CN114230805A - Organic polymer flame retardant, water-based fireproof flame-retardant coating and preparation method thereof - Google Patents
Organic polymer flame retardant, water-based fireproof flame-retardant coating and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 105
- 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 87
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 35
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 33
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940068041 phytic acid Drugs 0.000 claims abstract description 30
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 30
- 239000000467 phytic acid Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 239000006255 coating slurry Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- 101001039157 Homo sapiens Leucine-rich repeat-containing protein 25 Proteins 0.000 description 11
- 102100040695 Leucine-rich repeat-containing protein 25 Human genes 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an organic polymer flame retardant which is assembled by melamine and phytic acid, and overcomes the defects of insufficient thermal stability and poor water resistance of the existing flame retardant in the market. The flame retardant can expand at high temperature and has a flame retardant effect when applied to a fireproof coating, and the obtained carbon layer has high strength, excellent fireproof performance and good water resistance.
Description
Technical Field
The invention relates to the field of coatings, in particular to an organic polymer flame retardant, a water-based fireproof flame-retardant coating and a preparation method thereof.
Background
The fireproof paint is a good functional material for solving the fireproof problem of materials such as steel, wood and the like. The fireproof coating can provide certain physical protection when a fire disaster happens, and a flame-retardant layer is rapidly generated or flame-retardant gas is released to extinguish flame, so that the function of protecting a base material is achieved. The fire-proof coating can eliminate or slow down the continuous combustion of flame, and win time for rescue, thereby protecting the life and property safety of people.
The fireproof paint is a functional material, can play a role in decorating and protecting a base material, and generally consists of two parts, namely a base material and a flame retardant. Generally, the fireproof coating has the functions of corrosion resistance, acid and alkali resistance, rust resistance, rain resistance, moisture resistance, aging resistance, attractive appearance and the like under the condition of meeting fireproof safety. The fire-retardant coating has the function of flame retardant, and in recent years, people are always dedicated to developing different types of novel flame retardants to be applied to the coating, so that the fire-retardant coating with ideal effect is prepared.
The commonly used flame retardants in the fireproof coating include traditional halogen flame retardants, phosphorus-nitrogen flame retardants, intumescent flame retardants, biomass flame retardants, graphene flame retardants and the like. The phosphorus-nitrogen flame retardant is an environment-friendly flame retardant which is applied more at present, and can generate a relatively stable carbon layer in the combustion process so as to prevent heat transfer and further play a flame-retardant role. However, the flame retardant with one flame retardant mechanism hardly meets the flame retardant requirement of the material, and the phosphorus-nitrogen flame retardant is widely applied in the field of high-molecular flame retardant. Other applications such as halogen flame retardants are also quite widespread. In the future fireproof paint market, the fireproof paint which is environment-friendly, healthy, strong in adhesive force, simple and convenient to prepare, good in stability, thin in coating layer and good in flame retardant effect is favored by the market. With the higher and higher requirements of world laws, the application fields of the environment-friendly and efficient flame retardant and the multifunctional fireproof coating are necessarily wider.
The fire retardant in the existing fire-retardant coating on the market has insufficient thermal stability, and foaming, fire retardant decomposition and other phenomena are easily generated during processing and injection molding.
The existing flame retardant has poor water resistance, precipitation resistance and migration resistance, the flame retardant can be precipitated on the surface after being baked in an oven for a long time, and particularly, the flame retardant can be precipitated and dissolved in water after being soaked in hot water for a long time, so that the flame retardant effect is lost.
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides an organic polymer flame retardant, a water-based fireproof flame-retardant coating and a preparation method thereof, which overcome the defects of insufficient thermal stability and poor water resistance of the existing flame retardant in the market; the flame retardant can expand at high temperature and has a flame retardant effect when applied to a fireproof coating, and the obtained carbon layer has high strength, excellent fireproof performance and good water resistance.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
an organic polymer flame retardant is assembled by melamine and phytic acid, wherein the mass ratio of the melamine to the phytic acid is as follows: 1.2-3: 1;
the melamine is a nitrogen-rich organic base, has three amino groups and has pi-pi stacking capacity; phytic acid is an environmentally friendly organic acid having six phosphate groups; electropositive amino NH on melamine3+And electronegative acid sites O on the phytic acid form a two-dimensional organic polymer flame retardant through self-assembly of hydrogen bonds.
A preparation method of an organic polymer flame retardant comprises the following specific steps: respectively grinding melamine and phytic acid uniformly, stirring at the temperature of 50-120 ℃, dispersing 0.1-10g of melamine in 50-100mL of ultrapure water at the stirring speed of 300-1000rpm until the melamine is completely dissolved to form a uniform solution A;
then, adding 1-100g of phytic acid into 2-150mL of ultrapure water at the rotation speed of 500-1500rpm, and stirring for 0.2-2 hours to obtain a clear phytic acid aqueous solution with the mass fraction of 50-70 wt%, namely a solution B;
putting the solution A and the solution B in a mass ratio of 1-3:1 into a Teflon-lined stainless steel autoclave, mixing, standing at 60-200 ℃ for 2-8 hours, and cooling to room temperature to obtain a white precipitate; washing the white precipitate with deionized water until the supernatant is clear; finally, the white precipitate is freeze-dried for 8 to 36 hours to obtain the organic polymer flame retardant.
Further, the Teflon-lined stainless steel autoclave has a capacity of 100-.
The water-based fireproof flame-retardant coating is prepared from the following raw materials in parts by mass: 5 to 35 parts of water, 0.1 to 2.5 parts of wetting agent, 1 to 5 parts of dispersing agent, 0.1 to 1 part of pH regulator, 5 to 15 parts of titanium dioxide, 0.5 to 5 parts of talcum powder, 1 to 5 parts of aluminum hydroxide and 5 to 15 parts of charring agent, 5-15 parts of foaming agent, 10-30 parts of dehydrating agent, 1-20 parts of organic polymer flame retardant, 20-35 parts of acrylic emulsion, polyurethane emulsion or epoxy emulsion, 0.1-1 part of defoaming agent, 0.05-0.5 part of preservative, 0.2-5 parts of film-forming assistant and 0.1-1 part of thickening agent.
A preparation method of a water-based fireproof flame-retardant coating comprises the following specific steps: at the rotating speed of 600r/min, firstly adding water, wetting agent, dispersing agent and pH regulator into a dispersion kettle, stirring for 10 minutes, then adding pigment filler titanium dioxide, talcum powder and aluminum hydroxide, adjusting the rotating speed to 900r/min, and continuing stirring for 5 minutes;
adding a char forming agent, a foaming agent, a dehydrating agent and an organic polymer flame retardant, adjusting the rotating speed to 1500r/min, and stirring for 10 minutes until the fireproof coating slurry is uniformly dispersed;
transferring the obtained fireproof coating slurry into a grinding kettle, adding zirconium beads with the same weight as the fireproof coating slurry, stirring for 1 hour at the stirring speed of 2000r/min, and then filtering and removing the zirconium beads to obtain the grinded fireproof coating slurry;
and then adding the emulsion, the defoaming agent, the preservative, the film forming assistant and the thickening agent into the fireproof coating slurry under the condition that the stirring speed is 1200r/min, and stirring for 30 minutes to obtain the water-based fireproof flame-retardant coating.
Further, the diameter of the zirconium beads is 1 mm.
(III) advantageous effects
The invention has the beneficial effects that: when the organic polymer flame retardant (MAPA) disclosed by the invention is applied to the fireproof coating, the improvement effect on the fire resistance at high temperature is obvious, the expansion flame-retardant effect can be realized, the carbon layer has high expansion rate and high strength, and the carbon layer has excellent water resistance.
The preparation reaction condition of the organic polymer flame retardant (MAPA) provided by the invention is mild, the reaction process is controllable, and the yield is high.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
An organic polymer flame retardant is assembled by melamine and phytic acid, wherein the mass ratio of the melamine to the phytic acid is as follows: 1.2-3: 1;
the melamine is a nitrogen-rich organic base, has three amino groups and has pi-pi stacking capacity; phytic acid is an environmentally friendly organic acid having six phosphate groups; electropositive amino NH on melamine3+And electronegative acid sites O on the phytic acid form a two-dimensional organic polymer flame retardant through self-assembly of hydrogen bonds.
A preparation method of an organic polymer flame retardant comprises the following specific steps: respectively grinding melamine and phytic acid uniformly, stirring at the temperature of 50-120 ℃, dispersing 0.1-10g of melamine in 50-100mL of ultrapure water at the stirring speed of 300-1000rpm until the melamine is completely dissolved to form a uniform solution A;
then, adding 1-100g of phytic acid into 2-150mL of ultrapure water at the rotation speed of 500-1500rpm, and stirring for 0.2-2 hours to obtain a clear phytic acid aqueous solution with the mass fraction of 50-70 wt%, namely a solution B;
putting the solution A and the solution B in a mass ratio of 1-3:1 into a Teflon-lined stainless steel autoclave, mixing, standing at 60-200 ℃ for 2-8 hours, and cooling to room temperature to obtain a white precipitate; washing the white precipitate with deionized water until the supernatant is clear; finally, the white precipitate is freeze-dried for 8 to 36 hours to obtain the organic polymer flame retardant.
Further, the Teflon-lined stainless steel autoclave has a capacity of 100-.
The water-based fireproof flame-retardant coating is prepared from the following raw materials in parts by mass: 5 to 35 parts of water, 0.1 to 2.5 parts of wetting agent, 1 to 5 parts of dispersing agent, 0.1 to 1 part of pH regulator, 5 to 15 parts of titanium dioxide, 0.5 to 5 parts of talcum powder, 1 to 5 parts of aluminum hydroxide and 5 to 15 parts of charring agent, 5-15 parts of foaming agent, 10-30 parts of dehydrating agent, 1-20 parts of organic polymer flame retardant, 20-35 parts of acrylic emulsion, polyurethane emulsion or epoxy emulsion, 0.1-1 part of defoaming agent, 0.05-0.5 part of preservative, 0.2-5 parts of film-forming assistant and 0.1-1 part of thickening agent.
A preparation method of a water-based fireproof flame-retardant coating comprises the following specific steps: at the rotating speed of 600r/min, firstly adding water, wetting agent, dispersing agent and pH regulator into a dispersion kettle, stirring for 10 minutes, then adding pigment filler titanium dioxide, talcum powder and aluminum hydroxide, adjusting the rotating speed to 900r/min, and continuing stirring for 5 minutes;
adding a char forming agent, a foaming agent, a dehydrating agent and an organic polymer flame retardant, adjusting the rotating speed to 1500r/min, and stirring for 10 minutes until the fireproof coating slurry is uniformly dispersed;
transferring the obtained fireproof coating slurry into a grinding kettle, adding zirconium beads with the same weight as the fireproof coating slurry, stirring for 1 hour at the stirring speed of 2000r/min, and then filtering and removing the zirconium beads to obtain the grinded fireproof coating slurry; the diameter of the zirconium beads is 1 mm;
and then adding the emulsion, the defoaming agent, the preservative, the film forming assistant and the thickening agent into the fireproof coating slurry under the condition that the stirring speed is 1200r/min, and stirring for 30 minutes to obtain the water-based fireproof flame-retardant coating.
The flame retardant combines phosphorus and nitrogen flame retardant elements into the same molecule, and the multifunctional flame retardant elements can realize synergistic flame retardance, so that the flame retardant effect and the comprehensive performance can be effectively improved.
The flame retardant can release non-combustible gas to play a flame retardant role in the expansion process of the carbon layer, and has good thermal stability and char forming capability.
The flame retardant does not contain halogen elements and has excellent environmental protection property.
The melamine used in the flame retardant is organic alkali rich in nitrogen, has three amino groups and has pi-pi stacking capacity; phytic acid is an environmentally friendly organic acid having six phosphate groups. The two-dimensional MAPA supermolecule nano-sheet is formed by electropositive amino NH on MA3+And electronegative acid sites O on PA are assembled by hydrogen bonds.
The preparation method of the organic polymer flame retardant has the characteristics of mild reaction conditions, controllable reaction process, high yield and the like.
Example 1
The melamine and phytic acid were each ground uniformly, stirred at 50 ℃, and 2g of the melamine was dispersed in 50mL of ultrapure water at a stirring rate of 300rpm until the melamine was completely dissolved to form a uniform solution. Then, 2g of phytic acid was added to 25mL of ultrapure water at 500rpm, and stirred for 0.5 hour. The two solutions were mixed in a 100mL teflon lined stainless steel autoclave, allowed to stand at 60 ℃ for 8 hours and then cooled to room temperature. The resulting white precipitate was washed with deionized water until the supernatant was clear. Finally, the white precipitate was freeze-dried for 12 hours and the supramolecular organic polymer flame retardant was collected.
According to the test, the yield of the organic polymer flame retardant MAPA is 56%, and the carbon residue rate at 900 ℃ is 73.3%.
Example 2
The melamine and phytic acid were each ground uniformly, stirred at 60 ℃, and 4g of melamine was dispersed in 60mL of ultrapure water at a stirring rate of 500rpm until the melamine was completely dissolved to form a uniform solution. Then, 3g of phytic acid was added to 30mL of ultrapure water at 1000rpm, and stirred for 0.5 hour. The two solutions were mixed in a 100mL teflon lined stainless steel autoclave, allowed to stand at 80 ℃ for 8 hours and then cooled to room temperature. The resulting white precipitate was washed with deionized water until the supernatant was clear. Finally, the white precipitate was freeze-dried for 24 hours and the supramolecular organic polymer flame retardant was collected.
According to the test, the yield of the organic polymer flame retardant MAPA is 67%, and the carbon residue rate at 900 ℃ is 80.1%.
Example 3
Melamine and phytic acid were each ground uniformly, stirred at 100 ℃, and 6g of melamine was dispersed in 100mL of ultrapure water at a stirring rate of 1000rpm until the melamine was completely dissolved to form a uniform solution. Then, 4g of phytic acid was added to 50mL of ultrapure water at 1200rpm, and stirred for 1.5 hours. The two solutions were mixed in a 200mL Teflon lined stainless steel autoclave, allowed to stand at 100 ℃ for 6 hours and then cooled to room temperature. The resulting white precipitate was washed with deionized water until the supernatant was clear. Finally, the white precipitate was freeze-dried for 8 hours and the supramolecular organic polymer flame retardant was collected.
According to the test, the yield of the organic polymer flame retardant MAPA is 66.2%, and the carbon residue rate at 900 ℃ is 78.3%.
Example 4
The melamine and phytic acid were each ground uniformly, stirred at 80 ℃, and 5g of melamine was dispersed in 70mL of ultrapure water at a stirring rate of 600rpm until the melamine was completely dissolved to form a uniform solution. Then, 4g of phytic acid was added to 40mL of ultrapure water at 1200rpm, and stirred for 1 hour. The two solutions were mixed in a 200mL Teflon lined stainless steel autoclave, allowed to stand at 150 ℃ for 4 hours and then cooled to room temperature. The resulting white precipitate was washed with deionized water until the supernatant was clear. Finally, the white precipitate was freeze-dried for 12 hours and the supramolecular organic polymer flame retardant was collected.
The organic polymer flame retardant MAPA was tested at 64.9% yield and 75.2% char yield at 900 ℃.
Example 5
The melamine and phytic acid were each ground uniformly, stirred at 50 ℃, and 3g of melamine was dispersed in 60mL of ultrapure water at a stirring rate of 500rpm until the melamine was completely dissolved to form a uniform solution. Then, 4g of phytic acid was added to 50mL of ultrapure water at 800rpm, and stirred for 1.5 hours. The two solutions were mixed in a 150mL teflon-lined stainless steel autoclave, allowed to stand at 180 ℃ for 2 hours and then cooled to room temperature. The resulting white precipitate was washed with deionized water until the supernatant was clear. Finally, the white precipitate was freeze-dried for 10 hours and the supramolecular organic polymer flame retardant was collected.
The organic polymer flame retardant MAPA was tested to have a yield of 59.8% and a char yield at 900 deg.C of 68.7%.
When the organic polymer flame retardant MAPA prepared in example 4 was applied to the preparation of the fire-retardant coating, when the addition amount of the organic polymer flame retardant MAPA was 15% of the total amount of the coating, the fire-retardant coating had the longest flame retardant time and water-fast time, the preparation of the fire-retardant coating was as follows, and the specific test results are shown in Table I.
Watch 1
As can be seen from the table I, compared with the fireproof coating 1 and the fireproof coating 2, the organic polymer flame retardant MAPA of the invention has obvious flame retardant effect when being applied to the fireproof coating, the fire resistance time is obviously improved, and the water resistance time is also obviously improved. From the comparison of the fireproof coatings 3 and 4 and the fireproof coating 2, the improvement of the fire resistance and the water resistance is not facilitated by too much or too little adding amount of the fire retardant.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. The organic polymer flame retardant is characterized by being prepared by assembling melamine and phytic acid, wherein the mass ratio of the melamine to the phytic acid is as follows: 1.2-3: 1;
the melamine is a nitrogen-rich organic base, has three amino groups and has pi-pi stacking capacity; phytic acid is an environmentally friendly organic acid having six phosphate groups; electropositive amino NH on melamine3+And electronegative acid sites O on the phytic acid form a two-dimensional organic polymer flame retardant through self-assembly of hydrogen bonds.
2. A method for preparing the organic polymer flame retardant according to claim 1, which is characterized by comprising the following steps: respectively grinding melamine and phytic acid uniformly, stirring at the temperature of 50-120 ℃, dispersing 0.1-10g of melamine in 50-100mL of ultrapure water at the stirring speed of 300-1000rpm until the melamine is completely dissolved to form a uniform solution A;
then, adding 1-100g of phytic acid into 2-150mL of ultrapure water at the rotation speed of 500-1500rpm, and stirring for 0.2-2 hours to obtain a clear phytic acid aqueous solution with the mass fraction of 50-70 wt%, namely a solution B;
putting the solution A and the solution B in a mass ratio of 1-3:1 into a Teflon-lined stainless steel autoclave, mixing, standing at 60-200 ℃ for 2-8 hours, and cooling to room temperature to obtain a white precipitate; washing the white precipitate with deionized water until the supernatant is clear; finally, the white precipitate is freeze-dried for 8 to 36 hours to obtain the organic polymer flame retardant.
3. The method of claim 2, wherein the Teflon-lined stainless steel autoclave has a capacity of 100-200 mL.
4. The water-based fireproof flame-retardant coating is characterized by being prepared from the following raw materials in parts by mass: 5 to 35 parts of water, 0.1 to 2.5 parts of wetting agent, 1 to 5 parts of dispersing agent, 0.1 to 1 part of pH regulator, 5 to 15 parts of titanium dioxide, 0.5 to 5 parts of talcum powder, 1 to 5 parts of aluminum hydroxide and 5 to 15 parts of charring agent, 5-15 parts by mass of foaming agent, 10-30 parts by mass of dehydrating agent, 1-20 parts by mass of organic polymer flame retardant according to claim 1, 20-35 parts by mass of emulsion, 0.1-1 part by mass of defoaming agent, 0.05-0.5 part by mass of preservative, 0.2-5 parts by mass of film forming aid and 0.1-1 part by mass of thickener.
5. The aqueous fire retardant coating of claim 4, wherein the emulsion is an acrylic emulsion, a polyurethane emulsion or an epoxy emulsion.
6. The preparation method of the water-based fireproof flame-retardant coating according to claim 4, which is characterized by comprising the following steps: at the rotating speed of 600r/min, firstly adding water, wetting agent, dispersing agent and pH regulator into a dispersion kettle, stirring for 10 minutes, then adding pigment filler titanium dioxide, talcum powder and aluminum hydroxide, adjusting the rotating speed to 900r/min, and continuing stirring for 5 minutes;
adding a char forming agent, a foaming agent, a dehydrating agent and an organic polymer flame retardant, adjusting the rotating speed to 1500r/min, and stirring for 10 minutes until the fireproof coating slurry is uniformly dispersed;
transferring the obtained fireproof coating slurry into a grinding kettle, adding zirconium beads with the same weight as the fireproof coating slurry, stirring for 1 hour at the stirring speed of 2000r/min, and then filtering and removing the zirconium beads to obtain the grinded fireproof coating slurry;
and then adding the emulsion, the defoaming agent, the preservative, the film forming assistant and the thickening agent into the fireproof coating slurry under the condition that the stirring speed is 1200r/min, and stirring for 30 minutes to obtain the water-based fireproof flame-retardant coating.
7. The method of claim 6, wherein the zirconium beads have a diameter of 1 mm.
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