CN112812540A - Hydroxyl and amino modified anti-knock composite material and preparation method thereof - Google Patents
Hydroxyl and amino modified anti-knock composite material and preparation method thereof Download PDFInfo
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- CN112812540A CN112812540A CN202011621502.8A CN202011621502A CN112812540A CN 112812540 A CN112812540 A CN 112812540A CN 202011621502 A CN202011621502 A CN 202011621502A CN 112812540 A CN112812540 A CN 112812540A
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- 239000002131 composite material Substances 0.000 title claims abstract description 184
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 59
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 264
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 114
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000004880 explosion Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 126
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 67
- 229910021389 graphene Inorganic materials 0.000 claims description 66
- 238000005406 washing Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000002041 carbon nanotube Substances 0.000 claims description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 47
- 229920000570 polyether Polymers 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 32
- 150000002009 diols Chemical class 0.000 claims description 30
- 238000000967 suction filtration Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 238000011049 filling Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 239000005056 polyisocyanate Substances 0.000 claims description 16
- 229920001228 polyisocyanate Polymers 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- 125000004427 diamine group Chemical group 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- LVRYTNDTCNWJQC-UHFFFAOYSA-N 1-N,1-N'-di(pentan-2-yl)cyclohexane-1,1-diamine Chemical compound C(C)(CCC)NC1(CCCCC1)NC(C)CCC LVRYTNDTCNWJQC-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 239000000806 elastomer Substances 0.000 abstract description 13
- 229920002396 Polyurea Polymers 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- -1 hydroxyl modified graphene Chemical class 0.000 description 38
- 239000012634 fragment Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a hydroxyl and amino modified anti-knock composite material and a preparation method thereof, belonging to the technical field of anti-corrosion and anti-knock materials, wherein amino and hydroxyl are introduced into a composite material formed by nano-carbon and polyaniline, and in the process of introducing amino and hydroxyl into the composite material formed by nano-carbon and polyaniline, secondary doping and de-doping of polyaniline can be realized, then functionalized nano-carbon and a secondary doped polyaniline composite material are mixed with a polyurea elastomer material, the functionalized nano-carbon and polyaniline composite material is pre-functionalized and then is accessed into the anti-knock elastomer material in a mode of combining physical dispersion and chemical reaction, the defect of poor low-temperature flexibility of the material caused by enhancing the material by increasing the hard segment content in a resin system is avoided, and the anti-knock composite material can be used for improving the gas explosion impact resistance of petrochemical enterprise buildings, the explosion impact damage of the petrochemical enterprise building can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of anticorrosive and anti-explosion materials, in particular to a hydroxyl and amino modified anti-explosion composite material and a preparation method thereof.
Background
In recent years, explosion prevention problems of personnel centralized places such as petrochemical enterprise control rooms and the like have attracted much attention. The polyurea elastomer has high adhesion to substrates including metal and nonmetal, and can be well combined with most materials such as concrete, steel and aluminum after being processed by a proper substrate to form a layered and sandwich-shaped composite structure.
Accidents occurring in chemical enterprises in recent years show that the destructive power of steam cloud explosion (VCE) accidents caused by equipment leakage is huge, and a large amount of casualties of personnel in personnel concentration places near the device are often caused. However, only a few new chemical enterprises or devices in China take the anti-explosion safety design of personnel concentration places into consideration, for example, part of central control rooms or device control rooms are designed by anti-explosion control rooms, and most of internal personnel concentration buildings, such as device control rooms, office buildings, external operation rooms, cabinets and the like, which are closer to production devices, only take the fire protection requirements into consideration, most of the internal personnel concentration buildings do not meet the anti-explosion requirements, and do not meet the regulations of national standard petrochemical industry factory layout design specifications GB50984-2014 and petrochemical industry enterprise design fire protection standards GB50160-2018, so that the anti-explosion safety design system becomes a major potential safety hazard and is in urgent need of treatment. Because the newly-built integral anti-explosion building has long period and high cost, the building is not suitable for in-service production devices. Elastomeric coatings with antiknock properties have been shown to absorb impact energy, have excellent antiknock and impact properties, and can be used for in situ building modifications. Therefore, petrochemical enterprise personnel are developed to concentrate on advanced anti-explosion materials and equipment of buildings, the gas explosion impact resistance of the buildings of the petrochemical enterprises is improved, and the explosion impact damage of the buildings of the petrochemical enterprises can be effectively reduced.
The spray polyurea material has the characteristics of no solvent, environmental protection, high mechanical strength, quick construction and the like, and is widely applied to the fields of submarine pipelines, buried pipelines, storage tank corrosion prevention, concrete protection, water prevention, military skin, chassis protection and the like. The coating is applied to the field of military bullet-resistant explosion-proof protection materials, and the coating is required to have ultrahigh physical strength and to show good tear resistance under high-speed impact, but the conventional polyurea product is difficult to meet the requirements. The conventional solution today is to add specialty fillers to the polyurea resin system or to use pure polyurea systems and improve the performance by increasing the hard segment content. However, the filler is added too much, so that the filler and the resin are easily separated by the explosion-proof material under high-speed impact, and the strength of the coating film is rapidly reduced under the high-speed impact; although the strength of the material is increased by increasing the hard segment content of the resin, the hardness of the material is also greatly improved, so that the low-temperature flexibility of the material is poor, and the material loses the anti-elastic and anti-explosion effects in a low-temperature environment.
Disclosure of Invention
The invention provides a hydroxyl and amino modified anti-knock composite material and a preparation method thereof, which comprises the steps of preparing a functional nano carbon material and preparing a polyurea elastomer material, mixing the functional material and the polyurea elastomer material to obtain a hydroxyl and amino modified nano carbon material and polyaniline composite material, pre-functionalizing the nano carbon material, then connecting the functionalized nano carbon material into the anti-knock elastomer material in a mode of combining physical dispersion and chemical reaction, as the whole process does not contain non-reactive pigment and filler, the physical reinforcement of the filler to the material is abandoned, simultaneously avoids the defect of poor low-temperature flexibility of the material caused by reinforcing the material by increasing the content of the hard segment in the resin system, the method can be used for improving the gas explosion impact resistance of the petrochemical enterprise buildings and effectively reducing the explosion impact damage of the petrochemical enterprise buildings.
The specific technical scheme provided by the invention is as follows:
in a first aspect, the hydroxyl and amino modified anti-knock composite material provided by the invention comprises a semi-prepolymer A component and a semi-prepolymer B component, wherein the semi-prepolymer A component comprises the following raw materials in percentage by mass: 40-60% of polyether diol or polyester diol, 8-10% of polyisocyanate, and 30-35% of hydroxyl modified nanocarbon and secondary doped polyaniline composite material; the component B comprises the following raw materials in percentage by mass: 50-70% of amino-terminated polyether or carboxyl-terminated polyether, 10-30% of diamine chain extender, 0.5-1% of molecular sieve powder slurry, 0.5-1% of color paste and 0.1-0.5% of composite material of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline, wherein the polyether diol or polyester diol and the polyisocyanate exist in the component A of the semi-prepolymer in the form of isocyanate terminated semi-prepolymer.
Optionally, the amino-modified nanocarbon material and intrinsic polyaniline composite material is a composite material formed by dedoping the hydroxyl-modified nanocarbon and primary doped polyaniline composite material by introducing amino-terminated polyether and N, N-dimethyl formamide.
Optionally, the nanocarbon includes graphene, a carbon nanotube, or a composite nanocarbon material composed of graphene and a carbon nanotube.
Optionally, the nanocarbon and secondarily doped polyaniline composite material is a composite material formed by mixing a graphene and eigenstate polyaniline composite and a carbon nanotube and eigenstate polyaniline composite and then secondarily doping the mixture.
Optionally, the nanocarbon and doped polyaniline composite material is a composite material formed by mixing a graphene and intrinsic polyaniline composite and carbon nanotubes and then secondarily doping the mixture.
Optionally, the polyisocyanate comprises at least one of 4, 4-diphenylmethane diisocyanate (MDI-100), 2,4, diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, or naphthalene diisocyanate;
optionally, the diamine chain extender includes one or more of isophorone diamine, 4-bis-sec-butylamino-dicyclohexyl methane, 3-dimethyl-4, 4-bis-sec-butylamino-dicyclohexyl methane, methyl diethanolamine, diethyl toluene diamine, dimethyl thio toluene diamine, 4 '-methylene bis, 4-methylene bis, or N, N' -bis-sec-amyl cyclohexane diamine.
In a second aspect, the invention also provides a method for preparing a hydroxyl and amino modified anti-knock composite material, which comprises the following steps:
step 1: mixing a nano-carbon raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the hydroxyl modified nano-carbon and primary doped polyaniline composite material;
step 2: filling nitrogen into a dry flask, adding 0.1 part of a composite material of hydroxyl modified nano-carbon and primary doped polyaniline into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 2 hours, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, performing constant-temperature water bath at 60 ℃ and stirring for 5 hours, then washing with deionized water for multiple times, performing suction filtration to neutrality, then washing with acetone for multiple times, performing vacuum suction filtration, and placing in an oven at 80 ℃ and drying to constant weight to obtain a target product of the composite material of carboxyl modified nano-carbon and secondary doped polyaniline;
and step 3: filling N2 into a dry flask, adding 0.1 part of composite material of carboxyl modified nano carbon and secondary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in a 80 ℃ constant temperature water bath, washing with deionized water for multiple times and performing suction filtration to neutrality, washing with acetone for multiple times and performing vacuum suction filtration, and placing in an 80 ℃ oven to be dried to constant weight to obtain the composite material of the target product of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline;
and 4, step 4: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
and 5: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized hydroxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
step 6: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
and 7: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
In a third aspect, the invention also provides a method for preparing a hydroxyl and amino modified anti-knock composite material, which comprises the following steps:
step 1: mixing a graphene raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the composite material of hydroxyl modified graphene and primary doped polyaniline;
step 2: filling nitrogen into a dry flask, adding 0.1 part of the composite material of the hydroxyl modified graphene and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times and performing suction filtration until filtrate is neutral, and drying the product at 80 ℃ to obtain the composite material of the target product of the hydroxyl modified graphene and the intrinsic polyaniline;
and step 3: mixing a carbon nanotube raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the hydroxyl-modified carbon nanotube and primary doped polyaniline composite material;
and 4, step 4: filling nitrogen into a dry flask, adding 0.1 part of the composite material of the hydroxyl-modified carbon nanotube and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times and performing suction filtration until filtrate is neutral, and drying the product at 80 ℃ to obtain the target composite material of the hydroxyl-modified carbon nanotube and the intrinsic polyaniline;
and 5: mixing 0.1-10 parts of a composite material of hydroxyl modified graphene and eigenstate polyaniline and 0.1-10 parts of a composite material of hydroxyl modified carbon nano tube and eigenstate polyaniline, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, stirring for 5 hours in a constant-temperature water bath at 60 ℃, washing with deionized water for multiple times and performing suction filtration to neutrality, washing with acetone for multiple times and performing vacuum filtration, and drying in an oven at 80 ℃ to constant weight to obtain a target product of a composite material of carboxyl modified nano carbon and secondary doped state polyaniline;
step 6: charging N2 into the dried flask, adding 0.1 part of carboxyl modified nano carbon and secondary doped polyaniline composite material into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in 80 ℃ constant-temperature water bath, then washing with deionized water for multiple times and filtering to neutrality, finally washing with acetone for multiple times and filtering in vacuum, placing in an oven at 80 ℃ and drying to constant weight to obtain the target product of the composite material of amino modified nano-carbon, eigenstate polyaniline and secondary doped polyaniline, the composite material of the hydroxyl modified nano carbon and the secondary doped polyaniline comprises at least one of a composite material of the hydroxyl modified graphene and the secondary doped polyaniline and a composite material of the hydroxyl modified carbon nano tube and the primary doped polyaniline;
and 7: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
and 8: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized carboxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
and step 9: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
step 10: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
In a fourth aspect, the invention also provides a method for preparing a hydroxyl and amino modified anti-knock composite material, which comprises the following steps:
step 1: mixing a graphene raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the composite material of hydroxyl modified graphene and primary doped polyaniline;
step 2: filling nitrogen into a dry flask, adding 0.1 part of the composite material of the hydroxyl modified graphene and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times and performing suction filtration until filtrate is neutral, and drying the product at 80 ℃ to obtain the composite material of the target product of the hydroxyl modified graphene and the intrinsic polyaniline;
and step 3: mixing 0.1-10 parts of a composite material of hydroxyl modified graphene and intrinsic polyaniline and 0.1-10 parts of carbon nano tubes, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, carrying out constant-temperature water bath at 60 ℃, stirring for 5 hours, washing with deionized water for multiple times, carrying out suction filtration to neutrality, washing with acetone for multiple times, carrying out vacuum filtration, and placing in an oven at 80 ℃ to dry to constant weight to obtain a target product of a composite material of carboxyl modified nano carbon and secondary doped polyaniline;
and 4, step 4: charging N2 into the dried flask, adding 0.1 part of carboxyl modified nano carbon and secondary doped polyaniline composite material into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in 80 ℃ constant-temperature water bath, then washing with deionized water for multiple times and filtering to neutrality, finally washing with acetone for multiple times and filtering in vacuum, placing in an oven at 80 ℃ and drying to constant weight to obtain the target product of the composite material of amino modified nano-carbon, eigenstate polyaniline and secondary doped polyaniline, the composite material of the hydroxyl modified nano carbon and the secondary doped polyaniline comprises at least one of a composite material of the hydroxyl modified graphene and the secondary doped polyaniline and a composite material of the hydroxyl modified carbon nano tube and the primary doped polyaniline;
and 5: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
step 6: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized carboxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
and 7: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
and 8: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
The invention has the following beneficial effects:
the embodiment of the invention provides a hydroxyl and amino modified anti-knock composite material and a preparation method thereof, which can realize secondary doping and de-doping of polyaniline by preparing a functionalized nano-carbon functional material, introducing amino and hydroxyl into a composite material formed by nano-carbon and polyaniline, and introducing amino and hydroxyl into the composite material formed by nano-carbon and polyaniline, further introducing intrinsic polyaniline, doped polyaniline and secondarily doped polyaniline into the composite material, then mixing the functionalized nano-carbon and secondarily doped polyaniline composite material with a polyurea elastomer material, pre-functionalizing the nano-carbon and polyaniline composite material, then inserting the functionalized nano-carbon and polyaniline composite material into the anti-knock elastomer material in a mode of combining physical dispersion and chemical reaction, because the whole process does not contain non-reactive pigment and filler, the physical reinforcement of the filler to the material is abandoned, and the defect that the material has poor low-temperature flexibility caused by reinforcing the material by improving the content of the hard segment in the resin system is avoided, so that the gas explosion impact resistance of the petrochemical enterprise building can be improved, and the explosion impact damage of the petrochemical enterprise building can be effectively reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the hydroxyl and amino modified anti-explosion composite material and the preparation method thereof provided by the embodiment of the invention, the explosion impact relieving effect of the elastomer coating formed by the anti-explosion composite material is utilized, and the explosion protection problem of a petrochemical device personnel centralized place is solved.
Example one
The hydroxyl and amino modified anti-explosion composite material provided by the embodiment of the invention comprises a semi-prepolymer A component and a semi-prepolymer B component, wherein the semi-prepolymer A component comprises the following raw materials in percentage by mass: 40-60% of polyether diol or polyester diol, 8-10% of polyisocyanate, and 30-35% of hydroxyl modified nanocarbon and secondary doped polyaniline composite material; the component B comprises the following raw materials in percentage by mass: 50-70% of amino-terminated polyether or carboxyl-terminated polyether, 10-30% of diamine chain extender, 0.5-1% of molecular sieve powder slurry, 0.5-1% of color paste and 0.1-0.5% of composite material of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline, wherein polyether diol or polyester diol and polyisocyanate exist in the component A of the semi-prepolymer in the form of isocyanate terminated semi-prepolymer.
The hydroxyl-modified nano carbon and polyaniline composite material provided by the embodiment of the invention is a composite material formed by hydroxyl-modified nano carbon, eigenstate polyaniline, primary doped state polyaniline and secondary doped state polyaniline. That is, in the process of introducing hydroxyl into the nanocarbon and polyaniline composite material, polyaniline can undergo primary doping, de-doping and secondary doping reactions, so that polyaniline in the nanocarbon and polyaniline composite material modified by hydroxyl can undergo three states, namely primary doped polyaniline, intrinsic polyaniline and secondary doped polyaniline. The amino modified nano carbon material and the intrinsic polyaniline composite material are composite materials formed by de-doping hydroxyl modified nano carbon and primary doped polyaniline composite materials through introducing amino-terminated polyether and N, N-dimethyl formamide.
The nanocarbon adopted in the hydroxyl and amino modified anti-knock composite material provided by the embodiment of the invention comprises graphene, carbon nanotubes or a composite nanocarbon material consisting of graphene and carbon nanotubes.
One possible implementation manner is as follows: the nano carbon and secondary doped polyaniline composite material is a composite material formed by mixing a graphene and eigenstate polyaniline composite and a carbon nano tube and eigenstate polyaniline composite and then carrying out secondary doping. Namely, the graphene and polyaniline are doped for the first time and then are de-doped to obtain a compound of the graphene and the polyaniline in an eigenstate, the carbon nano tube and the polyaniline are doped for the first time and then are de-doped to obtain a compound of the carbon nano tube and the polyaniline in an eigenstate, and then the compound of the graphene and the polyaniline in an eigenstate and the compound of the carbon nano tube and the polyaniline in an eigenstate are mixed for the second time and then are doped for the second time to obtain the nano carbon and the polyaniline composite material in a secondary doping state. In the primary doping process, the carbon nano tube and the graphene can provide a growth template for polyaniline, so that primary doped polyaniline with excellent appearance can be obtained on the surface of the carbon nano tube or the graphene, and then after de-doping and mixing, the intrinsic polyaniline on the surface of the graphene and the intrinsic polyaniline on the surface of the carbon nano tube are connected with each other through secondary doping to form a skeleton structure, so that the carbon nano tube and the graphene can be prevented from being agglomerated after being mixed with each other, and the reinforcing performance of the carbon nano tube and the graphene after being mixed can be improved.
Another possible implementation is: the nano carbon and secondary doped polyaniline composite material is a composite material formed by mixing a graphene and intrinsic polyaniline composite and carbon nanotubes and then carrying out secondary doping. Namely, the graphene and polyaniline are doped for the first time and then are de-doped to obtain a compound of the graphene and the eigenstate polyaniline, and then the compound of the graphene and the eigenstate polyaniline and the carbon nano tube are mixed and then are doped for the second time to obtain the nano carbon and the secondary doped polyaniline composite material. In the primary doping process, graphene can provide a growth template for polyaniline, primary doped polyaniline with excellent appearance can be obtained on the surface of graphene, and a composite of graphene and eigen-state polyaniline is mixed with carbon nano tubes after de-doping. And the composite of the graphene and the intrinsic polyaniline and the carbon nano tube are mixed and then secondarily doped, in the secondary doping process, the graphene and the carbon nano tube can provide a growth template of polyaniline in the secondary doping process, the secondarily doped polyaniline on the surface of the graphene and the secondarily doped polyaniline on the surface of the carbon nano tube are mutually connected to form a skeleton structure through secondary doping, the carbon nano tube and the graphene can be further prevented from being agglomerated after being mixed, and the reinforcing performance of the composite material formed after the carbon nano tube and the graphene are mixed can be improved by curing the dispersion structures of the carbon nano tube and the graphene by adopting polyaniline.
The polyisocyanate used in the embodiments of the present invention includes at least one of 4, 4-diphenylmethane diisocyanate (i.e., MDI-100), 2,4, diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate or naphthalene diisocyanate. The diamine chain extender comprises one or more of isophorone diamine, 4-bis-sec-butylaminodicyclohexyl methane, 3-dimethyl-4, 4-bis-sec-butylaminodicyclohexyl methane, methyl diethanol amine, diethyl toluenediamine, dimethyl thio toluenediamine, 4 '-methylene bis, 4-methylene bis or N, N' -bis-sec-amyl cyclohexane diamine.
The polyether diol adopted by the embodiment of the invention comprises at least one of PTMG650, PTMG1000 and PTMG2000, wherein the relative molecular mass of the PTMG650 is 650 +/-50, and the hydroxyl value is 167-175 mgkoH/g; the PTMG1000 has the relative molecular mass of 1000 +/-50 and the hydroxyl value of 107-118 mgkoH/g; the PTMG2000 has a relative molecular mass of 2000 +/-50 and a hydroxyl value of 54.7-57.5 mgkoH/g; the polyester diol comprises at least one of polycaprolactone diol and polycarbonate diol.
The embodiment of the invention provides a hydroxyl and amino modified anti-knock composite material and a preparation method thereof, which can realize secondary doping and de-doping of polyaniline by preparing a functionalized nano-carbon functional material, introducing amino and hydroxyl into a composite material formed by nano-carbon and polyaniline, and introducing amino and hydroxyl into the composite material formed by nano-carbon and polyaniline, further introducing intrinsic polyaniline, doped polyaniline and secondarily doped polyaniline into the composite material, then mixing the functionalized nano-carbon and secondarily doped polyaniline composite material with a polyurea elastomer material, pre-functionalizing the nano-carbon and polyaniline composite material, then inserting the functionalized nano-carbon and polyaniline composite material into the anti-knock elastomer material in a mode of combining physical dispersion and chemical reaction, because the whole process does not contain non-reactive pigment and filler, the physical reinforcement of the filler to the material is abandoned, and the defect that the material has poor low-temperature flexibility caused by reinforcing the material by improving the content of the hard segment in the resin system is avoided, so that the gas explosion impact resistance of the petrochemical enterprise building can be improved, and the explosion impact damage of the petrochemical enterprise building can be effectively reduced.
Example two
Based on the same inventive concept, the second embodiment of the present invention provides a method for preparing the above hydroxyl and amino modified anti-knock composite material, which comprises:
step 1: mixing a nano-carbon raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the hydroxyl modified nano-carbon and primary doped polyaniline composite material.
Specifically, after aniline and ammonium persulfate are added according to the molar mass percentage of 0.8:1, aniline is subjected to polymerization reaction under the action of ammonium persulfate to generate polyaniline, and hydrogen ions H in a mixed solution of nanocarbon and mixed acid can be consumed in the synthesis process of polyaniline﹢The consumption rate of hydrogen ions in the acid washing process is accelerated, the rapid acid washing can be realized, and the consumption of deionized water in the acid washing process is reduced; and because the nano carbon exists in the mixed solution, a growth template is provided for the polymerization process of the aniline, namely the nano carbon can provide a template for the growth of the polyaniline after being dispersed, so that the polyaniline with excellent morphology can be obtained conveniently.
Step 2: filling nitrogen into a dry flask, adding 0.1 part of composite material of hydroxyl modified nano carbon and primary doped polyaniline into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 2 hours, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, performing constant-temperature water bath at 60 ℃ and stirring for 5 hours, then washing with deionized water for multiple times, performing suction filtration to neutrality, then washing with acetone for multiple times, performing vacuum suction filtration, and placing in an oven at 80 ℃ and drying to constant weight to obtain the target product of the composite material of carboxyl modified nano carbon and secondary doped polyaniline.
In the process, N-Dimethylformamide (DMF) is added to dedoping the composite material (GO-OH + ES-PANI) of hydroxyl modified nano carbon and primary doped polyaniline, after the polyaniline is dedoped into small molecular fragments, the excellent morphology of the doped polyaniline can be kept, and the small molecular fragments are mixed with each other and can be grafted with the nano carbon better. By introducing carboxylate radical, the intrinsic polyaniline (EB-PANI) formed after de-doping is secondarily doped while the nanocarbon is subjected to carboxylation functional modification, so that the conformation among polyaniline molecular chains and molecular chains is more beneficial to charge delocalization on the molecular chains, and the conductivity is improved by more sufficient delocalization degree.
And step 3: filling N2 into a dry flask, adding 0.1 part of composite material of carboxyl modified nano carbon and secondary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in a 80 ℃ constant temperature water bath, washing with deionized water for multiple times and performing suction filtration to neutrality, washing with acetone for multiple times and performing vacuum filtration, and placing in an 80 ℃ oven to be dried to constant weight to obtain the composite material of the target product of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline.
In the process, amino-terminated polyether is introduced, the secondary doped polyaniline (EB-PANI) is partially de-doped while the nanocarbon is subjected to amination modification, and the corrosion resistance of the system is remarkably improved due to the existence of the intrinsic polyaniline and the secondary doped polyaniline.
And 4, step 4: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
and 5: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized hydroxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
step 6: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
and 7: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
The embodiment of the invention provides a hydroxyl and amino modified anti-knock composite material and a preparation method thereof, which can realize secondary doping and de-doping of polyaniline by preparing a functionalized nano-carbon functional material, introducing amino and hydroxyl into a composite material formed by nano-carbon and polyaniline, and introducing amino and hydroxyl into the composite material formed by nano-carbon and polyaniline, further introducing intrinsic polyaniline, doped polyaniline and secondarily doped polyaniline into the composite material, then mixing the functionalized nano-carbon and secondarily doped polyaniline composite material with a polyurea elastomer material, pre-functionalizing the nano-carbon and polyaniline composite material, then inserting the functionalized nano-carbon and polyaniline composite material into the anti-knock elastomer material in a mode of combining physical dispersion and chemical reaction, because the whole process does not contain non-reactive pigment and filler, the physical reinforcement of the filler to the material is abandoned, and the defect that the material has poor low-temperature flexibility caused by reinforcing the material by improving the content of the hard segment in the resin system is avoided, so that the gas explosion impact resistance of the petrochemical enterprise building can be improved, and the explosion impact damage of the petrochemical enterprise building can be effectively reduced.
EXAMPLE III
Based on the same inventive concept, the third embodiment of the present invention provides a method for preparing the above hydroxyl and amino modified anti-knock composite material, which comprises:
step 1: mixing a graphene raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the composite material of the hydroxyl modified graphene and the primary doped polyaniline.
Specifically, after aniline and ammonium persulfate are added according to the molar mass percentage of 0.8:1, aniline is subjected to polymerization reaction under the action of ammonium persulfate to generate polyaniline, and hydrogen ions H in the mixed solution of graphene and mixed acid can be consumed in the process of synthesizing polyaniline﹢The consumption rate of hydrogen ions in the acid washing process is accelerated, the rapid acid washing can be realized, and the consumption of deionized water in the acid washing process is reduced; and due to the existence of the graphene in the mixed solution, a growth template is provided for the polymerization process of the aniline, namely the graphene can provide a template for the growth of the polyaniline after dispersion, so that the polyaniline with excellent morphology can be obtained conveniently.
Step 2: and (2) filling nitrogen into the dried flask, adding 0.1 part of the composite material of the hydroxyl modified graphene and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target composite material of the hydroxyl modified graphene and the intrinsic polyaniline.
In the process, N-Dimethylformamide (DMF) is added to perform de-doping on the composite material (GO-OH + ES-PANI) of the hydroxyl modified graphene and the primary doped polyaniline, and after the de-doping of the polyaniline is changed into small molecular fragments, the good morphology of the doped polyaniline can be kept, and the mutual grafting between the small molecular fragments and the graphene and the carbon nano tube can be better realized due to the mutual mixing of the small molecular fragments.
And step 3: mixing a carbon nanotube raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the hydroxyl-modified carbon nanotube and primary doped polyaniline composite material;
specifically, after aniline and ammonium persulfate are added according to the molar mass percentage of 0.8:1, aniline is subjected to polymerization reaction under the action of ammonium persulfate to generate polyaniline, and hydrogen ions H in the mixed solution of the carbon nano tube and the mixed acid can be consumed in the synthesis process of polyaniline﹢The consumption rate of hydrogen ions in the acid washing process is accelerated, the rapid acid washing can be realized, and the consumption of deionized water in the acid washing process is reduced; and because the carbon nano tubes exist in the mixed solution, a growth template is provided for the polymerization process of the aniline, namely the carbon nano tubes can provide a template for the growth of the polyaniline after being dispersed, so that the polyaniline with excellent morphology can be obtained conveniently.
And 4, step 4: and (2) filling nitrogen into the dried flask, adding 0.1 part of the composite material of the hydroxyl-modified carbon nanotube and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times and carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target composite material of the hydroxyl-modified carbon nanotube and the intrinsic polyaniline.
In the process, N-Dimethylformamide (DMF) is added to perform de-doping on the composite material (GO-OH + ES-PANI) of the hydroxyl modified graphene and the primary doped polyaniline, and after the de-doping of the polyaniline is changed into small molecular fragments, the good morphology of the doped polyaniline can be kept, and the mutual grafting between the small molecular fragments and the graphene and the carbon nano tube can be better realized due to the mutual mixing of the small molecular fragments.
And 5: mixing 0.1-10 parts of a composite material of hydroxyl modified graphene and eigenstate polyaniline and 0.1-10 parts of a composite material of hydroxyl modified carbon nano tube and eigenstate polyaniline, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, stirring for 5 hours in a constant-temperature water bath at 60 ℃, washing with deionized water for multiple times and performing suction filtration to neutrality, washing with acetone for multiple times and performing vacuum filtration, and drying in an oven at 80 ℃ to constant weight to obtain the target product of the composite material of carboxyl modified nano carbon and secondary doped state polyaniline.
By introducing carboxylate radical, the intrinsic polyaniline (EB-PANI) formed after de-doping is secondarily doped while the nanocarbon is subjected to carboxylation functional modification, so that the conformation among polyaniline molecular chains and molecular chains is more beneficial to charge delocalization on the molecular chains, and the conductivity is improved by more sufficient delocalization degree. And after the graphene and the polyaniline are doped for the first time, the graphene and the polyaniline are de-doped to obtain a compound of the graphene and the polyaniline in an eigenstate, after the carbon nanotube and the polyaniline are doped for the first time, the carbon nanotube and the polyaniline in an eigenstate are de-doped to obtain a compound of the carbon nanotube and the polyaniline in an eigenstate, and after the compound of the graphene and the polyaniline in an eigenstate and the compound of the carbon nanotube and the polyaniline in an eigenstate are mixed, the nano carbon and the polyaniline in a secondary doping state are obtained by secondary. In the primary doping process, the carbon nano tube and the graphene can provide a growth template for polyaniline, so that primary doped polyaniline with excellent appearance can be obtained on the surface of the carbon nano tube or the graphene, and then after de-doping and mixing, the intrinsic polyaniline on the surface of the graphene and the intrinsic polyaniline on the surface of the carbon nano tube are connected with each other through secondary doping to form a skeleton structure, so that the carbon nano tube and the graphene can be prevented from being agglomerated after being mixed with each other, and the reinforcing performance of the carbon nano tube and the graphene after being mixed can be improved.
Step 6: charging N2 into the dried flask, adding 0.1 part of carboxyl modified nano carbon and secondary doped polyaniline composite material into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in 80 ℃ constant-temperature water bath, then washing with deionized water for multiple times and filtering to neutrality, finally washing with acetone for multiple times and filtering in vacuum, placing in an oven at 80 ℃ and drying to constant weight to obtain the target product of the composite material of amino modified nano-carbon, eigenstate polyaniline and secondary doped polyaniline, the composite material of the hydroxyl modified nano-carbon and the secondary doped polyaniline comprises at least one of a composite material of the hydroxyl modified graphene and the secondary doped polyaniline and a composite material of the hydroxyl modified carbon nano-tube and the secondary doped polyaniline.
In the process, amino-terminated polyether is introduced, the secondary doped polyaniline (EB-PANI) is partially de-doped while the nanocarbon is subjected to amination modification, and the corrosion resistance of the system is remarkably improved due to the existence of the intrinsic polyaniline and the secondary doped polyaniline.
And 7: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
and 8: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized carboxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
and step 9: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
step 10: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
Example four
Based on the same inventive concept, the fourth embodiment of the present invention provides a method for preparing the above hydroxyl and amino modified anti-knock composite material, which comprises:
step 1: mixing a graphene raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the composite material of the hydroxyl modified graphene and the primary doped polyaniline.
Specifically, after aniline and ammonium persulfate are added according to the molar mass percentage of 0.8:1, aniline is subjected to polymerization reaction under the action of ammonium persulfate to generate polyaniline, and hydrogen ions H in the mixed solution of graphene and mixed acid can be consumed in the process of synthesizing polyaniline﹢The consumption rate of hydrogen ions in the acid washing process is accelerated, the rapid acid washing can be realized, and the consumption of deionized water in the acid washing process is reduced; and due to the existence of the graphene in the mixed solution, a growth template is provided for the polymerization process of the aniline, namely the graphene can provide a template for the growth of the polyaniline after dispersion, so that the polyaniline with excellent morphology can be obtained conveniently.
Step 2: filling nitrogen into a dry flask, adding 0.1 part of the composite material of the hydroxyl modified graphene and the primary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide for ultrasonic dispersion for 2 hours, then washing with deionized water for multiple times and performing suction filtration until filtrate is neutral, and drying the product at 80 ℃ to obtain the composite material of the target product of the hydroxyl modified graphene and the intrinsic polyaniline;
in the process, N-Dimethylformamide (DMF) is added to perform de-doping on the composite material (GO-OH + ES-PANI) of the hydroxyl modified graphene and the primary doped polyaniline, and after the de-doping of the polyaniline is changed into small molecular fragments, the good morphology of the doped polyaniline can be kept, and the mutual grafting between the small molecular fragments and the graphene and the carbon nano tube can be better realized due to the mutual mixing of the small molecular fragments.
And step 3: mixing 0.1-10 parts of a composite material of hydroxyl modified graphene and intrinsic polyaniline and 0.1-10 parts of carbon nano tubes, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, carrying out constant-temperature water bath at 60 ℃, stirring for 5 hours, washing with deionized water for multiple times, carrying out suction filtration to neutrality, washing with acetone for multiple times, carrying out vacuum filtration, and placing in an oven at 80 ℃ to dry to constant weight to obtain a target product of a composite material of carboxyl modified nano carbon and secondary doped polyaniline.
And after the graphene and polyaniline are doped for the first time, the graphene and polyaniline are de-doped to obtain a compound of the graphene and the eigenstate polyaniline, and then the compound of the graphene and the eigenstate polyaniline is mixed with the carbon nano tube and then is doped for the second time to obtain the nano carbon and polyaniline composite material in the secondary doping state. In the primary doping process, graphene can provide a growth template for polyaniline, primary doped polyaniline with excellent appearance can be obtained on the surface of graphene, and a composite of graphene and eigen-state polyaniline is mixed with carbon nano tubes after de-doping. And the composite of the graphene and the intrinsic polyaniline and the carbon nano tube are mixed and then secondarily doped, in the secondary doping process, the graphene and the carbon nano tube can provide a growth template of polyaniline in the secondary doping process, the secondarily doped polyaniline on the surface of the graphene and the secondarily doped polyaniline on the surface of the carbon nano tube are mutually connected to form a skeleton structure through secondary doping, the carbon nano tube and the graphene can be further prevented from being agglomerated after being mixed, and the reinforcing performance of the composite material formed after the carbon nano tube and the graphene are mixed can be improved by curing the dispersion structures of the carbon nano tube and the graphene by adopting polyaniline.
And 4, step 4: charging N2 into the dried flask, adding 0.1 part of carboxyl modified nano carbon and secondary doped polyaniline composite material into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in 80 ℃ constant-temperature water bath, then washing with deionized water for multiple times and filtering to neutrality, finally washing with acetone for multiple times and filtering in vacuum, placing in an oven at 80 ℃ and drying to constant weight to obtain the target product of the composite material of amino modified nano-carbon, eigenstate polyaniline and secondary doped polyaniline, the composite material of the hydroxyl modified nano-carbon and the secondary doped polyaniline comprises at least one of a composite material of the hydroxyl modified graphene and the secondary doped polyaniline and a composite material of the hydroxyl modified carbon nano-tube and the secondary doped polyaniline.
In the process, N-Dimethylformamide (DMF) is added to perform de-doping on the composite material (GO-OH + ES-PANI) of the hydroxyl modified graphene and the secondary doped polyaniline, and after the de-doping of the polyaniline is changed into small molecular fragments, the good morphology of the doped polyaniline can be kept, and the mutual grafting between the small molecular fragments and the graphene and the carbon nano tube can be better realized due to the mutual mixing of the small molecular fragments. By introducing the amino-terminated polyether, the secondary doped polyaniline (EB-PANI) is partially de-doped while the nano carbon is subjected to amination modification, and the corrosion resistance of the system is remarkably improved due to the existence of the intrinsic polyaniline and the secondary doped polyaniline.
And 5: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
step 6: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized carboxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
and 7: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
and 8: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments of the present invention without departing from the spirit or scope of the embodiments of the invention. Thus, if such modifications and variations of the embodiments of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to encompass such modifications and variations.
Claims (6)
1. The hydroxyl and amino modified anti-explosion composite material is characterized by comprising a semi-prepolymer A component and a semi-prepolymer B component, wherein the semi-prepolymer A component comprises the following raw materials in percentage by mass: 40-60% of polyether diol or polyester diol, 8-10% of polyisocyanate, and 30-35% of hydroxyl modified nanocarbon and secondary doped polyaniline composite material; the component B comprises the following raw materials in percentage by mass: 50-70% of amino-terminated polyether or carboxyl-terminated polyether, 10-30% of diamine chain extender, 0.5-1% of molecular sieve powder slurry, 0.5-1% of color paste and 0.1-0.5% of composite material of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline, wherein the polyether diol or polyester diol and the polyisocyanate exist in the component A of the semi-prepolymer in the form of isocyanate terminated semi-prepolymer.
2. The anti-knock composite material according to claim 1, wherein the composite material of the amino-modified nanocarbon material and the polyaniline in the intrinsic state and the polyaniline in the secondarily doped state is a composite material formed by introducing amino-terminated polyether and N, N-dimethylformamide for rear decomposition and doping of the composite material of the hydroxyl-modified nanocarbon and the polyaniline in the secondarily doped state.
3. The explosion-resistant composite material as recited in claim 1, wherein the nanocarbon comprises graphene, carbon nanotubes or a composite nanocarbon material of graphene and carbon nanotubes.
4. The antiknock composite of claim 1, wherein the polyisocyanate includes at least one of 4,4, -diphenylmethane diisocyanate (MDI-100), 2,4, diphenylmethane diisocyanate, 4, -diphenylmethane diisocyanate, isophorone diisocyanate, 4, -dicyclohexylmethane diisocyanate, or naphthalene diisocyanate;
5. the antiknock composite of claim 1, wherein the diamine chain extender comprises one or more of isophoronediamine, 4, -bis-sec-butylaminodicyclohexylmethane, 3, -dimethyl-4, 4, -bis-sec-butylaminodicyclohexylmethane, methyldiethanolamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4 '-methylenebis, 4-methylenebis, or N, N' -bis-sec-amylcyclohexanediamine.
6. A method for preparing the hydroxyl and amino modified anti-knock composite material as defined in any one of claims 1 to 5, wherein the method comprises the following steps:
step 1: mixing a nano-carbon raw material and mixed acid according to the mass percentage of 0.1:100, stirring for 6-8 h at 60 ℃ after ultrasonic dispersion is uniform, then washing with deionized water, adding aniline and ammonium persulfate according to the molar mass percentage of 0.8:1 when the pH value is 1, stirring for 2h at normal temperature, standing for reaction for 12h, then washing with deionized water for multiple times, carrying out suction filtration until the filtrate is neutral, and drying the product at 80 ℃ to obtain the target product, namely the hydroxyl modified nano-carbon and primary doped polyaniline composite material;
step 2: filling nitrogen into a dry flask, adding 0.1 part of a composite material of hydroxyl modified nano-carbon and primary doped polyaniline into the flask, vacuumizing again, filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 2 hours, adding 1 part of acrylic acid and 1 part of azodiisobutyronitrile, performing constant-temperature water bath at 60 ℃ and stirring for 5 hours, then washing with deionized water for multiple times, performing suction filtration to neutrality, then washing with acetone for multiple times, performing vacuum suction filtration, and placing in an oven at 80 ℃ and drying to constant weight to obtain a target product of the composite material of carboxyl modified nano-carbon and secondary doped polyaniline;
and step 3: filling N2 into a dry flask, adding 0.1 part of composite material of carboxyl modified nano carbon and secondary doped polyaniline into the flask, vacuumizing again and filling nitrogen, adding 80-100 parts of N, N-dimethylformamide, performing ultrasonic dispersion for 0.5h, adding 4 parts of amino-terminated polyether, stirring for 12h in a 80 ℃ constant temperature water bath, washing with deionized water for multiple times and performing suction filtration to neutrality, washing with acetone for multiple times and performing vacuum suction filtration, and placing in an 80 ℃ oven to be dried to constant weight to obtain the composite material of the target product of amino modified nano carbon, intrinsic polyaniline and secondary doped polyaniline;
and 4, step 4: stirring and heating polyether diol or polyester diol to 100-130 ℃ in an inert environment, dehydrating for 2-3 hours under the vacuum of-0.1 MPa, then removing the vacuum, cooling to below 60 ℃, adding polyisocyanate, reacting for 2-4 hours at 80-90 ℃, measuring the NCO value after the reaction is finished, discharging, and filtering to obtain an isocyanate-terminated semi-prepolymer;
and 5: mixing the prepared isocyanate-terminated semi-prepolymer with a composite material of functionalized hydroxyl modified nano-carbon and secondary doped polyaniline in an inert environment, then performing ultrasonic dispersion treatment at the temperature of 50-60 ℃ for 24 hours, measuring an NCO value after the reaction is finished, discharging, and filtering to obtain a semi-prepolymer component A;
step 6: in an inert environment, the weight ratio of 50-70%: 10-30%: 0.5-1%: dispersing, stirring and filtering 0.5-1% of amino-terminated polyether or hydroxyl-terminated polyether, diamine chain extender, molecular sieve powder slurry and color paste to obtain a B component premix, mixing the B component premix and the functionalized amino modified nanocarbon with the composite material of the intrinsic polyaniline and the secondarily doped polyaniline according to the mass ratio of 210: 0.2-1, and dispersing and filtering by adopting ultrasonic waves to obtain the B component;
and 7: before spraying, the component A and the component B of the semi-prepolymer are mixed with each other according to the volume ratio of 1:1 to obtain the hydroxyl and amino modified anti-explosion composite material.
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