CN105860742A - Low-smoke expansive type transparent fire-retardant coating and preparation method thereof - Google Patents
Low-smoke expansive type transparent fire-retardant coating and preparation method thereof Download PDFInfo
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- CN105860742A CN105860742A CN201610327819.8A CN201610327819A CN105860742A CN 105860742 A CN105860742 A CN 105860742A CN 201610327819 A CN201610327819 A CN 201610327819A CN 105860742 A CN105860742 A CN 105860742A
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- type transparent
- retardant coating
- phosphate ester
- transparent fire
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- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000000779 smoke Substances 0.000 title abstract description 27
- -1 phosphate ester Chemical class 0.000 claims abstract description 79
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 78
- 239000010452 phosphate Substances 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 17
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 150000007974 melamines Chemical class 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 229940059574 pentaerithrityl Drugs 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 229910000149 boron phosphate Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 239000009719 polyimide resin Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004640 Melamine resin Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000001629 suppression Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 239000004035 construction material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
- C07F9/092—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl substituted by B, Si or a metal
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- 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)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a low-smoke expansive type transparent fire-retardant coating and a preparation method thereof. The coating comprises a component A and a component B, wherein the component A comprises boric phosphate ester, and the component B comprises melamine resin. The low-smoke expansive type transparent fire-retardant coating has the following benefits: the low-smoke expansive type transparent fire-retardant coating effectively avoids coating transparency, mobility, compatibility and other problems caused by addition of a smoke suppressor, by introducing boron into matrix resin; in the low-smoke expansive type transparent fire-retardant coating, a carbon source, an acid source and a gas source of an expansion fire-retardant system are integrated, and polyethylene glycol boric acid ester is introduced, so that the low-smoke expansive type transparent fire-retardant coating has relatively good fire retardation, smoke suppression and flexibility; raw materials of the coating has wide sources, the cost is low, the preparation process is simple, and the operation is convenient.
Description
Technical field
The present invention relates to the fireproof material technology field of Chemical Engineering Technology, be coated with particularly to the fire prevention of a kind of low cigarette expansion-type transparent
Material and preparation method thereof.
Background technology
Transparent fire-resisting paint is that a kind of brushing at flammable substrate or requires on the object of special protection function, can keep work
The base material texture of journey structure, character pattern, quality aesthetic feeling, can play again the Novel fire retardant coating of fireproofing function, can extensively apply
In fields such as ancient building, modern architecture, historical relic's protection and high-grade decorations, have a extensive future.Transparent fire-resisting paint can be divided into swollen
Swollen type and non-expansion type, wherein the flameproof effect of expansion-type transparent fire-retardant coating becomes apparent from than non-expansion type, at present in fire prevention
Paint field is most widely used.
At present, research work for transparent fire-resisting paint is gradually paid attention to both at home and abroad.As, patent publication No. is
The patent documentation of CN104046201A discloses the generation technique of a kind of Flexible intumescent transparent fire-resisting paint, and wherein component A is
Polyphosphoric acids, butanediol, tetramethylolmethane and Polyethylene Glycol are 2:0.8:2:1 reaction preparation according to mol ratio, by component A methyl-etherified
The B component that amino resins is made obtains with mol ratio 1:2 mix homogeneously that pliability is good, crack resistance good, the expansion of cold curing
Type transparent fire-resisting paint.Patent publication No. CN102719168A reports a kind of with polyphosphoric acids, tetramethylolmethane and Polyethylene Glycol
The Polyethylene Glycol grafting condensed phosphate prepared for raw material is component A, with water-compatible amino resin as B component, A, B component is blended
Stirring obtains Bicomponent transparent finishing fire retardant coating, and this coating has preferable fire protecting performance and pliability concurrently.Patent publication No.
CN101050331A reports a kind of room temperature solidified expansion type flame-resistant fire retardant coating of epoxy resin, and this coating is by A, B component
Compounding forming, wherein component A is containing epoxy terminated resin, B component be phosphorus pentoxide, phosphoric acid and alcohol be acid prepared by principle
Formula phosphate ester, during use, A, B component mix with P-OH group molar ratio 1:1 in B component according to epoxide group.Patent publication No.
CN101747819A reports a kind of with ammonium dihydrogen phosphate, formaldehyde, tetramethylolmethane, carbamide, three ethanol glue, sodium hydroxide as raw material
Prepare component A according to a certain ratio, prepare B component according to a certain ratio with tripolycyanamide, formaldehyde, Borax, then by A, B component with matter
Measure to be blended than 1:1-2 and prepare expansion-type transparent fire-retardant coating.With amino resins as film forming polymer in above-mentioned patent, with phosphate ester
Compound is the expansion-type transparent fire-retardant coating that firming agent is prepared for excellent fireproof performance, wherein uses Polyethylene Glycol as flexibility
Segment grafting phosphate ester acid can also significantly improve the pliability of coating.But in the expansion transparent fireproof coating in existing report
Often contain substantial amounts of P elements, can promote to generate substantial amounts of dense smoke, corrosive gas and toxic gas in fire process, increase
Add fire hazard, personnel escape in fire has been had a negative impact.
Boron element is introduced phosphate ester acid by chemical method and prepares boracic phosphate compound by the present invention, is keeping painting
While the layer transparency, coating is made to have preferable fire resistance and smoke suppressing concurrently.
Summary of the invention
In order to reduce the raw smoke in expansion-type transparent fire-retardant coating combustion process, the invention provides a kind of low cigarette and expand
Type transparent fire-resisting paint and preparation method thereof.Boron element and soft segment are introduced phosphate ester acid and prepare the expansion of low cigarette by the present invention
Type transparent fire-resisting paint, ensure coating the transparency and flexible on the basis of, improve coating fire-retardant and smoke suppressing.
In order to realize foregoing invention purpose, the invention provides a kind of low cigarette expansion-type transparent fire-retardant coating, including component A
And B component, described component A comprises boracic phosphate ester, and described B component comprises melmac.
Boracic phosphate ester in described coating: melmac (or melamine resin) mass ratio is called 1:
1-2。
Described component A is the aqueous solution of boracic phosphate ester, and described B component is the aqueous solution of melmac.
Described melmac is methyl-etherified melmac or butylated melamine resins.
Wherein methyl-etherified melmac is also referred to as methyl-etherified melamine resin, and butylated melamine resins is also
Claim butylated melamine-formaldehyde resin；
Described boracic phosphate ester preparation method comprise the following steps:
A. the preparation of Polyethylene Glycol borate: by Polyethylene Glycol and boron compound according to mol ratio 1.5-2:1 at 120 DEG C-140
Hybrid reaction 2-4h at DEG C, obtains Polyethylene Glycol borate；
B. the preparation of phosphate ester acid: by phosphoric acid, tetramethylolmethane and n-butyl alcohol according to mol ratio 1:0.25-0.35:0.1-0.2
Hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtains phosphate ester acid；
C. the preparation of boracic phosphate ester: by the Polyethylene Glycol borate of preparation in step a and the acid phosphate of preparation in step b
Ester, according to mol ratio 0.1-0.2:1 hybrid reaction 3h-5h at 120 DEG C-140 DEG C, obtains boracic phosphate ester.
Using the boracic phosphate ester obtained as A component or using the boracic phosphate ester wiring solution-forming that obtains as component A.
During using the boracic phosphate ester wiring solution-forming that obtains as component A, preferably boracic phosphate ester is dissolved in distilled water and joining
It is set to the aqueous solution of boracic phosphate ester.
The molecular weight of described Polyethylene Glycol is 200 or 400.
Described boron compound is the one in boric acid, Firebrake ZB.
In order to preferably realize goal of the invention, the present invention also provides for the preparation side of a kind of low cigarette expansion-type transparent fire-retardant coating
Method, described preparation method comprises the following steps:
When component A is boracic phosphate ester, when B component is melmac, respectively by boracic phosphate ester and tripolycyanamide tree
Fat is configured to aqueous solution, the most by a certain percentage homogeneous blend, obtains low cigarette expansion-type transparent fire-retardant coating；
When the solution that component A is boracic phosphate ester, when B component is the solution containing melmac, directly by component A and B
Component homogeneous blend by a certain percentage obtains low cigarette expansion-type transparent fire-retardant coating；
When the solution that component A is boracic phosphate ester, the preferably aqueous solution of boracic phosphate ester；
When the solution that B component is containing melmac, the preferably aqueous solution of melmac；
Boracic phosphate ester in described low cigarette expansion-type transparent fire-retardant coating: melmac mass ratio is 1:1-2.
Described melmac is methyl-etherified melmac or butylated melamine resins.
The technical scheme that the embodiment of the present invention provides has the benefit that
1. boron element is introduced among matrix resin by the present invention low cigarette expansion-type transparent fire-retardant coating, is prevented effectively from because interpolation presses down
The problems such as coating transparent that fumicants causes, animal migration, the compatibility.
2. the carbon source of the present invention low cigarette expansion-type transparent fire-retardant coating collection Intumescent Retardant System, acid source are gentle comes from one,
And introduce Polyethylene Glycol borate, therefore have preferable fire resistance, smoke suppressing and pliability concurrently.
3. the raw material sources of the present invention are extensive, with low cost, and preparation technology is simple, easy to operate.
Detailed description of the invention
Big for the raw smoke of current expansion-type transparent fire-retardant coating, current measure reduces smoke can affect asking of the transparency
Topic, the present invention provides a kind of low cigarette expansion-type transparent fire-retardant coating and preparation method thereof.
Polyethylene glycol 200 (PEG200) Chemical Reagent Co., Ltd., Sinopharm Group, CAS No.25322-68-3
PEG400 (PEG400), Chemical Reagent Co., Ltd., Sinopharm Group,
Boric acid, Hunan Hui Hong reagent company limited, CAS No.11113-50-1
Phosphoric acid, content >=85%, Hunan Hui Hong reagent company limited, CAS No.7664-38-2
Tetramethylolmethane, purity >=98%, Shanghai is by force along chemical reagent company limited, CAS No.115-77-5
N-butyl alcohol, Chemical Reagent Co., Ltd., Sinopharm Group, AR CAS No.71-36-3
Methyl-etherified melmac Xinhua Resin Factory, Shanghai, model 5386-60
Butylated melamine resins Xinhua Resin Factory, Shanghai, model 582-2
Firebrake ZB, Zhenjiang sulfuric acid plant, CAS No.1332-07-6
Embodiment 1:
In the present embodiment, the preparation method of low cigarette expansion-type transparent fire-retardant coating comprises the following steps:
(1) preparation of boracic phosphate ester
A. the preparation of Polyethylene Glycol borate: equipped with agitator, thermometer, reflux condensing tube, the there-necked flask of water knockout drum
In, by PEG200 and boric acid according to mol ratio 2:1 hybrid reaction, reaction temperature is 130 DEG C, and the response time is 3h, prepares yellowish
Color Polyethylene Glycol borate product liquid；
B. the preparation of phosphate ester acid: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
Phosphoric acid, tetramethylolmethane, n-butyl alcohol are according to mol ratio 1:0.3:0.1 hybrid reaction, and reaction temperature is 120 DEG C, and the response time is 6h,
Obtain flaxen phosphate ester acid product liquid；
C. the preparation of boracic phosphate ester: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
In above-mentioned steps a, the Polyethylene Glycol borate of preparation and the phosphate ester acid of preparation in above-mentioned steps b are according to mol ratio 0.15:1
Hybrid reaction, reaction temperature is 120 DEG C, response time 3h, obtains flaxen boracic phosphate ester product liquid.
(2) preparation of low cigarette expansion-type transparent fire-retardant coating
Low cigarette expansion-type transparent fire-retardant coating includes component A and B component, and wherein component A contains boracic phosphate ester, and B component contains
Methyl-etherified melmac, is dissolved in the boracic phosphate ester that step (1) prepares in distilled water that to be made into mass percent be 60%
Aqueous solution, methyl-etherified melmac is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, by two kinds of aqueous solutions
The mix homogeneously of 1:1.2 in mass ratio prepares low cigarette expansion-type transparent fire-retardant coating；Make in low cigarette expansion-type transparent fire-retardant coating
Boracic phosphate ester: the mass ratio of methyl-etherified melmac is 1:1.2.
(3) performance characterization of expansion-type transparent fire-retardant coating
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 2.90g, char volume is 1.80cm3, layer of charcoal height be 12.5mm, flame propagate
Ratio is 6.55, and smoke density grade is 7.03%.
Embodiment 2:
The present embodiment is with the difference of embodiment 1: prepare boracic phosphate ester with Firebrake ZB for raw material in the present embodiment.
(1) preparation of boracic phosphate compound
A. the preparation of Polyethylene Glycol borate: equipped with agitator, thermometer, reflux condensing tube, the there-necked flask of water knockout drum
In, by PEG200 and Firebrake ZB according to mol ratio 2:1 hybrid reaction, reaction temperature is 130 DEG C, and the response time is 3h, prepares light
Yellow Polyethylene Glycol borate product liquid；
B. the preparation of phosphate ester acid: same as in Example 1；
C. the preparation of boracic phosphate ester: same as in Example 1.
(2) preparation of low cigarette expansion-type transparent fire-retardant coating: same as in Example 1.
(3) performance characterization of expansion-type transparent fire-retardant coating
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 2.60g, char volume is 1.10cm3, layer of charcoal height be 15mm, flame propagate ratio
Value is 5.85, and smoke density grade is 5.42%.
Embodiment 3
(1) preparation of boracic phosphate ester
A. the preparation of Polyethylene Glycol borate: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in,
Just PEG400 (PEG400) and boric acid are according to mol ratio 1.5:1 hybrid reaction 2h at 120 DEG C, obtain Polyethylene Glycol
Borate；
B. the preparation of phosphate ester acid: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
Phosphoric acid, tetramethylolmethane and n-butyl alcohol, according to mol ratio 1:0.35:0.2 hybrid reaction 3h at 140 DEG C, obtain flaxen acid
Formula phosphate ester；
C. the preparation of boracic phosphate ester: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
In step a in Polyethylene Glycol borate and step b of preparation the phosphate ester acid of preparation according to mol ratio 0.2:1 at 140 DEG C
Hybrid reaction 5h, obtains boracic phosphate ester.
(2) preparation of low cigarette expansion-type transparent fire-retardant coating:
Low cigarette expansion-type transparent fire-retardant coating includes component A and B component, and wherein component A is containing the boracic phosphoric acid that in steps prepared by (1)
Ester, B component contains butylated melamine resins, and boracic phosphate ester is dissolved in distilled water to be made into mass percent be 60%
Aqueous solution, butylated melamine resins is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, by two kinds of aqueous solutions
The mix homogeneously of 1:2 in mass ratio prepares low cigarette expansion-type transparent fire-retardant coating；The lowest cigarette expansion-type transparent fire-retardant coating contains
Boron phosphate ester: the mass ratio of butylated melamine resins is 1:2.
(3) performance characterization of expansion-type transparent fire-retardant coating
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 2.60g, char volume is 1.40cm3, layer of charcoal height be 14mm, flame propagate ratio
Value is 6.05, and smoke density grade is 5.62%.
Embodiment 4
(1) preparation of boracic phosphate ester
A. the preparation of Polyethylene Glycol borate: equipped with agitator, thermometer, reflux condensing tube, the there-necked flask of water knockout drum
In, by polyethylene glycol 200 (PEG200) with Firebrake ZB according to mol ratio 1.5:1 hybrid reaction 4h at 140 DEG C, obtain poly-second two
Alcohol borate；
B. the preparation of phosphate ester acid: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
Phosphoric acid, tetramethylolmethane and n-butyl alcohol, according to mol ratio 1:0.25:0.1 hybrid reaction 4h at 130 DEG C, obtain phosphate ester acid；
C. the preparation of boracic phosphate ester: by the Polyethylene Glycol borate of preparation in step a and the acid phosphate of preparation in step b
Ester, according to mol ratio 0.1:1 hybrid reaction 4h at 130 DEG C, obtains boracic phosphate ester.
(2) preparation of low cigarette expansion-type transparent fire-retardant coating:
Low cigarette expansion-type transparent fire-retardant coating includes component A and B component, and wherein component A is containing the boracic phosphoric acid that in steps prepared by (1)
Ester, B component contains butylated melamine resins, and boracic phosphate ester is dissolved in distilled water to be made into mass percent be 60%
Aqueous solution, butylated melamine resins is dissolved in distilled water and is made into the aqueous solution that mass percent is 60%, by two kinds of aqueous solutions
The mix homogeneously of 1:1 in mass ratio prepares low cigarette expansion-type transparent fire-retardant coating；The lowest cigarette expansion-type transparent fire-retardant coating contains
Boron phosphate ester: the mass ratio of butylated melamine resins is 1:1.
(3) performance characterization of expansion-type transparent fire-retardant coating
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 2.75g, char volume is 1.86cm3, layer of charcoal height be 12.50mm, flame pass
Broadcasting ratio is 7.65, and smoke density grade is 6.24%.
Comparative example 1:
In this comparative example, wherein component A is the aqueous solution of phosphate ester acid of mass percent 60%, and B component is mass percent
Being the aqueous solution of the methyl-etherified melmac of 60%, concrete preparation process is as follows:
(1) preparation of phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, by phosphoric acid, tetramethylolmethane, n-butyl alcohol
According to mol ratio 1:0.3:0.1 hybrid reaction, reaction temperature is 120 DEG C, and the response time is 6h, obtains flaxen acid phosphate
Ester product liquid, then phosphate ester acid is dissolved in distilled water prepares the aqueous solution that mass percent is 60%, it is component A.
(2) preparation of expansion-type transparent fire-retardant coating
According to mass ratio 1:1.2 homogeneous blend prepared by component A and B component expansion-type transparent fire-retardant coating, and wherein B component is matter
The aqueous solution of the methyl-etherified melmac of amount percent 60%.
(3) expansion-type transparent fire-retardant coating performance characterization
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 4.07g, char volume is 5.8cm3, layer of charcoal height be 2.5mm, flame propagation ratio
Being 16.67, smoke density grade is 17.97%.
Comparative example 2:
The present embodiment is essentially identical with comparative example 1, and difference is: in the present embodiment, component A is flexible phosphate ester.
(1) preparation of flexible phosphate ester
A. the preparation of phosphate ester acid: same as in Example 1；
B. the preparation of flexible phosphate ester: equipped with agitator, thermometer, reflux condensing tube, water knockout drum there-necked flask in, will
In above-mentioned steps a, the phosphate ester acid of preparation and PEG200 are according to mol ratio 0.15:1 hybrid reaction, and reaction temperature is 120 DEG C,
Response time 3h, obtains the flaxen flexible phosphate ester product liquid containing Polyethylene Glycol.Afterwards, flexibility phosphate ester is dissolved in steaming
Distilled water is made into the aqueous solution that mass percent is 60%, is component A.
(2) preparation of expansion-type transparent fire-retardant coating
Component A step (1) prepared and B component prepare expansion-type transparent fire-retardant coating according to mass ratio 1:1.2 homogeneous blend,
Wherein B component is the aqueous solution of methyl-etherified melmac of mass percent 60%.
(3) expansion-type transparent fire-retardant coating performance characterization
" construction material burning or the cigarette decomposed are close to use GB12441-2005 " finishing fire retardant paint " and GB/T 8626-2007
Degree test method " the fire-retardant of the expansion-type transparent fire-retardant coating prepared in the present embodiment and smoke suppressing are measured:
The mass loss in cell method of this coating is 3.50g, char volume is 2.80cm3, layer of charcoal height be 8mm, flame propagate ratio
Value is 14.32, and smoke density grade is 15.84%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. one kind low cigarette expansion-type transparent fire-retardant coating, it is characterised in that include that component A and B component, described component A comprise and contain
Boron phosphate ester, described B component comprises melmac.
Low cigarette expansion-type transparent fire-retardant coating the most according to claim 1, it is characterised in that boracic phosphoric acid in described coating
Ester: melmac mass ratio is 1:1-2.
Low cigarette expansion-type transparent fire-retardant coating the most according to claim 1 and 2, it is characterised in that described component A is boracic
The aqueous solution of phosphate ester, described B component is the aqueous solution of melmac.
4. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-3, it is characterised in that described tripolycyanamide
Resin is methyl-etherified melmac or butylated melamine resins.
5. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-4, it is characterised in that described boracic phosphoric acid
The preparation method of ester comprises the following steps:
A. the preparation of Polyethylene Glycol borate: by Polyethylene Glycol and boron compound according to mol ratio 1.5-2:1 at 120 DEG C-140
Hybrid reaction 2-4h at DEG C, obtains Polyethylene Glycol borate；
B. the preparation of phosphate ester acid: by phosphoric acid, tetramethylolmethane and n-butyl alcohol according to mol ratio 1:0.25-0.35:0.1-0.2
Hybrid reaction 3h-6h at 120 DEG C-140 DEG C, obtains phosphate ester acid；
C. the preparation of boracic phosphate ester: by the Polyethylene Glycol borate of preparation in step a and the acid phosphate of preparation in step b
Ester, according to mol ratio 0.1-0.2:1 hybrid reaction 3h-5h at 120 DEG C-140 DEG C, obtains boracic phosphate ester.
6. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-5, it is characterised in that described Polyethylene Glycol
Molecular weight be 200 or 400.
7. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-6, it is characterised in that described boron compound
For the one in boric acid, Firebrake ZB.
8., according to a preparation method for the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-7, its feature exists
In, described preparation method comprises the following steps:
When component A is boracic phosphate ester, when B component is melmac, respectively by boracic phosphate ester and tripolycyanamide tree
Fat is configured to aqueous solution, the most by a certain percentage homogeneous blend, obtains low cigarette expansion-type transparent fire-retardant coating；
When the solution that component A is boracic phosphate ester, when B component is the solution containing melmac, directly by component A and B
Component homogeneous blend by a certain percentage obtains low cigarette expansion-type transparent fire-retardant coating；
Boracic phosphate ester in described low cigarette expansion-type transparent fire-retardant coating: melmac mass ratio is 1:1-2.
9. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-8, it is characterised in that when component A is for containing
During the solution of boron phosphate ester, boracic phosphate ester is dissolved in distilled water the aqueous solution being configured to boracic phosphate ester；When B component is for containing
During the solution of melmac, melmac is dissolved in distilled water the aqueous solution being configured to melmac.
10. according to the arbitrary described low cigarette expansion-type transparent fire-retardant coating of claim 1-9, it is characterised in that described melamine
Polyimide resin is methyl-etherified melmac or butylated melamine resins.
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| CN115353792A (en) * | 2022-08-15 | 2022-11-18 | 中南大学 | Antibacterial weather-resistant multifunctional integrated intumescent transparent fireproof coating and preparation method thereof |
| CN115651441A (en) * | 2022-10-18 | 2023-01-31 | 浙江大学 | Preparation method and application of transparent waterproof intumescent flame-retardant coating |
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| CN106810761A (en) * | 2016-12-22 | 2017-06-09 | 阜阳市三郁包装材料有限公司 | Modified polypropylene flame redardant foamed board of a kind of hydridization polytetrafluoroethylene (PTFE) silica aerogel and preparation method thereof |
| CN110964363A (en) * | 2019-11-12 | 2020-04-07 | 应急管理部四川消防研究所 | Transparent fireproof coating and preparation method thereof |
| CN111662585A (en) * | 2020-06-24 | 2020-09-15 | 谭亮 | Fireproof coating with heat insulation and preservation performance |
| CN114605889A (en) * | 2022-04-13 | 2022-06-10 | 中国人民警察大学 | Water-based intumescent transparent fireproof coating and preparation method thereof |
| CN115353792A (en) * | 2022-08-15 | 2022-11-18 | 中南大学 | Antibacterial weather-resistant multifunctional integrated intumescent transparent fireproof coating and preparation method thereof |
| CN115651441A (en) * | 2022-10-18 | 2023-01-31 | 浙江大学 | Preparation method and application of transparent waterproof intumescent flame-retardant coating |
| CN115651441B (en) * | 2022-10-18 | 2024-01-02 | 浙江大学 | Preparation method and application of transparent waterproof intumescent flame retardant coating |
| CN116948485A (en) * | 2023-07-28 | 2023-10-27 | 斯坦途(福建)防火材料有限公司 | Aerogel compounded hydrophobic transparent intumescent fire-retardant coating and preparation method thereof |
| CN117210085A (en) * | 2023-10-13 | 2023-12-12 | 南平市鸿联环保新材料有限公司 | Fireproof coating based on modified amino resin and preparation method thereof |
| CN117210085B (en) * | 2023-10-13 | 2024-07-05 | 南平市鸿联环保新材料有限公司 | Fireproof coating based on modified amino resin and preparation method thereof |
| CN117624998A (en) * | 2024-01-26 | 2024-03-01 | 中建国际工程有限公司 | Intumescent fireproof flame-retardant decorative coating |
| CN117624998B (en) * | 2024-01-26 | 2024-04-30 | 中建国际工程有限公司 | Intumescent fireproof flame-retardant decorative coating |
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