CN112662012B - Organosilicone-modified phytate-coupled ammonium polyphosphate and fireproof coating prepared from organosilicone-modified phytate-coupled ammonium polyphosphate - Google Patents
Organosilicone-modified phytate-coupled ammonium polyphosphate and fireproof coating prepared from organosilicone-modified phytate-coupled ammonium polyphosphate Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 229920001276 ammonium polyphosphate Polymers 0.000 title claims abstract description 55
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class 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 title claims abstract description 51
- 239000004114 Ammonium polyphosphate Substances 0.000 title claims abstract description 50
- 235000019826 ammonium polyphosphate Nutrition 0.000 title claims abstract description 50
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- -1 silicon modified phytate Chemical class 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 238000006011 modification reaction Methods 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 44
- 229910000831 Steel Inorganic materials 0.000 claims description 24
- 239000010959 steel Substances 0.000 claims description 24
- 239000003365 glass fiber Substances 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- WPEXVRDUEAJUGY-UHFFFAOYSA-B hexacalcium;(2,3,4,5,6-pentaphosphonatooxycyclohexyl) phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([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 WPEXVRDUEAJUGY-UHFFFAOYSA-B 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- IWEDUKDKQUXPLH-NFJZTGFVSA-L [Mg++].OP(O)(=O)O[C@H]1[C@@H](OP(O)(O)=O)C(OP(O)([O-])=O)[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)C1OP(O)([O-])=O Chemical compound [Mg++].OP(O)(=O)O[C@H]1[C@@H](OP(O)(O)=O)C(OP(O)([O-])=O)[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)C1OP(O)([O-])=O IWEDUKDKQUXPLH-NFJZTGFVSA-L 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims 1
- MOWSUOKIHAQPCR-UHFFFAOYSA-N diethoxy-ethyl-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethoxy]silane Chemical compound C1C(C(C)O[Si](CC)(OCC)OCC)CCC2OC21 MOWSUOKIHAQPCR-UHFFFAOYSA-N 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 239000012747 synergistic agent Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 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 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Diphosphoinositol tetrakisphosphate Chemical compound 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 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- BDVMTRCCIQHRBL-UHFFFAOYSA-J phosphonato phosphate;titanium(4+) Chemical compound [Ti+4].[O-]P([O-])(=O)OP([O-])([O-])=O BDVMTRCCIQHRBL-UHFFFAOYSA-J 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical group CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an organic silicon modified phytate coupled ammonium polyphosphate and a fireproof coating prepared from the same, wherein an epoxy silane coupling agent and a phytate metal salt are respectively added into ammonium polyphosphate in proportion and are uniformly mixed, the modification reaction is carried out for a period of time at a high temperature, the mixture is crushed, the phytate coupled ammonium polyphosphate with high phosphorus content and good fluidity is obtained, and the fireproof coating prepared by mixing the phytate coupled ammonium polyphosphate with other synergists prolongs the stability and the storage time of the coating, the fire resistance time measured under a fire resistance limit test can reach 120min at most, a carbon layer after combustion is compact and continuous, the binding force with a bottom plate is good, the coating does not fall off, and the performance of the coating is superior to that of the fireproof coating prepared from the existing commercial APP in all aspects.
Description
Technical Field
The invention relates to the field of fireproof coatings, in particular to organic silicon modified phytate coupled ammonium polyphosphate and a fireproof coating prepared from the same.
Background
The steel structure building has the characteristics of short construction time, large span, modular design and the like, and has unique advantages in the fields of industrial and civil buildings. However, in case of fire, the strength of the steel structure is significantly reduced with the increase of temperature, for example, when the temperature is increased from 250 to 500 ℃, the mechanical strength of the steel structure is reduced to 50% of the original value, and when the temperature is reduced to more than 750 ℃, the mechanical strength is reduced by 90%, which causes the collapse of the steel structure building due to the loss of the bearing capacity at high temperature, and brings great difficulty for rescue and escape. Therefore, fire resistance of steel structure buildings is improved, safety of people, property and buildings is ensured, and fire prevention measures are required for the steel structure buildings. At present, the most widely used method is to use the intumescent fire-retardant coating on the steel structure building, once a fire disaster occurs, the intumescent fire-retardant coating can form a highly expanded foaming layer on the surface of the steel structure under the action of flame, and can effectively prevent heat from directly acting on the surface of the steel structure, thereby improving the fire resistance limit of the steel structure.
Chinese patent application CN108948839A (application date 2018, 7 and 19) discloses 'an intumescent fire retardant coating based on a high-efficiency synergist and a preparation method thereof', the invention takes water-based resin as a matrix, and the flame-retardant time of the fire retardant coating is greatly improved by adding a high-temperature-resistant synergist (zirconium nitride, zirconium oxide and zirconium silicate); chinese patent application CN111423779A (5/14/2020/application date) discloses a steel structure fireproof paint, a preparation method and application thereof, and the strength and the fire resistance limit of an expanded carbon layer are improved by adding carbon nano tubes and basalt fibers into the fireproof paint. China CN108455548A (application date 2018, 5, 15) discloses a preparation method of low-acid-value and low-viscosity crystal II-type ammonium polyphosphate, and after the ammonium polyphosphate is applied to a fireproof coating, the storage viscosity change rate of the coating is reduced from 67% to 20-30%, but the viscosity change is still large. The aim of improving the fire resistance of a steel structure is fulfilled by adding one or more synergists, but the synergists are high in price, are not beneficial to industrial production, are not remarkable in improvement of the fire resistance of the fire-retardant coating, and are neglected to influence the overall viscosity and the storage period.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an organic silicon modified phytate coupled ammonium polyphosphate flame retardant with higher flame retardant effect; it is also an object of the present invention to provide a highly effective intumescent fire retardant coating prepared by using the aforementioned fire retardant.
The technical scheme is as follows: in order to achieve the above object, the organic silicon modified phytate coupled ammonium polyphosphate is prepared by the following steps: respectively adding the epoxy silane coupling agent and the phytate metal salt into the ammonium polyphosphate according to the proportion, uniformly mixing, carrying out modification reaction at high temperature for a period of time, and crushing.
The phytate metal salt modified ammonium polyphosphate (PA-APP) prepared by the method has the following structural general formula:
in the formula, R1Is an epoxy silane coupling agent modifying group, R2N represents the degree of polymerization.
The metal phytate can contain a metal ion selected from any one of zinc phytate, copper phytate, aluminum phytate, nickel phytate, iron phytate, calcium phytate and magnesium phytate; the metal phytate may also contain two or more metal ions, such as phytin or phytin. Different metal phytate and flame retardant have different matching, and the preferable scheme comprises calcium phytate, zinc phytate and nickel phytate.
The phosphorus content of the ammonium polyphosphate fire retardant is 31-33% at present, the phosphorus content is improved to 33-37% by coupling the ammonium polyphosphate with the phytic acid, and the improvement of the phosphorus content can accelerate the degradation of a matrix and provide a material source for a carbon layer on one hand, and can react with a carbon forming agent on the other hand to form a more stable expanded foaming carbon layer structure, so that the heat insulation performance is improved, and the fire resistance of the coating is improved.
Further, the epoxy silane coupling agent is selected from the group consisting of but not limited to gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and (3,4 epoxycyclohexyl) -ethyltriethoxysilane.
After epoxy silane coupling is added into ammonium polyphosphate, the ammonium polyphosphate is activated in a high-temperature environment and further reacts with phytate metal salt. Generally, the high-temperature environment is 100-200 ℃, and the phytic acid groups can be completely activated and effectively linked after the reaction is carried out for 0.5-2.5 h at the temperature; as a further optimization of the method, the temperature is 140-180 ℃, and the preferable reaction time is 1-2 h.
The total adding amount of the epoxy silane coupling agent and the phytate metal salt is 1-5% of ammonium polyphosphate, and the ratio of the epoxy silane coupling agent to the phytate metal salt is 1: 0.5-3.5.
The invention provides a high-efficiency intumescent fire retardant coating, which comprises at least one acrylic emulsion, water and a synergist, wherein phytate is coupled with ammonium polyphosphate, at least one carbon source and melamine; the carbon source is any one of starch, pentaerythritol, glycerol and cellulose.
Wherein, the synergist is selected from any one or more of sodium montmorillonite, Layered Double Hydroxide (LDH), wollastonite, kaolin and sepiolite. As a further optimization of the invention, the synergist is any one of sodium montmorillonite, LDH and kaolin.
It is worth noting that there is a large surface energy difference between the polymer matrix and the synergists during the combustion process, which have achieved migration to the surface and formed enrichment before the polymer burns and even degrades, with a very good masking effect.
Further, the fire-retardant coating also comprises a dispersant which is selected from any one or more of a sodium polycarboxylate dispersant, an ammonium polyacrylate dispersant and an ammonium polycarboxylate dispersant.
Further, the fireproof coating also comprises glass fibers, and the glass fibers are selected from any one or combination of more of medium alkali glass fibers, chopped glass fibers and hollow glass fibers. The adding amount of the glass fiber is 3-15% of the total mass of the fireproof coating.
Further, the fireproof coating also comprises titanium dioxide, wherein the titanium dioxide is selected from any one of rutile type titanium dioxide and anatase type titanium dioxide, and the addition amount of the titanium dioxide is 6.5-22% of the total mass of the fireproof coating. A proper amount of titanium dioxide can react with acid substances generated by decomposing APP to form titanium pyrophosphate, and the titanium pyrophosphate is enriched on the surface of the substrate to play a good role in blocking.
The invention relates to a high-efficiency intumescent fire retardant coating which is characterized by comprising the following components in parts by weight:
in one embodiment of the invention, the metal salt is selected from zinc phytate, the silane coupling agent is selected from 3-glycidylpropyltrimethoxysilane, the ratio of the two is 2:1, and the addition amount is 5% of ammonium polyphosphate.
In another embodiment of the present invention, the metal salt is selected from calcium phytate, the silane coupling agent is selected from 3-glycidylpropyltrimethoxysilane, and the ratio of the two is 1:1, and the addition amount is 3%.
In yet another embodiment of the present invention, the metal salt is selected from nickel phytate, and the silane coupling agent is selected from gamma-glycidoxypropyltrimethoxysilane in a ratio of 3:1, added in an amount of 2%.
As further optimization of the invention, when the components of the high-efficiency intumescent fire-retardant coating are added, the dispersant, the synergist, the titanium dioxide and the glass fiber are added into water, the water-based acrylic resin is added after the high-speed stirring is carried out uniformly, and finally the carbon source, the melamine and the PA-APP are added in sequence.
Has the advantages that: the organic silicon modified phytate coupled ammonium polyphosphate provided by the invention is a novel ammonium polyphosphate flame retardant, and the phosphorus content of the flame retardant is about 20% more than that of other ammonium polyphosphate flame retardants. On one hand, the fireproof coating prepared by the flame retardant has better fluidity, can not form gel or even solidify after being stored for 30 days at normal temperature, and prolongs the stability and the storage time of the coating; on the other hand, the fire resistance of the coating can be obviously improved, and particularly, when the coating is coated on a steel structure, a continuous and compact carbon residue layer can be formed under the action of the temperature rise condition of cellulose fire, no obvious holes exist, and the barrier property is good.
In addition, the organic silicon modified phytate coupled ammonium polyphosphate is prepared by a solid phase modification method, the product yield is 100%, no solid-liquid waste is generated, and the environmental protection requirement is met;
the efficient intumescent fire-retardant coating prepared by using the phytate coupled ammonium polyphosphate adopts the flaky inorganic filler as the synergist, a large surface energy difference exists between the polymer and the flaky synergist in the combustion process, and the sheets are migrated to the surface and form enrichment before the polymer is combusted or even degraded, so that the efficient intumescent fire-retardant coating has a good shielding effect; meanwhile, the introduction of metal ions further improves the carbonization of the flame retardant and improves the fire resistance of the fireproof coating. By surface modification of ammonium polyphosphate, the stability of the coating in the coating is improved, the viscosity of the coating is prevented from increasing in the storage process, and the storage time is prolonged.
The high-efficiency intumescent fire retardant coating prepared by the invention is applied to a steel structure, the fire-resistant time can reach 120min to the maximum, a burnt carbon layer is compact and continuous, the bonding force with a bottom plate is good, the coating does not fall off, and the performance of the coating in all aspects is superior to that of the fire retardant coating prepared by the existing commercial APP.
Drawings
FIG. 1 is a carbon residue diagram of a high-efficiency intumescent fire retardant coating for a steel structure, which is described in example 7 of experimental example 1;
FIG. 2 is a carbon residue map of the fire retardant coating described in comparative example 1 in test example 1.
Detailed Description
The invention is further illustrated below with reference to specific embodiments and the accompanying drawings.
Example 1
Adding 0.5 wt% of KH560 (gamma-glycidoxypropyltrimethoxysilane) into ammonium polyphosphate, stirring at a high speed for 15s, uniformly mixing, then adding 1.5 wt% of nickel phytate, and continuously stirring at a high speed for 20s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 2 hours at 140 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample A which is white powder, wherein D50 is 12 um.
Example 2
Adding 0.5 wt% of KH560 (gamma-glycidyl ether oxypropyl trimethoxysilane) into ammonium polyphosphate, stirring at a high speed for 10s, uniformly mixing, then adding 4.0 wt% of zinc phytate, and continuously stirring at a high speed for 25s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 2.5 hours at 100 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample B which is white powder, wherein D50 is 20 um.
Example 3
Adding 2.5 wt% of KH-1770((3,4 epoxy cyclohexyl) -ethyl triethoxysilane) into ammonium polyphosphate, stirring at high speed for 40s, mixing uniformly, adding 1.0 wt% of zinc phytate, and stirring at high speed for 10s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 0.5 hour at 200 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample C which is white powder, wherein D50 is 16 um.
Example 4
Adding 0.5 wt% of KH560 (gamma-glycidoxypropyltrimethoxysilane) and 1 wt% of Z6040 (3-glycidoxypropyltrimethoxysilane) into ammonium polyphosphate, stirring at a high speed for 30s, uniformly mixing, then adding 2.5 wt% of zinc phytate, and continuously stirring at a high speed for 15s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 1.5 hours at 150 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample D which is white powder, wherein D50 is 21 um.
Example 5
Adding 0.5 wt% of KH560 (gamma-glycidoxypropyltrimethoxysilane) and 1 wt% of Z6040 (3-glycidoxypropyltrimethoxysilane) into ammonium polyphosphate, stirring at a high speed for 20s, uniformly mixing, then adding 2 wt% of calcium phytate, and continuously stirring at a high speed for 20s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 1.5 hours at 160 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample E which is white powder, wherein D50 is 19 um.
Example 6
Adding 1.5 wt% of KH-1770((3,4 epoxy cyclohexyl) -ethyl triethoxysilane) into ammonium polyphosphate, stirring at a high speed for 20s, mixing uniformly, adding 2 wt% of calcium phytate, and continuously stirring at a high speed for 20s to obtain a flame retardant primary product; taking out and putting into a high-temperature electronic oven to react for 2 hours at 130 ℃. And taking out after the reaction is finished, and crushing to obtain a PA-APP sample F which is white powder, wherein D50 is 20 um.
Example 7
The high-efficiency intumescent fire retardant coating for the steel structure comprises the following components in parts by weight: 18 parts of acrylic emulsion, 25 parts of water, 0.5 part of dispersant, 0.5 part of sodium montmorillonite, 1 part of glass fiber, 15 parts of titanium dioxide, 20 parts of PA-APP sample A described in example 1, 10 parts of pentaerythritol and 10 parts of melamine.
Example 8
The high-efficiency intumescent fire retardant coating for the steel structure comprises the following components in parts by weight: 15 parts of acrylic emulsion, 25 parts of water, 1.5 parts of dispersant, 3 parts of LDH, 3 parts of glass fiber, 15 parts of titanium dioxide, 20 parts of PA-APP sample B described in example 2, 10 parts of pentaerythritol and 7.5 parts of melamine.
Example 9
The high-efficiency intumescent fire retardant coating for the steel structure comprises the following components in parts by weight: 25 parts of acrylic emulsion, 25 parts of water, 1.5 parts of dispersing agent, 2.5 parts of kaolin, 1.5 parts of glass fiber, 8 parts of titanium dioxide, 25 parts of PA-APP sample C described in example 3, 7.5 parts of pentaerythritol and 4 parts of melamine.
Example 10
The high-efficiency intumescent fire retardant coating for the steel structure comprises the following components in parts by weight: 18 parts of acrylic emulsion, 25 parts of water, 0.5 part of dispersant, 0.5 part of sodium montmorillonite, 1 part of glass fiber, 15 parts of titanium dioxide, 20 parts of PA-APP sample E described in example 5, 10 parts of pentaerythritol and 10 parts of melamine.
Example 11
The high-efficiency intumescent fire retardant coating for the steel structure comprises the following components in parts by weight: 18 parts of acrylic emulsion, 25 parts of water, 0.5 part of dispersant, 0.5 part of sodium montmorillonite, 1 part of glass fiber, 15 parts of titanium dioxide, 20 parts of PA-APP sample F described in example 6, 10 parts of pentaerythritol and 10 parts of melamine.
Comparative example 1
The fireproof coating comprises the following components in parts by weight: 18 parts of acrylic emulsion, 25 parts of water, 1 part of dispersant, 1 part of glass fiber, 15 parts of titanium dioxide, 20 parts of commercially available ammonium polyphosphate (II type, n is more than 1000), 10 parts of pentaerythritol and 10 parts of melamine.
Comparative example 2
The fireproof coating comprises the following components in parts by weight: 18 parts of acrylic emulsion, 25 parts of water, 1 part of dispersing agent, 1 part of glass fiber, 15 parts of titanium dioxide, 20 parts of commercially available aluminum hypophosphite, 10 parts of pentaerythritol and 10 parts of melamine.
Test example 1
The fire-retardant coatings obtained in examples 7-11 and comparative examples 1 and 2 were mixed uniformly, and the fire endurance test was carried out according to the fire resistance test method in GB 14907-2018 Steel Structure fire-retardant coating, wherein the coating thickness was 1.0mm, and the measured fire resistance time, carbon layer state and carbon layer height under the condition of temperature rise of cellulose fire are shown in Table 1:
TABLE 1 Effect of organosilicon-modified phytate-coupled ammonium polyphosphate on fire resistance of coatings
| Group of | Time to fire | State of carbon layer | Height of carbon layer |
| Example 7 | 120min | Continuous, dense | 3.5 |
| Example 8 | 100min | Continuous, dense | 3.3 |
| Example 9 | 108min | Continuous, dense | 3.9 |
| Comparative example 10 | 105min | Continuous, dense | 3.2 |
| Example 11 | 102min | Continuous, dense | 3.3 |
| Comparative example 1 | 86min | Loose, porous | 2.1 |
| Comparative example 2 | 65min | Loose, porous | 1.5 |
As can be seen from the above table, the fire-retardant coatings provided in examples 7 to 11 have continuous and dense carbon residue layers, high expansion degree and good barrier property, and therefore have a relatively long fire-resistant time, while the carbon layer of comparative example 1 has relatively large pores, poor continuity, small expansion height of the carbon layer, and poor fire resistance, and the aluminum hypophosphite of comparative example 2 has 42% of phosphorus content, but has poor fire resistance and loose carbon layer. The result shows that the combination of the ammonium polyphosphate modified by the phytate metal salt and the specific synergist greatly improves the fire resistance of the fireproof coating compared with the prior art.
Test example 2
The fire retardant coatings obtained in examples 7 to 11 and comparative examples 1 and 2 were uniformly mixed, stored at normal temperature, and the viscosity of the coatings was measured at regular intervals using a rotary viscometer, and the specific values are shown in Table 2.
Table 2 effect of organosilicone-modified phytate-coupled ammonium polyphosphate on coating flowability and pot life
As can be seen from the table, the steel structure fireproof coating prepared from ammonium polyphosphate modified by phytate metal has small viscosity change along with the prolonging of the storage time, while the coating is gelled after 30 days in comparative example 1, and is gelled after 15 days in comparative example 2, which cannot be used. This can effectively demonstrate that the ammonium polyphosphate is modified by the phytate metal salt, the stability of the coating is improved, the viscosity of the coating is prevented from increasing in the storage process, and the storage time is prolonged.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (12)
1. An organic silicon modified phytate coupled ammonium polyphosphate is characterized by being prepared by the following method: adding an epoxy silane coupling agent into ammonium polyphosphate according to a proportion, uniformly mixing, then adding a metal phytate according to a proportion, mixing, carrying out modification reaction at a high temperature for a period of time, and crushing;
the metal phytate is selected from any one of zinc phytate, copper phytate, aluminum phytate, nickel phytate, iron phytate, calcium phytate, magnesium phytate, calcium magnesium phytate and zinc magnesium phytate.
2. The organosilicon modified phytate coupled ammonium polyphosphate according to claim 1, wherein: the epoxy silane coupling agent is one or a combination of more of gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and (3, 4-epoxycyclohexyl) -ethyltriethoxysilane.
3. The organosilicon modified phytate coupled ammonium polyphosphate according to claim 2, wherein: the modification reaction is carried out for 0.5 to 2.5 hours at the temperature of 100 ℃ and 200 ℃.
4. An organosilicon modified phytate coupled ammonium polyphosphate according to any one of claims 1 to 3, characterized in that: the total adding amount of the epoxy silane coupling agent and the phytate metal salt is 1-5% of that of the ammonium polyphosphate.
5. The organosilicon modified phytate coupled ammonium polyphosphate according to claim 4, wherein: the ratio of the epoxy silane coupling agent to the phytate metal salt is 1: 0.5-3.5.
6. The organosilicon modified phytate-coupled ammonium polyphosphate according to claim 5, characterized in that: the phosphorus content of the organic silicon modified phytate coupled ammonium polyphosphate is 33-37%, and the metal ion content is 0.5-1.5%.
7. An efficient intumescent fire retardant coating is characterized in that: comprises at least one acrylic emulsion, water, a synergist, the organic silicon modified phytate coupled ammonium polyphosphate PA-APP defined in claim 1, at least one carbon source and melamine; the carbon source is any one of starch, pentaerythritol, glycerol and cellulose.
8. A high efficiency intumescent fire retardant coating as claimed in claim 7, wherein: the synergist is any one or combination of more of sodium montmorillonite, double-layer double metal hydroxide (LDH), wollastonite, kaolin and sepiolite.
9. A high-efficiency intumescent fire-retardant coating as claimed in claim 8, characterized in that: the dispersant is one or more of a sodium polycarboxylate dispersant, an ammonium polyacrylate dispersant and a polycarboxylic ammonium salt dispersant.
10. The high-efficiency intumescent fire retardant coating for steel structures as claimed in claim 9, characterized in that: the fireproof coating further comprises glass fibers, wherein the glass fibers are selected from any one or combination of more of medium-alkali glass fibers, chopped glass fibers and hollow glass fibers, and the adding amount of the glass fibers is 3-15% of the total mass of the fireproof coating.
11. The high-efficiency intumescent fire retardant coating for steel structures as claimed in claim 10, characterized in that: the fireproof coating further comprises titanium dioxide, wherein the titanium dioxide is selected from any one of rutile type titanium dioxide and anatase type titanium dioxide, and the addition amount of the titanium dioxide is 6.5-22% of the total mass of the fireproof coating.
12. A high-efficiency intumescent fire retardant coating as claimed in claim 11, characterized by comprising the following components in parts by weight:
15-25 parts of acrylic emulsion,
15-25 parts of water, namely,
0.5 to 1.5 parts of a dispersant,
0.5 to 3 parts of a synergistic agent,
1 to 3 parts of glass fiber,
8-15 parts of titanium dioxide powder,
20-30 parts of PA-APP,
4-10 parts of pentaerythritol,
4-10 parts of melamine.
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