CN114889235B - SMAI (styrene-butadiene-styrene) fireproof flame-retardant material with mother-of-pearl structure, and preparation method and application thereof - Google Patents
SMAI (styrene-butadiene-styrene) fireproof flame-retardant material with mother-of-pearl structure, and preparation method and application thereof Download PDFInfo
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- CN114889235B CN114889235B CN202210569218.3A CN202210569218A CN114889235B CN 114889235 B CN114889235 B CN 114889235B CN 202210569218 A CN202210569218 A CN 202210569218A CN 114889235 B CN114889235 B CN 114889235B
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- flame retardant
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000003063 flame retardant Substances 0.000 title claims abstract description 180
- 239000000463 material Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title abstract description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 title abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002131 composite material Substances 0.000 claims abstract description 85
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 77
- 239000004917 carbon fiber Substances 0.000 claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000004744 fabric Substances 0.000 claims abstract description 76
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 58
- 239000004952 Polyamide Substances 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 57
- 229920002647 polyamide Polymers 0.000 claims abstract description 57
- -1 aromatic heterocyclic diamine Chemical class 0.000 claims abstract description 41
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 30
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 15
- 239000004305 biphenyl Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000009970 fire resistant effect Effects 0.000 claims description 40
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 10
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 239000002520 smart material Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 6
- 238000007731 hot pressing Methods 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000011449 brick Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 230000007334 memory performance Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000431 shape-memory polymer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- 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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
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- 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
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- 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
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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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
- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- 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
- B64C2001/0072—Fuselage structures substantially made from particular materials from composite materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
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- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Aviation & Aerospace Engineering (AREA)
- Physics & Mathematics (AREA)
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- Fluid Mechanics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a mother-of-pearl structure-imitated SMPI (styrene-butadiene-styrene) fireproof flame-retardant material and a preparation method thereof, wherein the preparation method of the mother-of-pearl structure-imitated SMPI fireproof flame-retardant material comprises the following steps: dissolving aromatic heterocyclic diamine containing imidazole in a solvent; adding biphenyl dianhydride into the aromatic heterocyclic diamine solution containing imidazole; mixing a portion of the polyamic acid solution with a flame retardant; casting another part of the polyamic acid solution onto carbon fiber cloth; pouring the flame retardant/polyamide acid composite solution onto the polyamide acid/carbon fiber cloth composite material; and stacking the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, hot-pressing, forming and carrying out secondary thermal imidization to obtain the SMAI fireproof flame retardant material with the imitation mother-of-pearl structure. The SMPI flame-retardant material with the imitation pearl shell structure prepared by the preparation method provided by the invention has good mechanical property, shape memory property and flame-retardant property, and lays a foundation for the application of the intelligent high polymer material in a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of fire-resistant flame-retardant materials, in particular to a mother-of-pearl structure-imitated SMPI fire-resistant flame-retardant material, a preparation method and application thereof.
Background
Shape memory polymers (Shape Memory Polymer, SMP) are smart materials that are capable of responding to external stimuli such as heat, light, electricity, magnetism, or chemicals, and polymers with shape memory effects retain a temporary shape after being shaped and return to their original shape prior to deformation under external stimuli. Polyimide (Shape Memory 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, expandable structures and the like.
Polyimide (PI) belongs to self-extinguishing materials, has a limiting oxygen index of up to 38%, can be carbonized when meeting open fire at high temperature, has no molten drop, self-extinguishes when being away from fire, is nontoxic, is a variety with the best heat resistance in the industrial high polymer materials, and can meet the flame retardant requirements in most fields. However, in some special fields, the flame retardant requirement on PI is more severe, so in order to meet the requirements in the special fields, the PI needs to be flame retardant modified to improve the flame retardant property of PI.
Disclosure of Invention
The invention solves the problem of how to provide the shape memory polyimide fire-resistant flame-retardant material with a mother-of-pearl structure, which has 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 problems, the invention provides a preparation method of a fire-resistant flame-retardant material of a mother-of-pearl structure-imitated SMPI, which comprises the following steps:
s1, dissolving imidazole-containing aromatic heterocyclic diamine in a solvent to obtain imidazole-containing aromatic heterocyclic diamine solution;
s2, adding biphenyl dianhydride into the aromatic heterocyclic diamine solution containing imidazoles under a protective atmosphere, and reacting for 96-120 hours to obtain 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;
s4, pouring another part of the polyamic acid solution onto carbon fiber cloth, and vacuum drying to obtain a polyamic acid/carbon fiber cloth composite material;
s5, pouring the flame retardant/polyamide acid composite solution onto the polyamide acid/carbon fiber cloth composite material, and vacuum drying to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
and S6, stacking the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary thermal imidization to obtain the SMAI flame-retardant material with the imitation mother-of-pearl structure.
Preferably, in the step S1, the imidazole-containing aromatic heterocyclic diamine includes 2- (4-aminophenyl) -5-aminobenzimidazole.
Preferably, in the step S2, the biphenyl dianhydride includes 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the mass 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 KH560.
Preferably, in the step S6, the hot press molding conditions are: maintaining at 175-185 deg.C for 5-15min, and maintaining at 245-255 deg.C for 55-65min under 3-5MPa.
Preferably, in the step S6, the secondary thermal imidization step is: the temperature rising rate is 1-2 ℃/min, the temperature rises to 245-255 ℃, and the temperature is kept for 1.5-2.5h; the temperature rising rate is 1-2 ℃/min, the temperature rises to 295-305 ℃, and the temperature is kept for 1.5-2.5h.
The invention forms a polyamic acid solution by polycondensing aromatic heterocyclic diamine containing imidazoles and biphenyldiamine, then forms a flame retardant/polyamic acid composite solution by partial polyamic acid solution and flame retardant, forms a polyamic acid/carbon fiber cloth composite material by partial polyamic acid pouring to carbon fiber cloth, then forms a polyimide with shape memory by flame retardant/polyamic acid/carbon fiber cloth composite material pouring to the polyamic acid/carbon fiber cloth composite material, and then forms a composite material with a 'brick-mud' structure by overlapping the flame retardant/polyamic acid/carbon fiber cloth composite material layer by layer and hot pressing, so that the composite material has a mother-of-pearl structure, and finally forms polyimide with shape memory by secondary thermal imidization; the glass transition temperature of the mother-of-pearl structure-imitated SMPI flame-retardant material prepared by the preparation method of the mother-of-pearl structure-imitated SMPI flame-retardant material is 380-410 ℃, the normal-temperature storage modulus is 4.36GPa, the flame-retardant temperature is greater than 1000 ℃, the tensile strength is 122.2MPa, the Young modulus is 3.6GPa, the shape fixation rate is 85-100%, the shape recovery rate is 80-100%, the mother-of-pearl structure-imitated SMPI flame-retardant material has good mechanical property, shape memory property and flame-retardant property, and a foundation is laid for the application of the intelligent high polymer material in a high-temperature environment.
The invention also aims to provide the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure, which is prepared by adopting the preparation method of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure.
Preferably, the thickness of the SMPI fire resistant and flame retardant material with the mother-of-pearl structure is 0.5-1.5mm.
Compared with the prior art, the SMPI flame-retardant material with the mother-of-pearl structure has the beneficial effects that the SMPI flame-retardant material with the mother-of-pearl structure is the same as the preparation method of the SMPI flame-retardant material with the mother-of-pearl structure, and the description is omitted.
The invention also aims to provide the application of the fire-resistant flame-retardant material of the mother-of-pearl structure-imitated SMPI as a fire-resistant intelligent material in the fields of high-speed aircrafts, active deformation wings and autonomous deformation skin materials.
Compared with the prior art, the application of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure has the beneficial effects that the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure is the same as the preparation method of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure, and the description is omitted.
Drawings
FIG. 1 is a flow chart of a method for preparing a mother-of-pearl structure imitated SMPI flame-resistant material according to an embodiment of the invention;
FIG. 2 is a schematic diagram of a preparation path of a flame retardant/polyimide/carbon fiber cloth composite material according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a mother-of-pearl "brick-mud" structure and flame retardant mechanism of a mother-of-pearl-like SMPI flame retardant material in an embodiment of the invention;
FIG. 4 is a graph showing the storage modulus of the SMPI refractory flame retardant material having a mother-of-pearl structure in example 1 of the present invention;
FIG. 5 is a graph of the loss factor of the SMPI refractory flame retardant material of the mother-of-pearl structure in example 1 of the present invention;
FIG. 6 is a drawing of a tensile curve of a mother-of-pearl structure imitated SMPI flame resistant material of example 1 of the present invention;
FIG. 7 is a drawing of a tensile curve of a non-mother-of-pearl structure SMPI refractory flame retardant material;
FIG. 8 is a thermal deformation recovery chart of the SMPI refractory flame retardant material with a mother-of-pearl structure in example 1 of the present invention;
FIG. 9 is a schematic diagram of the combustion of a mother-of-pearl structure imitated SMPI flame retardant material in a card furnace (1350 ℃ C.) according to example 1 of the present invention;
FIG. 10 is a diagram of the burning of a fire retardant, simulated nacre structured SMPI fire resistant material without flame retardant in a cartridge furnace (temperature 1350 ℃).
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that, without conflict, features in the embodiments of the present invention may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment, reagents are commercially available unless otherwise specified.
The embodiment of the invention provides a preparation method of a mother-of-pearl structure imitated SMPI fireproof flame-retardant material, as shown in figure 1, comprising the following steps:
s1, dissolving imidazole-containing aromatic heterocyclic diamine in a solvent to obtain imidazole-containing aromatic heterocyclic diamine solution;
s2, adding biphenyl dianhydride into the aromatic heterocyclic diamine solution containing imidazoles under a protective atmosphere, and reacting for 96-120 hours to obtain 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;
s4, pouring another part of the polyamic acid solution onto carbon fiber cloth, and vacuum drying to obtain a polyamic acid/carbon fiber cloth composite material;
s5, pouring the flame retardant/polyamide acid composite solution onto the polyamide acid/carbon fiber cloth composite material, and vacuum drying to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
and S6, stacking the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary thermal imidization to obtain the SMAI flame-retardant material with the imitation mother-of-pearl 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, especially 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 solvent is heated to dissolve, the reaction temperature is increased, thereby affecting the polycondensation reaction of the imidazole-containing aromatic heterocyclic diamine and the biphenyl dianhydride.
In the step S2, the biphenyl dianhydride comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), the mass ratio of the imidazole-containing aromatic heterocyclic diamine to the biphenyl dianhydride is 1:1-1.01, the concentration of the polyamide acid in the obtained polyamide acid solution is 6-16wt%, and the protective atmosphere comprises nitrogen atmosphere and is reacted at normal temperature.
In order to enable the aromatic heterocyclic diamine containing imidazole to react with biphenyl dianhydride more thoroughly, the reaction is carried out for 96-120h under the condition of the rotating speed of 200-500 r/min.
The polyamic acid solution obtained in the step S2 is divided into two parts, wherein one part is used for being mixed with a flame retardant, and the other part is used for being combined with carbon fiber cloth. Illustratively, the polyamic acid may be equally divided into two parts for subsequent steps.
In the 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 in an ultrasonic mode, wherein the ultrasonic time is 60-90min; the flame retardant comprises at least one of aluminum hydroxide and magnesium hydroxide, and in order to improve the compatibility of the flame retardant and polyamide acid and improve the interfacial binding force of the flame retardant and the composite material, the flame retardant is modified by a silane coupling agent, wherein the silane coupling agent comprises KH550 or KH560. 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 being flame retardant, so that the flame retardant is environment-friendly.
Wherein the addition amount of the flame retardant is 5-40wt% of the total amount of imidazole-containing aromatic heterocyclic diamine and biphenyl dianhydride, namely the flame retardant accounts for 5-40wt% of the total amount of imidazole-containing aromatic heterocyclic diamine and biphenyl dianhydride; the flame retardant is granular flame retardant with the size of 2-10 mu m.
And in the step S4, pouring another part of the polyamic acid solution onto carbon fiber cloth, and vacuum drying to obtain the polyamic acid/carbon fiber cloth composite material.
Specifically, pouring another part of the polyamic acid solution onto carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, maintaining the temperature at 45-55 ℃ for 11.5-12.5h, and vacuumizing to remove bubbles and solvents in the polyamic acid solution, thereby obtaining the polyamic acid/carbon fiber cloth composite material, 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 carbon content of more than 90%, has excellent high-temperature resistance, is an excellent material for manufacturing high-technology equipment such as aerospace and the like, has a theoretical temperature resistance of more than 2600 ℃, and can improve the high-temperature resistance of the material by using carbon fiber cloth.
And in the step S5, pouring the flame retardant/polyamide acid composite solution onto the polyamide acid/carbon fiber cloth composite material, and carrying out vacuum drying to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material.
Specifically, the flame retardant/polyamide acid composite solution is poured onto the polyamide acid/carbon fiber cloth composite material, the polyamide acid/carbon fiber cloth composite material is placed in a vacuum oven, the temperature is kept at 45-55 ℃ for 11.5-12.5 hours, and the solvent is removed, so that the flame retardant/polyamide acid/carbon fiber cloth composite material is obtained by combining the flame retardant/polyamide acid/carbon fiber cloth composite material. Wherein, the flame retardant/polyamide acid composite solution is equivalent to a mud layer in the mother-of-pearl imitation structure, and the polyamide acid/carbon fiber cloth composite material is equivalent to a brick layer in the mother-of-pearl imitation structure.
In step S6, the flame retardant/polyamide acid/carbon fiber cloth composite material is laminated layer by layer, hot-pressed and formed, and then subjected to secondary thermal imidization to obtain the SMAI flame-retardant material with the imitation mother-of-pearl structure.
The fire-resistant flame-retardant material of the SMAI with the mother-of-pearl structure consists of a plurality of flame retardant/polyimide/carbon fiber cloth composite materials which are laminated layer by layer. Illustratively, when the imidazole-containing aromatic heterocyclic diamine is DAPBI, the biphenyl diamine is BPDA, and the flame retardant is a silane coupling agent modified flame retardant, the path of the flame retardant/polyimide/carbon fiber cloth composite material is shown in fig. 2, DAPBI and BPDA are polycondensed to obtain polyamic acid, then the polyamic acid, the silane coupling agent modified flame retardant and the carbon fiber cloth are compounded, and then hot pressing and secondary thermal imidization are performed to obtain the flame retardant/polyimide/carbon fiber cloth composite material.
Specifically, the hot press molding conditions are: maintaining at 175-185 deg.C for 5-15min, and maintaining at 245-255 deg.C for 55-65min under 3-5MPa; the secondary thermal imidization step is as follows: the temperature rising rate is 1-2 ℃/min, the temperature rises to 245-255 ℃, and the temperature is kept for 1.5-2.5h; the temperature rising rate is 1-2 ℃/min, the temperature rises to 295-305 ℃, and the temperature is kept for 1.5-2.5h. 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 multi-layer 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 SMPI fire-resistant flame-retardant material with the simulated mother-of-pearl structure, after secondary thermal imidization, a layer of nano silica sol can be coated on the surface of the SMPI fire-resistant flame-retardant material, and then the SMPI fire-resistant flame-retardant material with the simulated mother-of-pearl structure, coated with a layer of nano silica, is obtained after drying at normal temperature. Because the silicon dioxide is still solid at the temperature of more than 1000 ℃, part of heat can be prevented from being transferred to the inside, and the silicon dioxide is in a molten state in a high-temperature environment at the temperature of more than 1500 ℃, oxides generated by high-temperature decomposition of hydroxide can be bonded together better, and thus, the flame retardant capability is further improved. Wherein the coating thickness of the nano silica sol is 10-50 mu m, and the nano silica sol is commercial nano silica sol.
The structure of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure is shown in figure 3, the structure comprises a plurality of mud layers and brick layers which are mutually spaced, the mother-of-pearl structure can improve the mechanical strength of the composite material, the structure is equivalent to the arrangement of the plurality of flame-retardant layers (namely the mud layers) and the composite material layers (namely the brick layers) at intervals, the fire-retardant layers can burn layer by layer during combustion, the shape memory performance of the composite material layers is maintained during combustion, and the active deformation action can be completed; in addition, during combustion, the flame retardant hydroxide can decompose oxide and water at high temperature, and the reaction needs to absorb a large amount of heat, and the oxide generated by the reaction can cover the surface of the polymer to block heat from being transferred to the inside of the composite material, and the nano silicon dioxide coated on the surface can still be solid at more than 1000 ℃ and also can block part of heat from being transferred to the inside, and is in a molten state in a high-temperature environment exceeding 1500 ℃, so that the oxide generated by the high-temperature decomposition of the hydroxide can be bonded together better, and the flame retardant capability is improved.
Another embodiment of the invention provides a fire-resistant flame-retardant material of the SMPI with the mother-of-pearl structure, which is prepared by adopting the preparation method of the fire-resistant flame-retardant material of the SMPI with the mother-of-pearl structure.
Wherein, the thickness of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure is 0.5-1.5mm.
The glass transition temperature of the mother-of-pearl structure-imitated SMPI flame-retardant material is 380-410 ℃, the normal-temperature storage modulus is 4.36GPa, the flame-retardant temperature is more than 1000 ℃, the tensile strength is 122.2MPa, the Young modulus is 3.6GPa, the shape fixation rate is 85-100%, the shape recovery rate is 80-100%, the glass transition temperature is good, the shape memory performance and the flame-retardant performance are good, and a foundation is laid for the application of the intelligent high polymer material in a high-temperature environment.
The invention further provides application of the mother-of-pearl structure imitated SMPI fireproof flame-retardant material as a fireproof intelligent material in the fields of high-speed aircrafts, active deformation wings and autonomous deformation skin materials.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
4.9872g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) was completely dissolved in 120mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
1.2, adding 6.5513g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) into imidazole diamine solution for 3 times, completing the feeding step within 30 minutes, reacting for 96 hours at the rotating speed of 250r/min in a nitrogen atmosphere at normal temperature to obtain 120mL of polyamic acid solution, and equally dividing the solution into two parts, wherein each part is 60mL;
1.3, 1.162g of silane coupling agent modified flame retardant aluminum hydroxide is put into one 60mL polyamide acid solution, and is subjected to ultrasonic treatment for 60min, and the mixture is uniformly mixed to obtain a flame retardant/polyamide acid composite solution;
1.4, pouring another 60mL polyamide acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, maintaining at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain a polyamide acid/carbon fiber cloth composite material;
1.5, pouring the flame retardant/polyamide acid composite solution onto the surface of the polyamide acid/carbon fiber cloth composite material, placing the material in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
1.6, stacking the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then performing hot press forming, wherein the hot press condition is 180 ℃ for 10min, then 250 ℃ for 60min, and the pressure is 4MPa; the total thickness is 1.02mm; carrying out secondary thermal imidization, wherein the condition of the secondary thermal imidization is that the heating rate is 1 ℃/min, heating to 250 ℃, and keeping for 2 hours; heating to 300 ℃ at a heating rate of 1 ℃/min, maintaining for 2 hours, coating a layer of nano silica sol with a 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 imitation mother-of-pearl structure.
Fig. 4, 5 and 6 are respectively storage modulus, loss factor and tensile curve graphs of the SMPI refractory flame retardant material with the mother-of-pearl structure prepared in this embodiment, and as can be seen from fig. 4 to 6, the storage modulus of the SMPI refractory flame retardant material with the mother-of-pearl structure prepared in this embodiment is 4.36GPa, 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 modulus is 3.6GPa.
By contrast, the flame retardant is directly mixed into the polyamic acid solution to obtain a composite solution, then the carbon fiber cloth is immersed into the composite solution, after the solvent is volatilized, the composite solution is hot-pressed, formed and coated with nano silica sol with the same thickness, and then dried at normal temperature to obtain the SMAI fireproof flame retardant material with a non-imitation mother-of-pearl structure, wherein the thickness of the SMAI fireproof flame retardant material is 1.02mm as the thickness of the SMAI fireproof flame retardant material in the embodiment; fig. 7 shows a tensile curve of the non-mother-of-pearl-like-structured SMPI fire-resistant flame-retardant material, and as can be seen from fig. 7, the tensile strength of the non-mother-of-pearl-like-structured SMPI fire-resistant flame-retardant material is 106.7MPa, which is significantly lower than that of the mother-of-pearl-like-structured SMPI fire-resistant flame-retardant material prepared in this example.
Fig. 8 is a thermal deformation recovery chart of the SMPI refractory flame retardant material with a mother-of-pearl structure prepared in this embodiment, and as can be seen from fig. 8, in a thermal environment at 428 ℃, external force is applied to shape the SMPI refractory flame retardant material with a mother-of-pearl structure, after the temperature is reduced to normal temperature, the external force is removed, the temporary shape of the curve is still maintained, and after the temperature is heated to 428 ℃, the original shape can be recovered. Wherein the shape fixation rate was 92% and the shape recovery rate was 95%.
FIG. 9 is a photograph of the mother-of-pearl structure imitated SMPI flame retardant material prepared in this example when burned in a card furnace, wherein the burning temperature of the card furnace is 1350 ℃; as can be seen from fig. 9, the SMPI refractory flame retardant material with the mother-of-pearl structure is burned by the clip type furnace without open flame, which indicates that the SMPI refractory flame retardant material has a good flame retardant effect.
By contrast, without adding flame retardant and nano silica sol during the preparation process, a mother-of-pearl structure-imitated SMPI flame-retardant material without flame retardant and nano silica sol is obtained, and FIG. 10 is a photograph of the mother-of-pearl structure-imitated SMPI flame-retardant material without flame retardant under the combustion of a card-type furnace, wherein the combustion temperature of the card-type furnace is 1350 ℃; as can be seen from fig. 10, when the fire retardant-free SMPI fire-resistant material with a mother-of-pearl structure is burned by a card furnace, open fire is generated, and the fire retardant performance is poor.
Example 2
2.6693g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) was completely dissolved in 80mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
2.2, adding 3.5211g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) into imidazole diamine solution for 4 times, completing the feeding step within 30min, reacting for 100h at the rotating speed of 250r/min in nitrogen atmosphere at normal temperature to obtain 80mL of polyamic acid solution, and equally dividing the solution into two parts, wherein each part is 40mL;
2.3, adding 0.9255g of silane coupling agent modified flame retardant magnesium hydroxide into one 40mL of polyamic acid solution, carrying out ultrasonic treatment for 60min, and uniformly mixing to obtain a 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, maintaining at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain a polyamic acid/carbon fiber cloth composite material;
2.5, pouring the flame retardant/polyamide acid composite solution onto the surface of the polyamide acid/carbon fiber cloth composite material, placing the material in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamide 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 performing hot press forming, wherein the hot press condition is that the temperature is 180 ℃ and the temperature is kept for 10min, then the temperature is 250 ℃ and the pressure is 5MPa; the total thickness is 0.76mm; carrying out secondary thermal imidization, wherein the condition of the secondary thermal imidization is that the temperature rising rate is 2 ℃/min, the temperature is raised to 250 ℃, and the temperature is kept for 2 hours; heating to 300 ℃ at a heating rate of 2 ℃/min, maintaining for 2h, coating a layer of nano silica sol with a 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 imitation mother-of-pearl structure.
The mother-of-pearl structure-imitated SMPI fireproof flame-retardant material prepared by the embodiment has the storage modulus of 4.28GPa, the shape memory transition temperature of 397 ℃, the tensile strength of 115.8MPa, the Young modulus of 3.5GPa, the shape fixation rate of 92% and the shape recovery rate of 95%.
Example 3
4.1497g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) was completely dissolved in 100mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
3.2, adding 5.4729g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) into imidazole diamine solution for 5 times, completing the feeding step within 30min, reacting for 120h at the rotating speed of 250r/min in nitrogen atmosphere at normal temperature to obtain 100mL of polyamic acid solution, and equally dividing the solution into two parts, wherein each part is 50mL;
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 the other 50mL of polyamic acid solution onto carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, maintaining at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain a polyamic acid/carbon fiber cloth composite material;
3.5, pouring the flame retardant/polyamide acid composite solution onto the surface of the polyamide acid/carbon fiber cloth composite material, placing the material in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamide 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 performing hot press forming, wherein the hot press condition is that the temperature is 180 ℃ and the temperature is kept for 10min, then the temperature is 250 ℃ and the pressure is 3MPa; the total thickness is 0.86mm; carrying out secondary thermal imidization, wherein the condition of the secondary thermal imidization is that the temperature rising rate is 2 ℃/min, the temperature is raised to 250 ℃, and the temperature is kept for 2 hours; heating to 300 ℃ at a heating rate of 2 ℃/min, maintaining for 2h, coating a layer of nano silica sol with a 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 imitation mother-of-pearl structure.
The mother-of-pearl structure-imitated SMPI fireproof flame-retardant material prepared by the embodiment has the storage modulus of 4.30GPa, the shape memory transition temperature of 397 ℃, the tensile strength of 119.0MPa, the Young modulus of 3.6GPa, the shape fixation rate of 92% and the shape recovery rate of 94%.
Example 4
4.9872g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) was completely dissolved in 120mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
4.2, adding 6.5423g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) into imidazole diamine solution for 4 times, completing the feeding step within 30 minutes, reacting for 110 hours at the rotating speed of 250r/min in a nitrogen atmosphere at normal temperature to obtain 120mL of polyamic acid solution, and equally dividing the solution into two parts, wherein each part is 60mL;
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 the other 60mL of polyamic acid solution onto carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, maintaining at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain a polyamic acid/carbon fiber cloth composite material;
4.5, pouring the flame retardant/polyamide acid composite solution onto the surface of the polyamide acid/carbon fiber cloth composite material, placing the material in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
4.6, stacking the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then performing hot press forming, wherein the hot press condition is 180 ℃ for 10min, then 250 ℃ for 60min, and the pressure is 5MPa; the total thickness is 1.03mm; carrying out secondary thermal imidization, wherein the condition of the secondary thermal imidization is that the temperature rising rate is 2 ℃/min, the temperature is raised to 250 ℃, and the temperature is kept for 2 hours; heating to 300 ℃ at a heating rate of 2 ℃/min, maintaining for 2h, coating a layer of nano silica sol with a 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 imitation mother-of-pearl structure.
The mother-of-pearl structure-imitated SMPI fireproof flame-retardant material prepared by the embodiment has the storage modulus of 4.27GPa, the shape memory transition temperature of 398 ℃, the tensile strength of 120.3MPa, the Young's modulus of 3.6GPa, the shape fixation rate of 91% and the shape recovery rate of 95%.
Example 5
2.6693g of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) was completely dissolved in 50mL of dimethyl sulfoxide to obtain an imidazole-containing aromatic heterocyclic diamine solution;
5.2, adding 3.5211g of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) into imidazole diamine solution for 4 times, completing the feeding step within 30min, reacting for 110h at the rotating speed of 250r/min in nitrogen atmosphere at normal temperature to obtain 50mL of polyamic acid solution, and equally dividing the solution into two parts, wherein each part is 25mL;
5.3, putting 1.1107g of silane coupling agent modified flame retardant aluminum hydroxide into one 25mL of polyamide acid solution, carrying out ultrasonic treatment for 60min, and uniformly mixing to obtain a flame retardant/polyamide acid composite solution;
5.4, pouring the other 25mL of polyamic acid solution onto the carbon fiber cloth, placing the carbon fiber cloth in a vacuum oven, maintaining at 50 ℃ for 12 hours, vacuumizing, and removing bubbles and solvent to obtain a polyamic acid/carbon fiber cloth composite material;
5.5, pouring the flame retardant/polyamide acid composite solution onto the surface of the polyamide acid/carbon fiber cloth composite material, placing the material in a vacuum oven, keeping the temperature at 50 ℃ for 12 hours, and removing the solvent to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
5.6, stacking the obtained flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, and then performing hot press forming, wherein the hot press condition is that the temperature is 180 ℃ and the temperature is kept for 10min, then the temperature is 250 ℃ and the pressure is 5MPa; the total thickness is 0.72mm; carrying out secondary thermal imidization, wherein the condition of the secondary thermal imidization is that the temperature rising rate is 2 ℃/min, the temperature is raised to 250 ℃, and the temperature is kept for 2 hours; heating to 300 ℃ at a heating rate of 2 ℃/min, maintaining for 2h, coating a layer of nano silica sol with a 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 imitation mother-of-pearl structure.
The mother-of-pearl structure-imitated SMPI fireproof flame-retardant material prepared by the embodiment has the storage modulus of 4.16GPa, the shape memory transition temperature of 396 ℃, the tensile strength of 116.9MPa, the Young's modulus of 3.3GPa, the shape fixation rate of 92% and the shape recovery rate of 93%.
In conclusion, the SMPI flame-retardant material with the imitated mother-of-pearl structure prepared by the embodiment of the invention has good mechanical property, shape memory property and flame-retardant property, and lays a foundation for the application of the intelligent high polymer material in a high-temperature environment.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (8)
1. The preparation method of the SMPI fire-resistant flame-retardant material with the mother-of-pearl structure is characterized by comprising the following steps:
s1, dissolving imidazole-containing aromatic heterocyclic diamine in a solvent to obtain imidazole-containing aromatic heterocyclic diamine solution;
s2, adding biphenyl dianhydride into the aromatic heterocyclic diamine solution containing imidazoles under a protective atmosphere, and reacting for 96-120 hours to obtain 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;
s4, pouring another part of the polyamic acid solution onto carbon fiber cloth, and vacuum drying to obtain a polyamic acid/carbon fiber cloth composite material;
s5, pouring the flame retardant/polyamide acid composite solution onto the polyamide acid/carbon fiber cloth composite material, and vacuum drying to obtain the flame retardant/polyamide acid/carbon fiber cloth composite material;
s6, stacking the flame retardant/polyamide acid/carbon fiber cloth composite material layer by layer, performing hot press molding, and performing secondary thermal imidization to obtain the SMAI flame-retardant material with the mother-of-pearl structure;
in the step S6, after secondary thermal imidization, a layer of nano silicon dioxide sol is coated on the surface, and then the surface is dried at normal temperature to obtain the SMPI flame-retardant material with the imitation pearl shell structure, which is coated with a layer of nano silicon dioxide;
the flame retardant comprises at least one of aluminum hydroxide and magnesium hydroxide;
in the step S1, the aromatic heterocyclic diamine containing imidazole comprises 2- (4-aminophenyl) -5-aminobenzimidazole;
in the step S2, the biphenyl dianhydride comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the mass ratio of the aromatic heterocyclic diamine containing imidazole to the biphenyl dianhydride is 1:1-1.01;
the addition amount of the flame retardant is 5-40wt% of the total amount of the imidazole-containing aromatic heterocyclic diamine and the biphenyl dianhydride.
2. The method for preparing the fire-resistant flame-retardant material of the SMPI with the mother-of-pearl structure according to claim 1 wherein the flame retardant is a modified flame retardant of a silane coupling agent, and the silane coupling agent comprises KH550 or KH560.
3. The method for preparing the SMPI refractory flame retardant material with a mother-of-pearl structure according to claim 1, wherein in the step S6, the hot press molding conditions are as follows: maintaining at 175-185 deg.C for 5-15min, and maintaining at 245-255 deg.C for 55-65min under 3-5MPa.
4. The method for preparing the fire-retardant material of the SMPI with the mother-of-pearl structure according to claim 1, wherein in the step S6, the secondary thermal imidization step is: the temperature rising rate is 1-2 ℃/min, the temperature rises to 245-255 ℃, and the temperature is kept for 1.5-2.5h; the temperature rising rate is 1-2 ℃/min, the temperature rises to 295-305 ℃, and the temperature is kept for 1.5-2.5h.
5. The fire-resistant flame-retardant material of the SMPI with the mother-of-pearl structure, which is characterized by being prepared by adopting the preparation method of the fire-resistant flame-retardant material of the SMPI with the mother-of-pearl structure as claimed in any one of claims 1 to 4.
6. The mother-of-pearl imitated SMPI fire resistant and flame retardant material according to claim 5 wherein the thickness is 0.5-1.5mm.
7. Use of the mother-of-pearl imitated SMPI fire resistant and resistant material according to any one of claims 5 to 6 as a fire resistant smart material in the field of high speed aircraft.
8. Use of the mother-of-pearl imitated SMPI fire resistant and resistant material according to any of claims 5 to 6 as an intelligent fire resistant material in actively deforming wings and autonomously deforming skin materials.
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| CN202210569218.3A CN114889235B (en) | 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 |
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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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Patent Citations (4)
| 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 |
| 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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