Phosphorus-nitrogen-based intumescent flame retardant and synthetic method and use thereof
10301548 ยท 2019-05-28
Assignee
Inventors
Cpc classification
C09D7/48
CHEMISTRY; METALLURGY
C08K5/0066
CHEMISTRY; METALLURGY
D21H17/71
TEXTILES; PAPER
International classification
C09D5/18
CHEMISTRY; METALLURGY
D21H17/00
TEXTILES; PAPER
Abstract
This disclosure provides high-efficiency and low-energy-consumption synthetic methods of a series of phosphorus-nitrogen-based intumescent flame retardants and the use thereof in paint flame retarding. 1 part by weight of a phosphorization agent and 0.5-4.0 parts by weight of a nitrogen-containing foaming agent are uniformly mixed and stirred at room temperature, and an amount of water is further added to emit heat and initiate reaction. 0.5-3.0 parts by weight of a charring agent and 0.5-4.0 parts by weight of a hydroxy-containing polyfuctional crosslinking agent are then added, and reacted with stirring. An amine compound is finally added for neutralization until pH value is 5-8, and solid liquid separation is performed. The solid portion is dried to obtain a main body portion of a phosphorus-nitrogen-based intumescent flame retardant. The resultant filtrate is diluted with - volume of water, and a flame retardant product is obtained. This flame retardant product is mainly used in the flame retarding of paper and cotton fabrics. The main body and different proportions of other nitrogen-containing foaming agents and charring agents are uniformly mixed and pulverized into nano- and micro-scale, and a phosphorus-nitrogen-based intumescent flame retardant is obtained. The nano- and micro-scale phosphorus-nitrogen intumescent flame retardant is mixed into a paint at a weight ratio of 15-30%, to obtain a flame-retardant paint which is capable of maintaining mechanical and physical properties of the paint. The phosphorus-nitrogen-based intumescent flame retardant of this disclosure is an intumescent flame retardant having a synergistic effect of phosphorus and nitrogen.
Claims
1. A phosphorus-nitrogen-based intumescent flame retardant, comprising a first nitrogen-containing foaming agent, a first charring agent, and a flame retardant main body, the flame retardant main body being a product of a reaction between a phosphorization agent, a second nitrogen-containing foaming agent, a second charring agent, and a hydroxy-containing polyfuctional crosslinking agent, wherein said first nitrogen-containing foaming agent and said second nitrogen-containing foaming agent are each independently selected from the group consisting of ammonium hydrogen carbonate, melamine, polyphosphamide, urea, semicarbazide, a hydrazine compound, a guanidine compound, and an azo compound; said first charring agent and said second charring agent are each independently selected from the group consisting of an amylose, a pullulan, a cyclodextrin, a saccharide compound, and a polyol amine compound; said phosphorization agent is red phosphorus, phosphorus pentaoxide, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphamide, polyphosphamide, or phosphorus oxychloride; and said hydroxy-containing polyfunctional crosslinking agent is ethylene glycol, glycerol, pentaerythritol, phloroglucinol, hydroquinone, aminoethanol, aminopropanol, or an alcoholamine compound.
2. The phosphorus-nitrogen-based intumescent flame retardant according to claim 1, wherein the ratio of said flame retardant main body to said first nitrogen-containing foaming agent to said first charring agent is 1-3:0.5-1.5:0.2-1.2.
3. The phosphorus-nitrogen-based intumescent flame retardant according to claim 1, wherein the weight ratio of said phosphorization agent to said second nitrogen-containing foaming agent is 1:0.5 to 1:4.0, the weight ratio of said phosphorization agent to said second charring agent is 1:0.5 to 1:3.0, the weight ratio of said phosphorization agent to said hydroxy-containing polyfuctional crosslinking agent is 1:0.5 to 1:4.0, the particle size of said flame retardant is 0.4-20.0 micrometers, the phosphorus content of said flame retardant is 8-23%, and/or the nitrogen content of said flame retardant is 10-34%.
4. A method of preparing the phosphorus-nitrogen-based intumescent flame retardant according to claim 1, comprising the following steps: a) a flame retardant main body preparing step, wherein a phosphorization agent, a second nitrogen-containing foaming agent, a second charring agent, and a hydroxy-containing polyfuctional crosslinking agent are reacted to obtain a reaction system containing a flame retardant main body; b) a filtering step, wherein the solid in the reaction system is filtered off to obtain a flame retardant main body; and c) a mixing step, wherein said flame retardant main body is mixed with a first nitrogen-containing foaming agent and a first charring agent.
5. The method of preparing a phosphorus-nitrogen-based intumescent flame retardant according to claim 4, wherein, in said flame retardant main body preparing step, said phosphorization agent and said second nitrogen-containing foaming agent are first reacted in the presence of an initiator, and then said second charring agent and said hydroxy-containing polyfuctional crosslinking agent are added.
6. A flame-retardant paint, comprising a paint body and the phosphorus-nitrogen-based intumescent flame retardant according to claim 1.
7. Use of the phosphorus-nitrogen-based intumescent flame retardant according to claim 1 in the flame retarding of wood, cotton cloth, and paper.
8. A flame-retardant wood, a flame-retardant cotton cloth, or a flame-retardant paper, containing the phosphorus-nitrogen-based intumescent flame retardant according to claim 1.
9. A flame-retardant paint, comprising a paint body and the phosphorus-nitrogen-based intumescent flame retardant according to claim 2.
10. A flame-retardant paint, comprising a paint body and the phosphorus-nitrogen-based intumescent flame retardant according to claim 3.
11. A flame-retardant wood, a flame-retardant cotton cloth, or a flame-retardant paper, containing the phosphorus-nitrogen-based intumescent flame retardant according to claim 2.
12. A flame-retardant wood, a flame-retardant cotton cloth, or a flame-retardant paper, containing the phosphorus-nitrogen-based intumescent flame retardant according to claim 3.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
DESCRIPTION OF EMBODIMENTS
EXAMPLES
Example 1
(8) In a 250-milliliter beaker, 10 grams of polyphosphoric acid were added, then 10 grams of a nitrogen-containing foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent, such as cellulose, were further added to continue the reaction; and then a hydroxy-containing polyfuctional crosslinking agent, such as 10 grams of hydroquinone and 5 grams of a polyol, was added. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at a temperature of 15-40 C. for neutralization until pH was 5-8. Subsequently filtration was performed and filter residue was dried to obtain a flame retardant main body. The resultant flame retardant main body, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a phosphorus-nitrogen intumescent flame retardant. The resultant byproduct filtrate was diluted with water, and a flame retardant product was obtained.
(9) 6 grams of this flame retardant were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(10) flame retarding time of 10 minutes (big panel method);
(11) flame propagation rate of 38% (tunnel method);
(12) carbonization volume, weight loss of 9 g (cabinet method);
(13) paint strip limiting oxygen index (LOI) of 30.1%.
(14) The mechanical and physical properties reached the standards of GB/T23997-2009 and GB18581-2009.
Example 2
(15) According to the method described in Example 1, the amount of polyphosphoric acid used was kept unchanged, but the ratio of polyphosphoric acid to the second charring agent (pentaerythritol) therein was changed to the values listed in Table 1, and the experiment described above was performed. The experimental results were given in Table 1.
(16) TABLE-US-00001 TABLE 1 Experimental results at different weight ratios of the phosphorization agent to the hydroxy-containing polyfuctional crosslinking agent Phosphorization Flame Flame agent:penta- retarding propa- Combustion Paint strip erythritol time gation weight loss limiting (weight ratio) (minute) rate (gram) oxygen index .sup.1:0.5 7 50% 12.5 24.3 1:1 8 42% 11 26.5 1:2 9 39% 10 28.9 1:3 7.5 45% 11.8 25.0 1:4 7 53% 13 24.5
(17) It can be seen from the above table that all ratios of the phosphorization agent to the crosslinking agent within 11 may obtain satisfactory results, and the result at 1:2 was particularly notable.
Example 3
(18) The Flame-Retardant Effect of the Flame Retardant Main Body:
(19) 6 grams of the flame retardant main body in Example 1 were added to 20 grams of a polyurethane paint, followed by uniform mixing, and they were coated onto a five-ply board base material By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(20) flame retarding time of 7 minutes (big panel method);
(21) flame propagation rate of 50% (tunnel method);
(22) carbonization volume, weight loss of 12.5 grams (cabinet method);
(23) paint strip limiting oxygen index (LOI) of 24.5%.
Example 4
(24) The Comparison in the Case where No Crosslinking Agent was Used:
(25) In a 250-milliliter beaker, 10 grams of polyphosphoric acid were added, then 10 grams of a nitrogen-containing foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent, such as cellulose, were further added and allowed for sufficient reaction, during this process no crosslinking agent was added. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at a temperature of 15-40 C. for neutralization until pH was 5-8. Subsequently filtration was performed and filter residue was dried. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing, and they were coated onto a five-ply board base material. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material are as follows:
(26) flame retarding time of 6.5 minutes (big panel method);
(27) flame propagation rate of 55% (tunnel method);
(28) carbonization volume, weight loss of 13 grams (cabinet method);
(29) paint strip limiting oxygen index (LOI) of 24%.
Example 5
(30) Following the same method as Example 4, but different crosslinking agents (10 grams) as shown in Table 2 were used, and the obtained results were shown in Table 2.
(31) TABLE-US-00002 TABLE 2 Experimental data of flame retardants obtained by using the same preparation method but changing different crosslinking agents Flame Flame retarding propa- Combustion Paint strip Crosslinking time gation weight loss limiting agent (minute) rate (gram) oxygen index None 6.5 55% 13 24.0 Hydroquinone 10 38% 9 30.1 Ethylene glycol 8 46% 11.2 26.5 Pentaerythritol 9 41% 10 28.6
(32) It can be seen from the above table that a polyol compound may be used as a crosslinking agent in this disclosure, and the effects of polyphenols were particularly notable.
Example 6
(33) The Comparison in the Case where Ammonium Hydrogen Carbonate was Used as a Foaming Agent:
(34) In a 250-milliliter beaker, 10 grams of polyphosphoric acid were added, then 10 grams of a foaming agent (ammonium hydrogen carbonate) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent such as cellulose and a polyol crosslinking agent were further added for further reaction. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at a temperature of 15-40 C. for neutralization until pH was 5-8. Subsequently, filtration was performed and filter residue was dried. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(35) flame retarding time of 5 minutes (big panel method);
(36) flame propagation rate of 60% (tunnel method);
(37) carbonization volume, weight loss of 14.5 grams (cabinet method);
(38) paint strip limiting oxygen index (LOI) of 22.0%.
Example 7
(39) Following the same method as Example 6, but 10 grams of foaming agents as shown in Table 3 were used, and the obtained results were given in Table 3.
(40) TABLE-US-00003 TABLE 3 Experimental data of flame retardants obtained by using the same preparation method but changing different foaming agents Flame Flame retarding propa- Combustion Paint strip time gation weight loss limiting Foaming agent (minute) rate (gram) oxygen index Melamine 10 38% 9 30.1 Polyphosphamide 9 41% 10 28.5 Urea 9 43% 10.5 27.8 Semicarbazide 11 36% 9 29.6 Guanidine 8 46% 12 26.8 phosphate Aminoethanol 7 51% 13 24.5
(41) It can be seen from the above table that an amine compound may be used as a foaming agent in this disclosure, and the effect of semicarbazide was particularly notable.
Example 8
(42) The Comparison in the Case where Phloroglucinol was Used as a Charring Agent:
(43) In a 250-milliliter beaker, 10 grams of polyphosphoric acid were added, then 8 grams of a foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent (phloroglucinol) and a polyol crosslinking agent were further added for further reaction. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at a temperature of 15-40 C. for neutralization until pH was 5-8, and subsequently filtration was performed and filter residue was dried. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(44) flame retarding time of 8 minutes (big panel method);
(45) flame propagation rate of 46% (tunnel method);
(46) carbonization volume, weight loss of 11.5 grams (cabinet method);
(47) paint strip limiting oxygen index (LOI) of 26.5%.
Example 9
(48) Following the same method as Example 8, but 6 grams of charring agents as shown in Table 4 were used, and the obtained results were shown in Table 4.
(49) TABLE-US-00004 TABLE 4 Experimental data of flame retardants obtained by using the same preparation method but changing different charring agents Flame Flame Second retarding propa- Combustion Paint strip charring time gation weight loss limiting agent (minute) rate (gram) oxygen index Cellulose 8 44% 12 26.8 Starch 6 64% 14 24.2 Cyclodextrin 8 43% 11.5 27.0 Trisphenol 9 38% 10 29.2 Glycerol 8 45% 12 26.6
(50) It can be seen from the above table that a hydroxy compound may be used as a charring agent in this disclosure, and the effect of trisphenol was particularly notable.
Example 10
(51) The Comparison in the Case where Phosphoric Acid was Used as a Phosphorization Agent:
(52) In a 250-milliliter beaker, 10 grams of phosphoric acid were added, then 8 grams of a foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent (cellulose) and a polyol crosslinking agent were further added for further reaction. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at 15-40 C. for neutralization until pH was 5-8, and subsequently filtration was performed and filter residue was dried. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(53) flame retarding time of 7.5 minutes (big panel method);
(54) flame propagation rate of 47% (tunnel method);
(55) carbonization volume, weight loss of 12.5 grams (cabinet method);
(56) paint strip limiting oxygen index (OI) of 25.1%.
Example 11
(57) Following the same method as Example 10, but different phosphorization agents (8-14 grams) as shown in Table 5 were used, and the obtained results were given in Table 5.
(58) TABLE-US-00005 TABLE 5 Experimental data obtained by using the same method but different phosphorization agents Flame Flame retarding propa- Combustion Paint strip Phosphoriza- time gation weight loss limiting tion agent (minute) rate (gram) oxygen index Yield Polyphos- 10 38% 9 30.1 82% phoric acid Pyrophos- 14 31% 8.0 35.0 67% phoric acid Phosphoric 7.5 47% 12.5 25.1 74% acid Phosphorus 11 35% 8.5 31.0 45% pentaoxide
(59) It can be seen from the above table that a phosphoric acid compound may be used as a phosphorization agent in this disclosure, and the effect of polyphosphoric acid was particularly notable.
Example 12
(60) The Comparison in the Case where an Aqueous Sodium Hydroxide Solution was Used as an Alkali for Neutralization:
(61) In a 250-milliliter beaker, 10 grams of phosphoric acid were added, then 8 grams of a foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent (cellulose) and a polyol crosslinking agent were further added for further reaction. After the reaction was complete, the product was cooled to room temperature. An aqueous sodium hydroxide solution was then added at 15-40 C. for neutralization until pH was 5-8, and subsequently filtration was performed and filter residue was dried. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(62) flame retarding time of 8 minutes (big panel method);
(63) flame propagation rate of 45% (tunnel method);
(64) carbonization volume, weight loss of 11.5 grams (cabinet method);
(65) paint strip limiting oxygen index (OI) of 26.5%.
Example 13
(66) Following the same method as Example 12, but different alkalis (usage amounts of 5-14 grams) as shown in Table 6 were used for neutralization to neutral pH, and the obtained results were shown in Table 6.
(67) TABLE-US-00006 TABLE 6 Experimental data obtained by using the same method but different alkalis for neutralization Flame Flame retarding propa- Combustion Paint strip time gation weight loss limiting Alkali (minute) rate (gram) oxygen index Yield Methylamine 10 38% 9 30.1 86% Triethyl- 8 45% 11 28.1 85% amine Aniline 7 50% 13 25.1 63% Aqueous 9 41% 10 28.5 78% ammonia
(68) It can be seen from the above table that an amine compound may be used for neutralization, and the effect of methylamine was particularly notable.
Example 14
(69) The Comparison Between Neutralizations to pH=3 and to pH=10:
(70) In a 250-milliliter beaker, 10 grams of phosphoric acid were added, then 8 grams of a foaming agent (melamine) were added in batches, followed by uniform stirring. An appropriate amount of water was added to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent (cellulose) and a polyol crosslinking agent were further added for further reaction. After the reaction was complete, the product was cooled to room temperature. An amine such as an aqueous methylamine solution was then added at a temperature of 15-40 C. for neutralization until pH=3 or pH=10. In neutralization to pH=3, a small amount of relatively viscous solid was obtained. This solid has relatively great damage to mechanical and physical properties of base material and is not suitable as a flame retardant main body. In neutralization to pH=10, a solid was obtained. The resultant solid, melamine phosphate, and pentaerythritol were mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were uniformly pulverized to obtain a solid powder. 6 grams of this solid powder were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(71) flame retarding time of 10 minutes (big panel method);
(72) flame propagation rate of 40% (tunnel method);
(73) carbonization volume, weight loss of 10 grams (cabinet method);
(74) paint strip limiting oxygen index (OI) of 28.8%.
Example 15
(75) The pH values after neutralizations in Example 14 were changed to the values in Table 7, and the obtained results were shown in Table 7.
(76) TABLE-US-00007 TABLE 7 Experimental data from neutralizations to different pHs Flame Flame retarding propa- Combustion Paint strip pH time gation weight loss limiting value (minute) rate (gram) oxygen index Yield 3 10 38% 9 30.5 36% 5-8 10 38% 9 29.4 85% 10 10 40% 10 28.8 80%
(77) It can be seen from the above table that the flame-retardant effect and the reaction yield reached an optimal balance effect when pH is in a range of 5-8.
Example 16
(78) The Comparison of Large-Particle Flame Retardants:
(79) The solid obtained in Example 1 was pulverized to a size of 50 micrometers or more, 6 grams of which were added to 20 grams of a polyurethane paint, followed by uniform mixing. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the properties of the flame-retardant paint after being coated onto a wood five-ply board base material were as follows:
(80) flame retarding time of 7.5 minutes (big panel method);
(81) flame propagation rate of 49% (tunnel method);
(82) carbonization volume, weight loss of 12.0 g (cabinet method);
(83) paint strip limiting oxygen index (OI) of 25.6%.
(84) TABLE-US-00008 TABLE 8 Flame Flame retarding propa- Combustion Paint strip Particle size time gation weight loss limiting (micrometer) (minute) rate (gram) oxygen index 5-20 10 38% 9 30.1 50 7.5 49% 12 25.6
(85) It can be seen from Table 8 that large-particle flame retardants resulted in the reduction of mechanical and physical properties of paints. For example, when the paint was apparently dried, the gloss was substantially lost and the adherence was reduced.
Example 17
(86) In a 250-milliliter small-size ceramic reaction tank, 10 grams of pyrophosphoric acid were added, then 8 grams of melamine phosphate were added in batches, followed by uniform stirring. An appropriate amount of water was used to initiate reaction, and sufficient reaction was allowed. 6 grams of a charring agent (starch) were further added to continue the reaction. A crosslinking agent (aminopropanol) and a charring agent (pentaerythritol) were subsequently added. After the reaction was complete, the product was cooled to room temperature. An amine was further added for neutralization until pH was 5-8. This turbid liquid was filtered and the obtained filter residue was dried. The resultant solid, a first nitrogen-containing foaming agent, and a first charring agent were uniformly mixed at a ratio of (1-3:0.5-1.5:0.2-1.2) and were pulverized, and a phosphorus-nitrogen-based intumescent paint flame retardant was obtained.
(87) 7 grams of this flame retardant were added to 20 grams of an epoxy resin paint, followed by uniform mixing, and they were coated onto a wood base material board. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the detected properties of the flame-retardant paint were as follows:
(88) flame retarding time of 14 minutes (big panel method);
(89) flame propagation rate of 31% (tunnel method);
(90) carbonization volume, weight loss of 8.0 g (cabinet method);
(91) paint strip limiting oxygen index (OI) of 35%.
(92) The mechanical and physical properties reached the standards of GB/T23997-2009 and GB18581-2009.
Example 18
(93) The Comparison in the Case of No First Charring Agent:
(94) The flame retardant main body obtained in Example 10 and a first nitrogen-containing foaming agent were uniformly mixed at a ratio of 1:1 and were pulverized, and thus a phosphorus-nitrogen-based intumescent paint flame retardant without first charring agent was obtained.
(95) 7 grams of this flame retardant were added to 20 grams of an epoxy resin paint, followed by uniform mixing, and they were coated onto a wood base material board. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the detected properties of the flame-retardant paint were as follows:
(96) flame retarding time of 9 minutes (big panel method);
(97) flame propagation rate of 41% (tunnel method);
(98) carbonization volume, weight loss of 9.5 grams (cabinet method);
(99) paint strip limiting oxygen index (OI) of 27.8%.
Example 19
(100) The Comparison in the Case of No First Foaming Agent:
(101) The flame retardant main body obtained in Example 10 and a first charring agent were uniformly mixed at a ratio of 1:2 and were pulverized, and thus a phosphorus-nitrogen-based intumescent paint flame retardant without first foaming agent was obtained.
(102) 7 grams of this flame retardant were added to 20 grams of an epoxy resin paint, followed by uniform mixing, and they were coated onto a wood base material board. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the detected properties of the flame-retardant paint were as follows:
(103) flame retarding time of 8.5 minutes (big panel method);
(104) flame propagation rate of 42% (tunnel method);
(105) carbonization volume, weight loss of 10 g (cabinet method);
(106) paint strip limiting oxygen index (OI) of 27.1%.
Example 20
(107) The Application in Alkyd Paints:
(108) 7 grams of the phosphorus-nitrogen-based intumescent paint flame retardant prepared in Example 10 were added to an alkyd paint, followed by uniform mixing, and they were coated onto a wood three-ply board base material. By means of GB12441-2005, a national standard for fireproof coatings (there was no standard for flame-retardant paints at present), the detected properties of the flame-retardant paint were as follows:
(109) flame retarding time of 11 minutes (big panel method);
(110) flame propagation rate of 36% (tunnel method);
(111) carbonization volume, weight loss of 8.5 grams (cabinet method);
(112) limiting oxygen index (OI) of 30%.
(113) The mechanical and physical properties reached the standards of GB/T23997-2009 and GB18581-2009.
Example 21
(114) The ratio of flame retardant main body:first foaming agent:first charring agent (the mass of the main body is 10 grams) was changed as shown in Table 9, and the obtained results were shown in Table 9.
(115) TABLE-US-00009 TABLE 9 Experimental data from different ratios of flame retardant main body:first foaming agent:first charring agent Flame retardant main Flame Flame Paint strip body:first foaming retarding propa- Combustion limiting agent:first charring time gation weight loss oxygen agent (weight ratio) (minute) rate (gram) index 1:0.5:0.2 7 50% 13 25 2:1:0.5 8 45% 12 27.5 3:1:0.5 8.5 41% 11 28.3 2:1.5:1 8 45% 12 27.2 1:0.5:1.2 6.5 55% 14 24.1 2:1:1.2 9 39% 10 29.3 3:1:1.2 10 35% 9 30.0
(116) It can be seen from Table 9 that the best limiting oxygen index was provided when the ratio of flame retardant main body:first foaming agent:first charring agent (weight ratio) was 3:1:1.2.
Example 22
(117) Wood boards of 9019020 mm and 190100020 mm were placed in a flame retardant, soaked under boiling condition for 10 minutes, and then were withdrawn to be air-dried or oven-dried. Measurement was then performed according to standard GB 8624-88. Test pieces had an average value of remaining length>150 mm and an average smoke temperature<200 C. Additionally, the wood board strip after this treatment had a limiting oxygen index (OI)>40%. The wood board treated with this flame retardant was a fire retardant building material.
Example 23
(118) Cotton fabrics were placed in a flame retardant and soaked at normal temperature for 10 minutes, and then were withdrawn to be air-dried or oven-dried. Measurement was then performed according to standard GB8624-2006. A test pieces was subjected to a vertical combustion test, and had an average after-flame time of 0 second, an average afterglow time of 0 second, an average damaged length of 105 mm, and a limiting oxygen index (OI) of 37.5%.
(119) Those described above are only preferable specific embodiments of this invention, and the scope of this invention is not limited thereto. Within the technical scope disclosed by this application, any person skilled in the art will easily conceive variations or replacements, which should be covered by the scope of this invention. Therefore, the protection scope of this invention should be determined by the scope described in the claims.