot centrifugation and ethanol washing on the obtained reaction product for 2-3 times, and then drying the reaction product to finally obtain solid powder, namely the finished product of the efficient flame retardant;
the preparation method of the modified graphene oxide comprises the following steps: firstly, carrying out ultrasonic dispersion treatment on a graphene oxide aqueous solution with the concentration of 6-15 mg/mL, and then injecting a refrigerant into the obtained graphene oxide dispersion liquid until the obtained mixed liquid is solidified when meeting condensation; and then, carrying out freeze drying treatment on the obtained solid material at the temperature of-40 to-60 ℃ for 15 to 50 hours to finally obtain a modified graphene oxide finished product.
2. The flame-retardant composite foam board for the vehicle according to claim 1, wherein the preparation method of the modified polytetrafluoroethylene comprises the following steps: soaking the polytetrafluoroethylene granules in coupling agent hydrolysate with the mass 5-8 times of that of the polytetrafluoroethylene granules, soaking for 2-4 h in a water bath/oil bath environment at the temperature of 50-60 ℃, filtering out the polytetrafluoroethylene granules, and drying the polytetrafluoroethylene granules to finish the modification of the polytetrafluoroethylene.
3. The flame retardant composite foam board for the vehicle according to claim 2, wherein the preparation method of the coupling agent hydrolysate is as follows: respectively weighing 15-25 parts of coupling agent, 70-100 parts of ethanol and 12-20 parts of deionized water according to parts by weight, uniformly mixing the raw materials, and adjusting the pH value to 2.5-3.2; then mechanically stirring the obtained coupling agent mixed solution for 40-60 min at the temperature of 45-55 ℃, thus obtaining the finished product of the coupling agent hydrolysate.
4. The flame retardant composite foam sheet according to claim 2 or 3, wherein: the coupling agent is selected from silane coupling agents, and the silane coupling agents are selected from any one of KH792, KH550, KH560 and KH 570.
5. The flame retardant composite foam board for vehicles according to claim 1, wherein: the ultrasonic dispersion frequency is 20-25 kHz during ultrasonic dispersion, and the ultrasonic dispersion time is 2-3 h.
6. The flame retardant composite foam sheet according to claim 1, wherein: the refrigerant is liquid nitrogen, and the injection rate of the refrigerant is 40-60 mL/min.
7. The flame retardant composite foam board for vehicles according to claim 1, wherein: the organic flame retardant is any one of melamine, ammonium polyphosphate and tributyl phosphate.
8. The process for preparing the flame retardant composite foam sheet for vehicles according to any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, weighing the raw materials according to the formula amount, respectively placing the weighed raw materials in a drying box for drying treatment, and respectively storing the raw materials for later use;
s2, transferring the dried raw materials into a multi-screw extruder together, and extruding and granulating the raw materials under the conditions that the temperature of the extruder is 150-250 ℃ and the rotating speed of a screw is 80-150 rpm, and storing the obtained polypropylene/polytetrafluoroethylene beads for later use;
s3, transferring the obtained polypropylene/polytetrafluoroethylene beads into a supercritical die-pressing foaming machine, ensuring that the total volume of the added materials is not more than one third of the volume of the container, and then performing supercritical CO at the pressure of 10-25 MPa and the intermittent foaming temperature of 150-250 DEG C 2 Soaking for 2-5 h under the condition of foaming agent; finally, carrying out pressure relief at the speed of 12-20 MPa/s; what is needed isThe obtained foaming material is processed to prepare a foam board product, namely a finished product of the flame-retardant composite foam board for the vehicle.
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| CN202111404104.5A CN113980337B (en) | 2021-11-24 | 2021-11-24 | Flame-retardant composite foam board for vehicle and preparation process thereof |
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| CN202111404104.5A CN113980337B (en) | 2021-11-24 | 2021-11-24 | Flame-retardant composite foam board for vehicle and preparation process thereof |
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| CN113980337A CN113980337A (en) | 2022-01-28 |
| CN113980337B true CN113980337B (en) | 2022-12-23 |
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| DE102005039976A1 (en) * | 2005-08-23 | 2007-03-08 | Basf Ag | Production of foam plates combining uniform density distribution with good mechanical properties involves pressing coated prefoamed particles in a mold in the absence of water vapor |
| DE102010001588A1 (en) * | 2010-02-04 | 2011-08-04 | Henkel AG & Co. KGaA, 40589 | Curable compositions with improved fire properties |
| CN103012832B (en) * | 2012-11-19 | 2014-04-16 | 中国科学院长春应用化学研究所 | Preparation method of foamed polypropylene |
| CN106810761A (en) * | 2016-12-22 | 2017-06-09 | 阜阳市三郁包装材料有限公司 | Modified polypropylene flame redardant foamed board of a kind of hydridization polytetrafluoroethylene (PTFE) silica aerogel and preparation method thereof |
| CN110128693B (en) * | 2018-02-09 | 2021-10-08 | 中国科学院宁波材料技术与工程研究所 | Polyolefin foam material and preparation method thereof |
| CN108727679A (en) * | 2018-05-21 | 2018-11-02 | 福州大学 | A kind of fire-retardant eva foam composite material of ammonium polyphosphate modifying/graphene |
| CN110643073A (en) * | 2019-08-22 | 2020-01-03 | 安徽建筑大学 | Graphene hybrid containing boron, nitrogen, cobalt, zinc and silicon and preparation method thereof |
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