CN114889235A - Pearl shell structure-imitated SMPI fire-resistant flame-retardant material and preparation method and application thereof - Google Patents

Pearl shell structure-imitated SMPI fire-resistant flame-retardant material and preparation method and application thereof Download PDF

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CN114889235A
CN114889235A CN202210569218.3A CN202210569218A CN114889235A CN 114889235 A CN114889235 A CN 114889235A CN 202210569218 A CN202210569218 A CN 202210569218A CN 114889235 A CN114889235 A CN 114889235A
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flame
smpi
retardant
polyamic acid
fire
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CN114889235B (en
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冷劲松
王晓飞
何阳
刘彦菊
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C1/06—Frames; Stringers; Longerons ; Fuselage sections
    • B64C1/12—Construction or attachment of skin panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C3/00—Wings
    • B64C3/38—Adjustment of complete wings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C2001/0054—Fuselage structures substantially made from particular materials
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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Abstract

The invention provides a nacre-like structure SMPI fire-resistant flame-retardant material and a preparation method thereof, wherein the preparation method of the nacre-like structure SMPI fire-resistant flame-retardant material comprises the following steps: dissolving imidazole-containing aromatic heterocyclic diamine in a solvent; adding biphenyl dianhydride into the imidazole-containing aromatic heterocyclic diamine solution; mixing a portion of the polyamic acid solution with a flame retardant; pouring another part of the polyamic acid solution onto the carbon fiber cloth; pouring the flame retardant/polyamic acid composite solution onto the polyamic acid/carbon fiber cloth composite material; and (3) laminating the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary hot imidization to obtain the SMPI flame-retardant material with the nacre-like structure. The SMPI fire-resistant flame-retardant material with the nacre-like structure prepared by the preparation method provided by the invention has good mechanical property, shape memory property and fire-resistant flame-retardant property, and lays a foundation for the application of an intelligent high polymer material in a high-temperature environment.

Description

Pearl shell structure-imitated SMPI fire-resistant flame-retardant material and preparation method and application thereof
Technical Field
The invention relates to the technical field of fire-resistant flame-retardant materials, in particular to a nacre-like structure SMPI fire-resistant flame-retardant material and a preparation method and application thereof.
Background
Shape Memory Polymer (SMP) is an intelligent material capable of responding to external stimuli such as heat, light, electricity, magnetism or chemistry, and the Polymer with Shape Memory effect can keep a certain temporary Shape after shaping and return to the original Shape before deformation under the external stimuli. Polyimide (SMPI) with Shape Memory has excellent Shape Memory effect, thermal stability, radiation resistance and good mechanical properties, and can be applied to the fields of sensors, deployable structures and the like.
Polyimide (PI) belongs to a self-extinguishing material, has a limit oxygen index of up to 38 percent, can be carbonized when exposed to fire at high temperature, has no molten drops, is self-extinguished after being separated from the fire, is non-toxic, is the best heat-resistant variety in the obtained industrialized high polymer materials, and can meet the flame-retardant requirements of most fields. However, in some special fields, the flame retardant requirement for PI is more severe, so in order to meet the requirement in these special fields, PI needs to be modified in flame retardant to improve the flame retardant property.
Disclosure of Invention
The invention solves the problem of how to provide a nacre-like structure shape memory polyimide fire-resistant flame-retardant material with better fire-resistant flame-retardant performance, and improves the application prospect of the shape memory polyimide in the flame-retardant field.
In order to solve at least one aspect of the above problems, the present invention provides a preparation method of a nacre-like SMPI fire-resistant flame-retardant material, comprising the following steps:
step S1, dissolving the imidazole-containing aromatic heterocyclic diamine in a solvent to obtain an imidazole-containing aromatic heterocyclic diamine solution;
step S2, adding biphenyl dianhydride into the imidazole-containing aromatic heterocyclic diamine solution under a protective atmosphere, and reacting for 96-120h to obtain a polyamic acid solution;
step S3, mixing a part of the polyamic acid solution with a flame retardant to obtain a flame retardant/polyamic acid composite solution;
step S4, pouring the other part of the polyamic acid solution onto the carbon fiber cloth, and drying in vacuum to obtain a polyamic acid/carbon fiber cloth composite material;
step S5, pouring the flame retardant/polyamic acid composite solution onto the polyamic acid/carbon fiber cloth composite material, and drying in vacuum to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
and S6, laminating the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary hot imidization to obtain the SMPI flame-retardant material with the nacre-like structure.
Preferably, in step S1, the imidazole-containing aromatic heterocyclic diamine includes 2- (4-aminophenyl) -5-aminobenzimidazole.
Preferably, in step S2, the biphenyl dianhydride includes 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, and the amount ratio of the imidazole-containing aromatic heterocyclic diamine to the biphenyl dianhydride is 1: 1-1.01.
Preferably, the flame retardant includes at least one of aluminum hydroxide and magnesium hydroxide.
Preferably, the flame retardant is a silane coupling agent modified flame retardant, and the silane coupling agent comprises KH550 or KH 560.
Preferably, in step S6, the hot press forming conditions are: keeping the temperature at 175-185 ℃ for 5-15min, and then keeping the temperature at 245-255 ℃ for 55-65min, and the pressure is 3-5 MPa.
Preferably, in step S6, the secondary thermal imidization step is: the heating rate is 1-2 ℃/min, the temperature is raised to 245 ℃ and 255 ℃, and the temperature is kept for 1.5-2.5 h; the heating rate is 1-2 ℃/min, the temperature is raised to 295-305 ℃, and the temperature is kept for 1.5-2.5 h.
According to the invention, imidazole-containing aromatic heterocyclic diamine and biphenyldiamine are subjected to polycondensation to form polyamic acid solution, then part of polyamic acid solution and a flame retardant are subjected to composition of flame retardant/polyamic acid composite solution, part of polyamic acid is poured onto carbon fiber cloth to form polyamic acid/carbon fiber cloth composite material, then the flame retardant/polyamic acid composite solution is poured onto the polyamic acid/carbon fiber cloth composite material to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material, then the flame retardant/polyamic acid/carbon fiber cloth composite material is superposed layer by layer, and hot pressing is carried out to form the composite material with a brick-mud structure, so that the composite material has a mother-of-pearl-like structure, and finally, the polyamic acid is subjected to secondary thermal imidization to form polyimide with shape memory; the SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure prepared by the preparation method provided by the invention has the advantages that the glass transition temperature is 380-410 ℃, the normal-temperature storage modulus is 4.36GPa, the fire-resistant temperature is more than 1000 ℃, the tensile strength is 122.2MPa, the Young modulus is 3.6GPa, the shape fixing rate is 85-100%, the shape recovery rate is 80-100%, and the SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure has good mechanical property, shape memory property and fire-resistant flame-retardant property, thereby laying a foundation for the application of an intelligent high polymer material in a high-temperature environment.
The invention also aims to provide the nacre-like structure SMPI fire-resistant flame-retardant material which is prepared by the preparation method of the nacre-like structure SMPI fire-resistant flame-retardant material.
Preferably, the thickness of the SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure is 0.5-1.5 mm.
Compared with the prior art, the SMPI fire-resistant flame-retardant material with the pearl shell imitating structure has the same beneficial effects as the preparation method of the SMPI fire-resistant flame-retardant material with the pearl shell imitating structure, and the details are not repeated herein.
The invention further aims to provide application of the SMPI fire-resistant flame-retardant material with the pearl shell imitating structure as a fire-resistant intelligent material in the fields of high-speed aircrafts, active morphing wings and self-morphing skin materials.
Compared with the prior art, the application of the SMPI fire-resistant flame-retardant material with the pearl-like mother-of-pearl structure provided by the invention has the same beneficial effect as the preparation method of the SMPI fire-resistant flame-retardant material with the pearl-like mother-of-pearl structure, and is not repeated herein.
Drawings
FIG. 1 is a flow chart of a method for preparing an SMPI fire-resistant and flame-retardant material with a mother-of-pearl imitation structure in an embodiment of the invention;
FIG. 2 is a schematic diagram of a process for preparing a flame retardant/polyimide/carbon fiber cloth composite material according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of the nacre-like brick-mud structure and the flame retardant mechanism of the SMPI fire-resistant flame retardant material with the nacre-like structure in the embodiment of the invention;
FIG. 4 is a graph showing the storage modulus of the SMPI fire-resistant flame-retardant material with the mother-of-pearl imitation structure in example 1 of the present invention;
FIG. 5 is a graph showing the loss factor of the SMPI fire-resistant flame-retardant material with the mother-of-pearl imitation structure in example 1 of the present invention;
FIG. 6 is a drawing graph of the SMPI fire-resistant and flame-retardant material with the mother-of-pearl imitation structure in the embodiment 1 of the invention;
FIG. 7 is a drawing curve diagram of a non-mother-of-pearl SMPI fire-resistant and flame-retardant material;
FIG. 8 is a thermal driving deformation recovery diagram of the SMPI fire-resistant flame-retardant material with the mother-of-pearl imitation structure in example 1 of the present invention;
FIG. 9 is a burning diagram of the SMPI fire-resistant flame-retardant material with the mother-of-pearl imitation structure in the card type furnace (temperature 1350 deg.C) in the embodiment 1 of the invention;
FIG. 10 is a graph of the burning of a nacre-like SMPI fire resistant flame retardant material without flame retardant in a cassette furnace (temperature 1350 ℃).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.
It should be noted that the features in the embodiments of the present invention may be combined with each other without conflict. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment and reagents are commercially available unless otherwise specified.
The embodiment of the invention provides a preparation method of a mother-of-pearl SMPI-like fire-resistant flame-retardant material, as shown in figure 1, comprising the following steps:
step S1, dissolving the imidazole-containing aromatic heterocyclic diamine in a solvent to obtain an imidazole-containing aromatic heterocyclic diamine solution;
step S2, adding biphenyl dianhydride into the imidazole-containing aromatic heterocyclic diamine solution under a protective atmosphere, and reacting for 96-120h to obtain a polyamic acid solution;
step S3, mixing a part of the polyamic acid solution with a flame retardant to obtain a flame retardant/polyamic acid composite solution;
step S4, pouring the other part of the polyamic acid solution onto the carbon fiber cloth, and drying in vacuum to obtain a polyamic acid/carbon fiber cloth composite material;
step S5, pouring the flame retardant/polyamic acid composite solution onto the polyamic acid/carbon fiber cloth composite material, and drying in vacuum to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
and S6, laminating the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary hot imidization to obtain the SMPI flame-retardant material with the nacre-like structure.
In step S1, the imidazole-containing aromatic heterocyclic diamine includes 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI), the solvent includes Dimethyl Sulfoxide (DSMO), and the DSMO has good solubility for the imidazole-containing aromatic heterocyclic diamine and is soluble at normal temperature, and particularly when 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) is selected as a precursor, N-dimethylacetamide, N-methylpyrrolidone, or N, N-dimethylformamide cannot be dissolved at normal temperature, and if the DSMO is dissolved by heating, the reaction temperature is increased, thereby affecting the polycondensation reaction of the imidazole-containing aromatic heterocyclic diamine and biphenyl dianhydride.
In step S2, the biphenyl dianhydride includes 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride (BPDA), and the mass ratio of the imidazole-containing aromatic heterocyclic diamine to the biphenyl dianhydride is 1:1-1.01, and the concentration of the polyamic acid in the obtained polyamic acid solution is 6-16 wt%, where the protective atmosphere includes a nitrogen atmosphere, and the reaction is performed at normal temperature.
In order to ensure that the aromatic heterocyclic diamine containing imidazole and the biphenyl dianhydride react more completely, the reaction is carried out for 96-120h under the condition that the rotating speed is 200-500 r/min.
The polyamic acid solution obtained in step S2 is divided into two parts, one of which is used for mixing with the flame retardant and the other of which is used for bonding with the carbon fiber cloth. Illustratively, the polyamic acid may be equally divided into two portions for the subsequent steps.
In step S3, mixing a part of the polyamic acid solution with a flame retardant to obtain a flame retardant/polyamic acid composite solution; uniformly mixing the polyamic acid solution and the flame retardant by an ultrasonic mode, wherein the ultrasonic time is 60-90 min; the flame retardant comprises at least one of aluminum hydroxide and magnesium hydroxide, and is modified by a silane coupling agent in order to improve the compatibility of the flame retardant and polyamic acid and improve the interfacial bonding force of the flame retardant and the composite material, wherein the silane coupling agent comprises KH550 or KH 560. The hydroxide flame retardant does not generate harmful gas and smoke in the whole flame retardant process, and the decomposed product can absorb the harmful gas and smoke generated by the combustion of the high polymer material while resisting flame, so that the hydroxide flame retardant is environment-friendly.
Wherein the addition amount of the flame retardant is 5-40 wt% of the total amount of the imidazole-containing aromatic heterocyclic diamine and the biphenyl dianhydride, namely the flame retardant accounts for 5-40 wt% of the total amount of the imidazole-containing aromatic heterocyclic diamine and the biphenyl dianhydride; the flame retardant is granular flame retardant with the size of 2-10 μm.
In step S4, another part of the polyamic acid solution is poured onto the carbon fiber cloth, and vacuum-dried to obtain the polyamic acid/carbon fiber cloth composite material.
Specifically, the other part of the polyamic acid solution is poured onto the carbon fiber cloth, the carbon fiber cloth is placed in a vacuum oven, the temperature is kept at 45-55 ℃ for 11.5-12.5h, vacuum pumping is carried out, air bubbles and solvents in the polyamic acid solution are removed, and the polyamic acid/carbon fiber cloth composite material is obtained, wherein the mass ratio of the polyamic acid to the carbon fiber cloth is 1: 1.
The carbon fiber is high-strength high-modulus fiber with the carbon content of more than 90 percent, has excellent high-temperature resistance, is an excellent material for manufacturing high-technology equipment such as aerospace and the like, theoretically has the temperature resistance of more than 2600 ℃, and can improve the high-temperature resistance of the material by using the carbon fiber cloth.
In step S5, the flame retardant/polyamic acid composite solution is poured onto the polyamic acid/carbon fiber cloth composite material, and vacuum dried to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material.
Specifically, the flame retardant/polyamic acid composite solution is poured onto the polyamic acid/carbon fiber cloth composite material, the polyamic acid/carbon fiber cloth composite material is placed in a vacuum oven, the polyamic acid/carbon fiber cloth composite material is kept at the temperature of 45-55 ℃ for 11.5-12.5h, and the solvent is removed, so that the flame retardant/polyamic acid/carbon fiber cloth composite material is obtained by combining the polyamic acid/carbon fiber cloth composite material and the solvent. Wherein, the flame retardant/polyamic acid composite solution is equivalent to a mud layer in a simulated mother-of-pearl structure, and the polyamic acid/carbon fiber cloth composite material is equivalent to a brick layer in the simulated mother-of-pearl structure.
In step S6, the flame retardant/polyamic acid/carbon fiber cloth composite material is laminated, hot-pressed, and then subjected to secondary hot imidization to obtain the SMPI flame-retardant material with the nacre-like structure.
The SMPI fire-resistant flame-retardant material with the nacre-like structure is composed of a plurality of flame retardant/polyimide/carbon fiber cloth composite materials which are stacked layer by layer. Illustratively, when the imidazole-containing aromatic heterocyclic diamine is DAPBI, the biphenyldiamine is BPDA, and the flame retardant is a silane coupling agent modified flame retardant, the route of obtaining the flame retardant/polyimide/carbon fiber cloth composite material is shown in fig. 2, and DAPBI and BPDA are polycondensed to obtain polyamic acid, and then the polyamic acid, the silane coupling agent modified flame retardant and the carbon fiber cloth are compounded, and then hot-pressing and secondary hot imidization are performed to obtain the flame retardant/polyimide/carbon fiber cloth composite material.
Specifically, the hot press molding conditions are as follows: keeping the temperature at 175-185 ℃ for 5-15min, and then keeping the temperature at 245-255 ℃ for 55-65min under the pressure of 3-5 MPa; the secondary thermal imidization step comprises: the heating rate is 1-2 ℃/min, the temperature is raised to 245 ℃ and 255 ℃, and the temperature is kept for 1.5-2.5 h; the heating rate is 1-2 ℃/min, the temperature is raised to 295-305 ℃, and the temperature is kept for 1.5-2.5 h. Namely, firstly, a plurality of flame retardant/polyamide acid/carbon fiber cloth composite materials with mud layers and brick layers are hot-pressed to obtain a multilayer structure, and then polyamide acid is subjected to secondary thermal imidization to form polyimide (SMPI) with shape memory, so that the SMPI flame-retardant material with the mother-of-pearl structure is obtained.
In addition, in order to further improve the performance of the nacre-like structure SMPI fire-resistant flame-retardant material, after secondary thermal imidization, a layer of nano-silica sol can be coated on the surface of the nacre-like structure SMPI fire-resistant flame-retardant material, and then the nacre-like structure SMPI fire-retardant material coated with a layer of nano-silica can be obtained by drying the nacre-like structure SMPI fire-resistant flame-retardant material at normal temperature. The silicon dioxide is still solid at the temperature of more than 1000 ℃, can block partial heat from being transferred to the interior, and is molten at the high temperature of more than 1500 ℃, so that oxides generated by the high-temperature decomposition of the hydroxide can be better bonded together, and the flame retardant capability is further improved. Wherein the coating thickness of the nano-silica sol is 10-50 μm, and the used nano-silica sol is commercial nano-silica sol.
The structure of the nacre-like structure SMPI fire-resistant flame-retardant material is shown in figure 3, and comprises a plurality of mud layers and brick layers which are mutually spaced, the nacre-like structure can improve the mechanical strength of the composite material, namely, the nacre-like structure is formed by arranging a plurality of flame-retardant layers (namely, the mud layers) and composite material layers (namely, the brick layers) at intervals, the nacre-like structure can burn layer by layer during burning, and the composite material layers keep shape memory performance during burning, so that active deformation action can be completed; in addition, during combustion, the flame retardant hydroxide can decompose oxides and water at high temperature, the reaction needs to absorb a large amount of heat, the oxides generated by the reaction can cover the surface of the polymer and prevent the heat from being transferred to the interior of the composite material, the nano silicon dioxide coated on the surface can still be in a solid state at the temperature of more than 1000 ℃, and can also prevent partial heat from being transferred to the interior, and the nano silicon dioxide is in a molten state at the high temperature of more than 1500 ℃, so that the oxides generated by the high-temperature decomposition of the hydroxide are better bonded together, and the flame retardant capability is improved.
The invention also provides a nacre-like structure SMPI fire-resistant flame-retardant material which is prepared by the preparation method of the nacre-like structure SMPI fire-resistant flame-retardant material.
Wherein, the thickness of the SMPI fire-resistant flame-retardant material with the nacre-like structure is 0.5-1.5 mm.
The SMPI fire-resistant flame-retardant material with the nacre-like structure has the glass transition temperature of 380-410 ℃, the normal-temperature storage modulus of 4.36GPa, the fire-resistant temperature of more than 1000 ℃, the tensile strength of 122.2MPa, the Young modulus of 3.6GPa, the shape fixing rate of 85-100 percent and the shape recovery rate of 80-100 percent, has good mechanical property, shape memory property and fire-resistant flame-retardant property, and lays a foundation for the application of an intelligent high polymer material in a high-temperature environment.
The invention further provides application of the nacre-like SMPI fire-resistant flame-retardant material as a fire-resistant intelligent material in the fields of high-speed aircrafts, active morphing wings and self-morphing skin materials.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
1.1, completely dissolving 4.9872g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) in 120mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
1.2, 6.5513g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added into an imidazole diamine solution for 3 times, the feeding step is completed within 30min, the reaction is carried out for 96h at the rotating speed of 250r/min in a nitrogen atmosphere at normal temperature to obtain 120mL of polyamic acid solution, and the solution is divided into two parts, each part is 60 mL;
1.3, putting 1.162g of silane coupling agent modified flame retardant aluminum hydroxide into one 60mL of polyamic acid solution, carrying out ultrasonic treatment for 60min, and uniformly mixing to obtain a flame retardant/polyamic acid composite solution;
1.4, pouring another 60mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and a solvent to obtain a polyamic acid/carbon fiber cloth composite material;
1.5, pouring the flame retardant/polyamic acid composite solution onto the surface of the polyamic acid/carbon fiber cloth composite material, placing the polyamic acid/carbon fiber cloth composite material into a vacuum oven, keeping the polyamic acid/carbon fiber cloth composite material at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
1.6, laminating the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then carrying out hot press molding under the conditions that the hot press is kept at 180 ℃ for 10min and then kept at 250 ℃ for 60min and the pressure is 4 MPa; the total thickness is 1.02 mm; then carrying out secondary thermal imidization, wherein the conditions of the secondary thermal imidization are that the heating rate is 1 ℃/min, the temperature is increased to 250 ℃, and the temperature is kept for 2 h; heating to 300 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, then coating a layer of nano silica sol with the thickness of 20 mu m on the surface of the material, and airing at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the nacre-like structure.
Fig. 4, fig. 5 and fig. 6 are graphs showing the storage modulus, the loss factor and the tensile strength of the nacre-like SMPI fire-resistant flame-retardant material prepared in this example, respectively, and it can be seen from fig. 4 to fig. 6 that the storage modulus of the nacre-like SMPI fire-resistant flame-retardant material prepared in this example is 4.36GPa at normal temperature, the glass transition temperature (Tg) is 398 ℃, that is, the shape memory transition temperature is 398 ℃, the tensile strength is 122.2MPa, and the young's modulus is 3.6 GPa.
For comparison, a flame retardant is directly mixed into a polyamic acid solution to obtain a composite solution, then carbon fiber cloth is soaked into the composite solution, after a solvent is volatilized, the carbon fiber cloth is subjected to hot press forming, nano silica sol with the same thickness is coated on the carbon fiber cloth, and then the carbon fiber cloth is dried at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the non-imitation nacre structure, wherein the thickness of the SMPI fire-resistant flame-retardant material is 1.02mm which is the same as that of the embodiment; fig. 7 is a tensile curve of the SMPI fire-resistant flame-retardant material with a non-imitation nacre structure, and it can be seen from fig. 7 that the tensile strength of the SMPI fire-resistant flame-retardant material is 106.7MPa, which is significantly lower than that of the SMPI fire-resistant flame-retardant material with an imitation nacre structure prepared in the present example.
Fig. 8 is a heat-driven deformation recovery diagram of the nacre-like SMPI fire-resistant flame-retardant material prepared in this embodiment, and as can be seen from fig. 8, under a 428 ℃ thermal environment, an external force is applied to shape the nacre-like SMPI fire-resistant flame-retardant material, the external force is removed after the temperature is reduced to normal temperature, the curved temporary shape is still maintained, and the nacre-like SMPI fire-retardant material can recover to the original shape after being heated to 428 ℃. Wherein the shape fixation rate is 92% and the shape recovery rate is 95%.
FIG. 9 is a photograph of the SMPI fire-resistant flame-retardant material with a mother-of-pearl imitation structure prepared in the present example, which is burned in a cassette furnace at a temperature of 1350 ℃; as can be seen from FIG. 9, the SMPI fire-resistant flame-retardant material with the nacre-like structure generates no open fire when being burnt by the cassette furnace, which shows that the SMPI fire-resistant flame-retardant material has good flame-retardant effect.
For comparison, in the preparation process, a flame retardant and a nano silica sol are not added, so as to obtain the nacre-like structure SMPI flame-resistant flame-retardant material without the flame retardant and the nano silica sol, and fig. 10 is a photograph of the nacre-like structure SMPI flame-resistant flame-retardant material without the flame retardant when the flame retardant is burned in a cassette furnace, wherein the burning temperature of the cassette furnace is 1350 ℃; as can be seen from FIG. 10, the SMPI fire-resistant flame-retardant material with the nacre-like structure containing no flame retardant generates open fire when being burnt by a cassette furnace, and has poor flame-retardant performance.
Example 2
2.1, completely dissolving 2.6693g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) in 80mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
2.2, 3.5211g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added into the imidazole diamine solution 4 times, the feeding step is completed within 30min, the reaction is carried out for 100h at the rotating speed of 250r/min in the nitrogen atmosphere at normal temperature to obtain 80mL of polyamic acid solution, and the solution is divided into two parts, each part is 40 mL;
2.3, 0.9255g of silane coupling agent modified flame retardant magnesium hydroxide is put into one part of 40mL of polyamic acid solution, ultrasonic treatment is carried out for 60min, and uniform mixing is carried out to obtain flame retardant/polyamic acid composite solution;
2.4, pouring another 40mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain the polyamic acid/carbon fiber cloth composite material;
2.5, pouring the flame retardant/polyamic acid composite solution onto the surface of the polyamic acid/carbon fiber cloth composite material, placing the polyamic acid/carbon fiber cloth composite material in a vacuum oven, keeping the polyamic acid/carbon fiber cloth composite material at the temperature of 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
2.6, stacking the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then carrying out hot press molding under the condition that the hot press is kept at 180 ℃ for 10min and then kept at 250 ℃ for 60min, wherein the pressure is 5 MPa; the total thickness is 0.76 mm; then carrying out secondary thermal imidization, wherein the conditions of the secondary thermal imidization are that the heating rate is 2 ℃/min, the temperature is increased to 250 ℃, and the temperature is kept for 2 h; heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, then coating a layer of nano silica sol with the thickness of 20 mu m on the surface of the material, and airing at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the nacre-like structure.
The SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure prepared by the embodiment has the storage modulus of 4.28GPa at normal temperature, the shape memory transition temperature of 397 ℃, the tensile strength of 115.8MPa, the Young modulus of 3.5GPa, the shape fixing rate of 92% and the shape recovery rate of 95%.
Example 3
3.1, completely dissolving 4.1497g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) in 100mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
3.2, 5.4729g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added into the imidazole diamine solution for 5 times, the feeding step is completed within 30min, the reaction is carried out for 120h at the rotating speed of 250r/min in the nitrogen atmosphere at normal temperature to obtain 100mL of polyamide acid solution, and the solution is divided into two parts, each part is 50 mL;
3.3, putting 1.9200g of silane coupling agent modified flame retardant magnesium hydroxide into one 50mL of polyamic acid solution, performing ultrasonic treatment for 60min, and uniformly mixing to obtain a flame retardant/polyamic acid composite solution;
3.4, pouring another 50mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain the polyamic acid/carbon fiber cloth composite material;
3.5, pouring the flame retardant/polyamic acid composite solution onto the surface of the polyamic acid/carbon fiber cloth composite material, placing the polyamic acid/carbon fiber cloth composite material in a vacuum oven, keeping the polyamic acid/carbon fiber cloth composite material at the temperature of 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
3.6, stacking the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then carrying out hot press molding under the condition that the hot press is kept at 180 ℃ for 10min and then kept at 250 ℃ for 60min, wherein the pressure is 3 MPa; the total thickness is 0.86 mm; then carrying out secondary thermal imidization, wherein the conditions of the secondary thermal imidization are that the heating rate is 2 ℃/min, the temperature is increased to 250 ℃, and the temperature is kept for 2 h; heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, then coating a layer of nano silica sol with the thickness of 20 mu m on the surface of the material, and airing at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the nacre-like structure.
The SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure prepared by the embodiment has the storage modulus of 4.30GPa at normal temperature, the shape memory transition temperature of 397 ℃, the tensile strength of 119.0MPa, the Young modulus of 3.6GPa, the shape fixing rate of 92% and the shape recovery rate of 94%.
Example 4
4.1, completely dissolving 4.9872g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) in 120mL of dimethyl sulfoxide to obtain an aromatic heterocyclic diamine solution containing imidazole;
4.2, 6.5423g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added into the imidazole diamine solution 4 times, the feeding step is completed within 30min, the reaction is carried out for 110h at the rotating speed of 250r/min in the nitrogen atmosphere at normal temperature to obtain 120mL of polyamic acid solution, and the solution is divided into two parts, each part is 60 mL;
4.3, putting 0.9323g of silane coupling agent modified flame retardant magnesium hydroxide into one 60mL of polyamic acid solution, performing ultrasonic treatment for 60min, and uniformly mixing to obtain a flame retardant/polyamic acid composite solution;
4.4, pouring another 60mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain the polyamic acid/carbon fiber cloth composite material;
4.5, pouring the flame retardant/polyamic acid composite solution onto the surface of the polyamic acid/carbon fiber cloth composite material, placing the polyamic acid/carbon fiber cloth composite material in a vacuum oven, keeping the polyamic acid/carbon fiber cloth composite material at the temperature of 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
4.6, laminating the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then carrying out hot press molding under the condition that the hot press is kept at 180 ℃ for 10min and then kept at 250 ℃ for 60min, wherein the pressure is 5 MPa; the total thickness is 1.03 mm; then carrying out secondary thermal imidization, wherein the conditions of the secondary thermal imidization are that the heating rate is 2 ℃/min, the temperature is increased to 250 ℃, and the temperature is kept for 2 h; heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, then coating a layer of nano silica sol with the thickness of 20 mu m on the surface of the material, and airing at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the nacre-like structure.
The SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure prepared by the embodiment has the storage modulus of 4.27GPa at normal temperature, the shape memory transition temperature of 398 ℃, the tensile strength of 120.3MPa, the Young modulus of 3.6GPa, the shape fixing rate of 91 percent and the shape recovery rate of 95 percent.
Example 5
5.1, completely dissolving 2.6693g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) in 50mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
5.2, 3.5211g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) is added into the imidazole diamine solution for 4 times, the feeding step is completed within 30min, the reaction is carried out for 110h at the rotating speed of 250r/min in the nitrogen atmosphere at normal temperature to obtain 50mL of polyamide acid solution, and the solution is divided into two parts, each part is 25 mL;
5.3, putting 1.1107g of silane coupling agent modified flame retardant aluminum hydroxide into one 25mL of polyamic acid solution, performing ultrasonic treatment for 60min, and uniformly mixing to obtain a flame retardant/polyamic acid composite solution;
5.4, pouring another 25mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain the polyamic acid/carbon fiber cloth composite material;
5.5, pouring the flame retardant/polyamic acid composite solution onto the surface of the polyamic acid/carbon fiber cloth composite material, placing the polyamic acid/carbon fiber cloth composite material in a vacuum oven, keeping the polyamic acid/carbon fiber cloth composite material at the temperature of 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
5.6, laminating the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then carrying out hot press molding under the condition that the hot press is kept at 180 ℃ for 10min and then kept at 250 ℃ for 60min, wherein the pressure is 5 MPa; the total thickness is 0.72 mm; then carrying out secondary thermal imidization, wherein the conditions of the secondary thermal imidization are that the heating rate is 2 ℃/min, the temperature is increased to 250 ℃, and the temperature is kept for 2 h; heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, then coating a layer of nano silica sol with the thickness of 20 mu m on the surface of the material, and airing at normal temperature to obtain the SMPI fire-resistant flame-retardant material with the nacre-like structure.
The SMPI fire-resistant flame-retardant material with the imitated mother-of-pearl structure prepared by the embodiment has the storage modulus of 4.16GPa at normal temperature, the shape memory transition temperature of 396 ℃, the tensile strength of 116.9MPa, the Young modulus of 3.3GPa, the shape fixing rate of 92% and the shape recovery rate of 93%.
In conclusion, the SMPI fire-resistant flame-retardant material with the nacre-like structure prepared by the embodiment of the invention has good mechanical property, shape memory property and fire-resistant flame-retardant property, and lays a foundation for the application of an intelligent high polymer material in a high-temperature environment.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. A preparation method of an SMPI (surface Mount Polymer) fireproof flame-retardant material with a mother-of-pearl imitating structure is characterized by comprising the following steps:
step S1, dissolving the imidazole-containing aromatic heterocyclic diamine in a solvent to obtain an imidazole-containing aromatic heterocyclic diamine solution;
step S2, adding biphenyl dianhydride into the imidazole-containing aromatic heterocyclic diamine solution under a protective atmosphere, and reacting for 96-120h to obtain a polyamic acid solution;
step S3, mixing a part of the polyamic acid solution with a flame retardant to obtain a flame retardant/polyamic acid composite solution;
step S4, pouring the other part of the polyamic acid solution onto the carbon fiber cloth, and drying in vacuum to obtain a polyamic acid/carbon fiber cloth composite material;
step S5, pouring the flame retardant/polyamic acid composite solution onto the polyamic acid/carbon fiber cloth composite material, and drying in vacuum to obtain the flame retardant/polyamic acid/carbon fiber cloth composite material;
and S6, laminating the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary hot imidization to obtain the SMPI flame-retardant material with the nacre-like structure.
2. The method for preparing the SMPI fire-resistant and flame-retardant material with the nacre-like structure as recited in claim 1, wherein in the step S1, the imidazole-containing aromatic heterocyclic diamine comprises 2- (4-aminophenyl) -5-aminobenzimidazole.
3. The method for preparing the SMPI fire-resistant flame-retardant material with the nacre-like structure as claimed in claim 1, wherein in the step S2, the biphenyl dianhydride comprises 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, and the mass ratio of the imidazole-containing aromatic heterocyclic diamine to the biphenyl dianhydride is 1: 1-1.01.
4. The method of claim 1, wherein the flame retardant comprises at least one of aluminum hydroxide and magnesium hydroxide.
5. The method for preparing the nacre-like SMPI fire-resistant flame-retardant material according to claim 1, wherein the flame retardant is a silane coupling agent modified flame retardant, and the silane coupling agent comprises KH550 or KH 560.
6. The method for preparing the SMPI flame-retardant material with the mother-of-pearl structure according to claim 1, wherein in the step S6, the hot-press molding conditions are as follows: keeping the temperature at 175-185 ℃ for 5-15min, and then keeping the temperature at 245-255 ℃ for 55-65min, and the pressure is 3-5 MPa.
7. The method for preparing the SMPI flame retardant material with the mother-of-pearl imitated structure according to claim 1, wherein in the step S6, the secondary thermal imidization step is: the heating rate is 1-2 ℃/min, the temperature is raised to 245 ℃ and 255 ℃, and the temperature is kept for 1.5-2.5 h; the heating rate is 1-2 ℃/min, the temperature is raised to 295-305 ℃, and the temperature is kept for 1.5-2.5 h.
8. An SMPI fire-resistant flame-retardant material with a mother-of-pearl imitation structure, which is prepared by the preparation method of the SMPI fire-resistant flame-retardant material with the mother-of-pearl imitation structure according to any one of claims 1-7.
9. The SMPI flame retardant material of claim 8, wherein the thickness is 0.5-1.5 mm.
10. Use of the SMPI flame-retardant material with a mother-of-pearl structure obtained by the method for preparing the SMPI flame-retardant material with a mother-of-pearl structure according to any one of claims 1 to 7 or the SMPI flame-retardant material with a mother-of-pearl structure according to any one of claims 8 to 9 as a flame-retardant smart material in the fields of high-speed aircrafts, active morphing wings and self-morphing skin materials.
CN202210569218.3A 2022-05-24 2022-05-24 SMAI (styrene-butadiene-styrene) fireproof flame-retardant material with mother-of-pearl structure, and preparation method and application thereof Active CN114889235B (en)

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CN104553177A (en) * 2014-12-15 2015-04-29 中航复合材料有限责任公司 Flame-retardant modified carbon fiber prepreg and composite material product
CN108641355A (en) * 2018-04-25 2018-10-12 哈尔滨工业大学 A kind of high-modulus shape memory composite polyimide material and preparation method thereof
CN109651611A (en) * 2018-12-29 2019-04-19 哈尔滨工业大学 A kind of shape memory polyimides prepreg, composite material and preparation method
CN114773601A (en) * 2022-05-24 2022-07-22 哈尔滨工业大学 high-Tg and high-modulus shape memory flame-retardant polyimide and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104553177A (en) * 2014-12-15 2015-04-29 中航复合材料有限责任公司 Flame-retardant modified carbon fiber prepreg and composite material product
CN108641355A (en) * 2018-04-25 2018-10-12 哈尔滨工业大学 A kind of high-modulus shape memory composite polyimide material and preparation method thereof
CN109651611A (en) * 2018-12-29 2019-04-19 哈尔滨工业大学 A kind of shape memory polyimides prepreg, composite material and preparation method
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