CN102659959A - Preparation method of three-in-one intumescent fire retardant - Google Patents

Preparation method of three-in-one intumescent fire retardant Download PDF

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Publication number
CN102659959A
CN102659959A CN2012101073053A CN201210107305A CN102659959A CN 102659959 A CN102659959 A CN 102659959A CN 2012101073053 A CN2012101073053 A CN 2012101073053A CN 201210107305 A CN201210107305 A CN 201210107305A CN 102659959 A CN102659959 A CN 102659959A
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China
Prior art keywords
flame retardant
expansion type
type flame
source
fire retardant
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CN2012101073053A
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Chinese (zh)
Inventor
王正洲
孔清锋
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Tongji University
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Tongji University
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Priority to CN2012101073053A priority Critical patent/CN102659959A/en
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Abstract

The invention belongs to the technical field of materials and specifically relates to a preparation method of a three-in-one intumescent fire retardant. The preparation method comprises the following concrete steps of: performing a reaction between 1-10g of chitosan and 5-80g of phosphoric acid, stirring and heating to 60-150 DEG C, cooling the temperature of the system to 50 DEG C after reacting for 0.5-3.5h, adding a mixed liquor composed of 5-84g of melamine and 50-300g of a solvent, reacting for 0.5-2h at 60-120 DEG C, cooling, filtering and drying to obtain the faint yellow three-in-one intumescent fire retardant powder. The intumescent fire retardant has good fluidity, low water-solubility, and can be used for flame retardation of materials such as plastic, rubber, timber, fabric, paint and the like.

Description

A kind of preparation method of three-source integrated expansion type flame retardant
Technical field
The invention belongs to the material technology field, be specifically related to OnePlant the preparation method of three-source integrated expansion type flame retardant.
Background technology
It is the composite flame-retardant agent of main nucleus that expansion type flame-retarding system (IFR) typically refers to phosphorus, nitrogen, carbon, and it generally is made up of three parts: carbonized agent (carbon source), charing catalyst (acid source) and swelling agent (source of the gas).When being heated, can form certain thickness porous charcoal layer with its fire-retardant polymkeric substance on its surface, that this charcoal layer has is heat insulation, oxygen barrier, press down the function of cigarette and anti-molten drop, thereby plays the good flame effect.At present, expansion type flame retardant is widely used in the fire-retardant of materials such as plastics, rubber, fiber, coating, timber.
Though IFR has advantages such as flame retarding efficiency height, low price, toxicity are lower, also exist poor with the polymer phase capacitive, be prone to moisture absorption and defective such as ooze out.It is for example, commonly used that expansion type flame retardant---low polymerization degree ammonium polyphosphate (APP) and tetramethylolmethane (PER) all are water miscible.Therefore when adding these expansion type flame-retardant polymer materials and using in (rain, water) or the moist environment out of doors, expansion type flame retardant can and ooze out to the surface of polymer material migration, can reduce the flame retardant properties of material, even not have fire-retardant or the flameproof protection effect.
For the problem of the poor water resistance that solves IFR, report according to Chinese patent (compound method of environment protective fire-retartant agent MP, application number 02112971); Equimolar trimeric cyanamide is got in employing and phosphoric acid reacted 0.5-1.5 hour under 92-100 ℃ of temperature condition in excessive water, cools off then, filters, the resulting MP product in dry back; Has good flame-retardant effect; Water-soluble low, give birth to during burning the cigarette amount low, do not produce toxic gas, advantage such as environmentally friendly.According to another bibliographical information ( Polymer Degradation and Stability2005,90 (3): 523-534.), MP at some polymkeric substance (like Vestolen PP 7052) though in have certain fire retardation; But flame retardant effect is not so good; This mainly is because MP is a kind of gentle expansion type flame retardant that comes from one of acid source that collects, and lacks the carbon source part in its molecule, still needs in some application scenarios and carbon source (like tetramethylolmethane) is composite could obtain flame retardant effect preferably.Yet it is not fine adopting the water tolerance of the expansion type flame-retarding system of water-soluble tetramethylolmethane and the composite composition of MP, still exists fire retardant to ooze out to its fire-retardant material surface migration.
Therefore research collection acid source, the gentle one that comes from of carbon source, promptly " three-source integrated " water-soluble low, have certain theory significance and using value with the good expansion type flame retardant of polymer phase capacitive.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of three-source integrated polymer expansion type flame retardant.
The preparation method of the three-source integrated polymer expansion type flame retardant that the present invention proposes, concrete steps are following:
With 1-10 g chitosan and 5-80 g phosphatase reaction, continue stirring and be warming up to 60-150 ℃, behind the reaction times 0.5-3.5 h; System temperature is reduced to 50 ℃, add the mixed solution of 5-84 g trimeric cyanamide and 50-300 g solvent again, behind 60-120 ℃ of reaction 0.5-2 h; Cooling is filtered, with washing with alcohol sample number time; More than dry 6 h under 90 ℃ of vacuum conditions, obtain linen three-source integrated expansion type flame retardant powder.
Among the present invention, the molecular weight of said chitosan is 2-60 ten thousand.
Among the present invention, said solvent is an alcohols, like methyl alcohol, ethanol, or in their mixed solvent any.
The three-source integrated polymer expansion type flame retardant that utilizes the inventive method to prepare, its molecular formula is as follows.
 
Beneficial effect of the present invention is to select for use the chitosan that contains great amount of hydroxy group as carbon source; A large amount of amino in its molecule can also serve as action of gas source simultaneously; Adopt chemical reaction that expansion type flame retardant three sources are attached on the macromole, improve its flame retarding efficiency, water tolerance and and polymkeric substance between consistency; And preparation technology is easy.
Description of drawings
Fig. 1 is used reactant (CS), the esterification products (PCS) of CS and the infrared spectrogram of product (PCSM) of preparation " three-source integrated " expansion type flame retardant.
Embodiment
Further specify the present invention through embodiment below, rather than limit scope of the present invention.
Embodiment 1:
The first step: phosphoric acid and chitosan (CS) esterification
Take by weighing and constantly be warming up to 120 ℃ under the uniform condition of dispersed with stirring after 10 g CS are dissolved in phosphoric acid 76.8 g, and under this temperature, react 3 h.
Second step: source of the gas is introduced
System temperature is reduced to 50 ℃, add 84 g source of the gas trimeric cyanamides and 200 g alcoholic acid mixed solutions, react 1 h down at 78 ℃.
After above-mentioned reaction finished, suction filtration, with washing with alcohol product number time placed 90 ℃ of vacuum drying ovens down more than dry 6 h, obtains flaxen three-source integrated expansion type flame retardant powder 149.1 g.
Embodiment 2:
The first step: phosphoric acid and chitosan esterification
Take by weighing and be warming up to 150 ℃ after 5 g CS and phosphoric acid 38.4g stir, and insulation reaction 1.5 h.
Second step: source of the gas is introduced
System temperature is reduced to 50 ℃, add 42 g source of the gas trimeric cyanamides and 100 g alcoholic acid mixed solutions, react 0.5 h down at 78 ℃.
After above-mentioned reaction finished, suction filtration, with washing with alcohol product number time placed 90 ℃ of vacuum drying ovens down more than dry 6 h, obtains gray three-source integrated expansion type flame retardant powder 71.4 g.
Embodiment 3:
The first step: phosphoric acid and chitosan esterification
Take by weighing and be warming up to 100 ℃ after 5 g CS and phosphoric acid 38.4g stir, and insulation reaction 0.5 h.
Second step: source of the gas is introduced
System temperature is reduced to 50 ℃, add the mixed solution of 21 g source of the gas trimeric cyanamides and 250 g methyl alcohol, react 0.5 h down at 64 ℃.
After above-mentioned reaction finished, suction filtration, with washing with alcohol product number time placed 90 ℃ of vacuum drying ovens down more than dry 6 h, obtains gray three-source integrated expansion type flame retardant powder 49.7 g.
The solubleness of " three-source integrated " expansion type flame retardant in water prepared among the embodiment 1-3 is seen table 1.
The solubleness of table " three-source integrated " expansion type flame retardant
? Embodiment 1 Embodiment 2 Embodiment 3
25 ℃ of solubleness (g/100ml) 0.9 1.1 1.3
Fig. 1 is used reactant (CS), the esterification products (PCS) of CS and the infrared spectrogram of product (PCSM) of preparation " three-source integrated " expansion type flame retardant.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.

Claims (4)

1. the preparation method of a three-source integrated expansion type flame retardant is characterized in that concrete steps are following:
With 1-10 g chitosan and 5-80 g phosphoric acid; Stirring is warming up to 60-150 ℃ of reaction, behind the reaction times 0.5-3.5 h, system temperature is reduced to 50 ℃; The mixed solution that adds 5-84 g trimeric cyanamide and 50-300 g solvent again stops behind 60-120 ℃ of reaction 0.5-2 h; Filtration, drying obtain three-source integrated expansion type flame retardant.
2. preparation method according to claim 1 is characterized in that said solvent is an alcohols.
3. preparation method according to claim 1, the molecular weight that it is characterized in that said chitosan is 2-60 ten thousand.
4. preparation method according to claim 1 is characterized in that the polymer expansion type flame retardant that gained is three-source integrated, and its molecular formula is following:
CN2012101073053A 2012-04-13 2012-04-13 Preparation method of three-in-one intumescent fire retardant Pending CN102659959A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103951870A (en) * 2014-05-07 2014-07-30 浙江理工大学 Preparation method of phosphor-nitrogen-containing polyelectrolyte complex flame-retardant EVA (ethylene vinyl acetate)
CN104072633A (en) * 2014-07-10 2014-10-01 齐齐哈尔大学 Phosphorus-containing fire retardant as well as preparation method and application thereof
CN105330986A (en) * 2015-11-12 2016-02-17 浙江百纳橡塑设备有限公司 Inflaming retarding ethylene-propylene-diene-monomer rubber foam material and preparing method thereof
CN106565854A (en) * 2016-10-19 2017-04-19 重庆大学 Preparation method of oligochitosan-grafted melamine
CN107523024A (en) * 2017-09-12 2017-12-29 太原理工大学 CNT base Chitosan Phosphate composite flame-retardant agent and its preparation method and application
CN108951164A (en) * 2018-06-06 2018-12-07 苏州印丝特纺织数码科技有限公司 A kind of pure cotton fabric antiflaming finishing agent and preparation method thereof
CN109401321A (en) * 2018-09-27 2019-03-01 唐山师范学院 Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber
CN110039626A (en) * 2019-03-01 2019-07-23 中国林业科学研究院木材工业研究所 Assist into charcoal biology base expansion type flame-retarding timber
CN110042658A (en) * 2019-04-22 2019-07-23 青岛大学 A kind of flame-proof antibiotic liquid and its preparation method and application
CN110483663A (en) * 2019-08-14 2019-11-22 东南大学 A kind of modification of chitosan fire retardant and preparation method thereof

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US5089559A (en) * 1989-02-13 1992-02-18 Blount David H Fire-retardant organic-phosphorus salts
CN102344510A (en) * 2011-07-13 2012-02-08 同济大学 Preparation method of three-source-in-one expansion type fire retardant

Patent Citations (2)

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US5089559A (en) * 1989-02-13 1992-02-18 Blount David H Fire-retardant organic-phosphorus salts
CN102344510A (en) * 2011-07-13 2012-02-08 同济大学 Preparation method of three-source-in-one expansion type fire retardant

Non-Patent Citations (1)

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Title
SHUANG HU ET AL.: "Thermal Properties and Combustion Behaviors of Chitosan Based Flame Retardant Combining Phosphorus and Nickel", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESSEARCH》, vol. 51, 6 February 2012 (2012-02-06) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103951870A (en) * 2014-05-07 2014-07-30 浙江理工大学 Preparation method of phosphor-nitrogen-containing polyelectrolyte complex flame-retardant EVA (ethylene vinyl acetate)
CN104072633A (en) * 2014-07-10 2014-10-01 齐齐哈尔大学 Phosphorus-containing fire retardant as well as preparation method and application thereof
CN105330986A (en) * 2015-11-12 2016-02-17 浙江百纳橡塑设备有限公司 Inflaming retarding ethylene-propylene-diene-monomer rubber foam material and preparing method thereof
CN106565854A (en) * 2016-10-19 2017-04-19 重庆大学 Preparation method of oligochitosan-grafted melamine
CN106565854B (en) * 2016-10-19 2019-01-11 重庆大学 A kind of preparation method of chitosan oligosaccharide grafting melamine
CN107523024A (en) * 2017-09-12 2017-12-29 太原理工大学 CNT base Chitosan Phosphate composite flame-retardant agent and its preparation method and application
CN108951164A (en) * 2018-06-06 2018-12-07 苏州印丝特纺织数码科技有限公司 A kind of pure cotton fabric antiflaming finishing agent and preparation method thereof
CN108951164B (en) * 2018-06-06 2021-03-19 苏州印丝特纺织数码科技有限公司 Flame-retardant finishing agent for pure cotton fabric and preparation method thereof
CN109401321A (en) * 2018-09-27 2019-03-01 唐山师范学院 Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber
CN110039626A (en) * 2019-03-01 2019-07-23 中国林业科学研究院木材工业研究所 Assist into charcoal biology base expansion type flame-retarding timber
CN110042658A (en) * 2019-04-22 2019-07-23 青岛大学 A kind of flame-proof antibiotic liquid and its preparation method and application
CN110042658B (en) * 2019-04-22 2021-08-31 青岛大学 Flame-retardant antibacterial liquid and preparation method and application thereof
CN110483663A (en) * 2019-08-14 2019-11-22 东南大学 A kind of modification of chitosan fire retardant and preparation method thereof

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