CN1075760C - Synthetic process of wood fire-retardant agent - Google Patents
Synthetic process of wood fire-retardant agent Download PDFInfo
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- CN1075760C CN1075760C CN97118353A CN97118353A CN1075760C CN 1075760 C CN1075760 C CN 1075760C CN 97118353 A CN97118353 A CN 97118353A CN 97118353 A CN97118353 A CN 97118353A CN 1075760 C CN1075760 C CN 1075760C
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- guanyl
- phosphate
- urea
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- fire retardant
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Abstract
The present invention relates to a synthetic method for a fire retardant agent for processing wood and other cellulosic materials. Dicyanodiamide, phosphoric acid and water can react at 90 to 120 DEG C so as to synthesize guanylurea phosphate via a high yield, and the guanylurea phosphate and boric acid can be mixed so as to prepare the fire retardant agent. The fire retardant agent of the present invention not only has good fire retardant property, but also has good corrosion prevention and termite killing capability, and the fire retardant agent has the advantages of low toxicity and little moisture absorption and can not generate pollutant in the processes of production and use.
Description
The invention belongs to a kind of synthetic method of fire retardant.
With water-soluble inorganic salts such as diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP)s timber is carried out the common method that flame treatment is treating of wood industry, still constantly have the recent studies on achievement to deliver (WO9600,763, CN1,093,393) in recent years.The advantage of this based flame retardant is that anti-flammability is better, toxicity is little and cost is lower, gone out, handle critical defects such as the big and Yi Fanshuan of material hygroscopicity, corroding metal device by the water drop but have easily, thereby application is restricted.Go out performance and reduce hygroscopicity in order to improve anti-drop, many researchers have carried out with the research work as wood fire retardant of the phosphate of low polymerization degree amino-compound-aldehyde condensation polymer product.Yet,, reduced the intensity of timber owing to the higher solidification temperature of needs though anti-the going out property of drop and the hygroscopicity of this based flame retardant have clear improvement.
Discovered in recent years not only has fire-retardant synergy between phosphorus and nitrogen element, and also has tangible fire-retardant synergy between phosphorus, nitrogen and the boron three elements.Utilize fire-retardant synergy,, can under the situation that reduces dosing, improve fire resistance by designing suitable flame-retardant system.It is the fire retardant that the incomplete reaction product under 70 ℃ to 90 ℃ is constituted by dicyandiamide, phosphoric acid, boric acid and water in temperature that William J.Oberley (US4,373,010) has invented a kind of, its good flame resistance, and hygroscopicity obviously reduces than the ammonium salt based flame retardant.But in order to prevent or reduce the generation of insoluble substance, this invention requires that dicyandiamide and phosphoric acid can not transform fully in the reaction raw materials, and 5% to 20% residue must be arranged.Because of the extent of reaction is difficult for composition difference, the unstable product quality that accurately control causes each batch products, there is the shortcoming that can not fully effectively utilize raw material on the other hand so on the one hand.In addition, because thoroughly reaction of phosphoric acid, the acidity of product is bigger, cause timber after the processing in the process of drying because of acid catalysis degraded deterioration takes place.
The object of the present invention is to provide a kind of synthetic method that is applicable to the efficient low-poison and combustion-resisting agent of timber and other cellulose material, overcome the shortcoming and defect of existing method.
Basic design of the present invention is, making dicyandiamide, phosphoric acid and water (water is as reactant and solvent) is that 90 ℃ to 120 ℃ following complete reactions generate guanyl-urea-phosphate in temperature, reaction product solution makes the guanyl-urea-phosphate solid product through separation method separation such as crystallization isolated by filtration or decompression concentrate dryings, and filtrate or condensed water are recyclable to be recycled; Guanyl-urea-phosphate and boric acid mixed promptly obtain flame retardant products.The mol ratio of material is a dicyandiamide: phosphoric acid: water=1: (1.0 to 1.2): (6 to 200); Guanyl-urea-phosphate: boric acid=1: (0.35 to 2.2).
With the solid flame retardant solution that is mixed with debita spissitudo soluble in water that the present invention synthesizes, the treatment fluid that promptly can be used as timber or other cellulosic material uses.According to the characteristics of material processing technique, also the fire retardant that the present invention can be synthesized mixes in sizing material or is used for the processing of wood-base fibre and particle panel material or other cellulose material as powder additive.
Under the situation that does not have long term storage or remote transportation problem, also can be easily the direct flame retardant products of synthetic fluid state.That is, the guanyl-urea-phosphate solution that reaction obtains after finishing needn't be through separating, and directly add boric acid, and dissolving is diluted to behind the debita spissitudo standby.
The invention solves dicyandiamide and phosphoric acid and in the aqueous solution, react a difficult problem that easily generates insoluble substance, raw material is transformed fully and obtain high yield, stay-in-grade guanyl-urea-phosphate, guaranteed the reliable and stable of flame retardant products quality, whole technical process does not discharge pollutants.
Because boron compound has antimycotic and kills termite character, the fire retardant that the present invention synthesize is anti-flammability height but also give processed material certain anticorrosion and termite-proof ability not only, and toxicity is very low, safe in utilization.
With three examples content of the present invention is described below.
Embodiment 1:
On 250ml four-hole round-bottomed flask, thermometer, agitating device, reflux condensing tube and dropping funel are installed, add 42.1g dicyandiamide and 80ml water, after being heated to 100 ℃, under agitation drip 85% phosphoric acid 57.7g by dropping funel, in temperature is to react under 100 ℃ to 120 ℃ to dicyandiamide to transform fully, and the judgement of reaction end can or be used infra-red sepectrometry according to the variation of pH value.After question response is finished, cooling, crystallization is filtered and with the 10ml cold water washing, in temperature be 80 ℃ to 100 ℃ dry down.Get white powder guanyl-urea-phosphate product 74g, molar yield 74%.
1 mole of guanyl-urea-phosphate and 1.2 moles of boric acid are mixed, get the solid flame retardant product.
During preparation treating of wood liquid, the solid flame retardant that the present invention is synthesized is dissolved in the water and is mixed with the colourless transparent solution that concentration is 8% (weight) clarification, pH value about 4.5.
In the infrared spectrogram of synthetic guanyl-urea-phosphate product, do not have cyano group (characteristic absorption peak CN) (the raw material dicyandiamide has strong absorption in this wave number) shows not contain dicyandiamide in the product at 2100 to 2200 wave number places.Phosphate radical is thoroughly precipitated synthetic guanyl-urea-phosphate product and the reaction of superfluous lime water with the form of calcium salt, filter.Filtrate makes dicyandiamidines be converted into sulfate with the dilute sulfuric acid neutralization, concentrates then, and crystallization separates drying.The infrared spectrogram of synthetic guanyl-urea-phosphate conforms to fully with the Sadtler standard spectrogram of standard sample, illustrates that the structure of product is correct.
Embodiment 2:
The filtrate that is produced divided by synthetic guanyl-urea-phosphate among the embodiment 1 replaces repeating embodiment 1 described guanyl-urea-phosphate compound experiment outside the 80ml water, real guanyl-urea-phosphate product 92.0g, the molar yield 92.0% of getting.Replace water to carry out the circulation repeated experiments six times with the filtrate of last time testing successively again, the molar yield of guanyl-urea-phosphate is 99.5%, 95.5%, 100.2%, 97.8%, 99.0% and 98.0% successively.
The infrared spectrum of above-mentioned seven repeated experiments guanyl-urea-phosphate products conforms to the product spectrogram of embodiment 1.The guanyl-urea-phosphate sample dissolution of 0.5g respectively being tested gained is in 4.5g distilled water respectively, and obtaining concentration is the colourless transparent solution of 10% clarification.As seen, filtrate can be recycled.
Embodiment 3:
On 1000ml four-hole round-bottomed flask, thermometer, agitating device, reflux condensing tube and dropping funel are installed, add 42.04g dicyandiamide and 200ml water, after being heated to 100 ℃, under agitation by dripping 85% phosphoric acid 57.7g in the dropping funel, in temperature is to react under 100 ℃ to 120 ℃ to dicyandiamide to be converted into guanyl-urea-phosphate fully, stops heating.Add 30.9g boric acid and 533ml water, be cooled to room temperature after the dissolving, getting concentration is the liquid flame retardant of 15% (weight), pH value 3.0.During use, can be diluted to the treating of wood liquid of debita spissitudo as required with water.
Claims (2)
1, a kind of method for synthesizing flame retardant that is used for timber and other cellulosic materials, main employing dicyandiamide, phosphoric acid, boric acid and water are raw material, it is characterized in that dicyandiamide, phosphoric acid and water are the synthetic guanyl-urea-phosphates of 90 ℃ to 120 ℃ following complete reactions in temperature, then by guanyl-urea-phosphate and the composite fire retardant that makes of boric acid, guanyl-urea-phosphate to the mol ratio of boric acid be 1: 0.35 to 2.2, dicyandiamide to the mol ratio of phosphoric acid be 1: 1.0 to 1.2; Dicyandiamide to the mol ratio of water be 1: 6 to 200.
2, method for synthesizing flame retardant according to claim 1, after the reaction that it is characterized in that synthetic guanyl-urea-phosphate was finished, reactant mixture can use crystallization, filtration method separation, and filtrate is recyclable to be recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118353A CN1075760C (en) | 1997-10-08 | 1997-10-08 | Synthetic process of wood fire-retardant agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118353A CN1075760C (en) | 1997-10-08 | 1997-10-08 | Synthetic process of wood fire-retardant agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1213603A CN1213603A (en) | 1999-04-14 |
| CN1075760C true CN1075760C (en) | 2001-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97118353A Expired - Fee Related CN1075760C (en) | 1997-10-08 | 1997-10-08 | Synthetic process of wood fire-retardant agent |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6652633B2 (en) * | 2001-03-01 | 2003-11-25 | Arch Wood Protection, Inc. | Fire retardant |
| CN100443273C (en) * | 2004-12-16 | 2008-12-17 | 龙有前 | Wood protective agent |
| CN101153119B (en) * | 2007-09-07 | 2011-01-12 | 东北林业大学 | Nethod of producing Clubbed composite material of wood-wool |
| CN102152359B (en) * | 2010-12-30 | 2013-10-23 | 浙江农林大学 | Method for producing high-efficiency cooperative bamboo wood flame retardant |
| CN102152360B (en) * | 2011-02-28 | 2013-05-08 | 王彦林 | Method for preparing halogen-free wood flame retardant |
| CN102490220A (en) * | 2011-12-20 | 2012-06-13 | 徐州盛和木业有限公司 | Preparation method of antiflaming mothproof natural veneer overlay decorative board |
| CN104072088B (en) * | 2014-06-05 | 2016-03-30 | 安徽中益新材料科技有限公司 | A kind of environmental-friendly walling fireproof heated board and preparation method thereof |
| CN105773765A (en) * | 2016-02-01 | 2016-07-20 | 东北林业大学 | Water-soluble loss-resisting flame retardant and method for preparing flame retardant wood with water-soluble loss-resisting flame retardant |
| CN113733266A (en) * | 2021-09-18 | 2021-12-03 | 国家林业和草原局泡桐研究开发中心 | Manufacturing method of multi-layer flame-retardant fireproof board made of paulownia wood |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192305A (en) * | 1975-02-04 | 1976-08-13 | SERUROOSUKEIZAIRYONO TAINETSUNANNENKASHORIHOHO | |
| US4373010A (en) * | 1980-10-14 | 1983-02-08 | Koppers Company, Inc. | Non-resinous, uncured tire retardant and products produced therewith |
| JPH02235704A (en) * | 1989-03-10 | 1990-09-18 | Sanyo Mokuzai Boufu Kk | Flame-retarded timber |
| JPH02277603A (en) * | 1989-04-19 | 1990-11-14 | Yamaha Corp | Fire retardant treatment of lumber |
| JPH02277601A (en) * | 1989-04-19 | 1990-11-14 | Yamaha Corp | Bonding and working method of fire retardant lumber |
| JPH02279302A (en) * | 1989-04-21 | 1990-11-15 | Yamaha Corp | Coating method for flame-retardant timber |
-
1997
- 1997-10-08 CN CN97118353A patent/CN1075760C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192305A (en) * | 1975-02-04 | 1976-08-13 | SERUROOSUKEIZAIRYONO TAINETSUNANNENKASHORIHOHO | |
| US4373010A (en) * | 1980-10-14 | 1983-02-08 | Koppers Company, Inc. | Non-resinous, uncured tire retardant and products produced therewith |
| JPH02235704A (en) * | 1989-03-10 | 1990-09-18 | Sanyo Mokuzai Boufu Kk | Flame-retarded timber |
| JPH02277603A (en) * | 1989-04-19 | 1990-11-14 | Yamaha Corp | Fire retardant treatment of lumber |
| JPH02277601A (en) * | 1989-04-19 | 1990-11-14 | Yamaha Corp | Bonding and working method of fire retardant lumber |
| JPH02279302A (en) * | 1989-04-21 | 1990-11-15 | Yamaha Corp | Coating method for flame-retardant timber |
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| Publication number | Publication date |
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| CN1213603A (en) | 1999-04-14 |
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