CN105924645A - Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant - Google Patents

Abstract

The invention discloses a halogen-free expansion type flame retardant containing a polymerized macromolecular triazine ring and a preparation method. The flame retardant introduces diamines of benzene rings, which improves the thermal stability of the product and increases its char formation It can be directly used in various thermoplastic and thermosetting materials without the synergistic effect of APP. At the same time, each triazine monocyclic ring contains 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octyl, which contains phosphorus and has a high amount of hydroxyl groups, and can be used as Reactive intumescent flame retardant. The halogen-free expansion type flame retardant containing polymerized macromolecular triazine ring of the present invention is cyanuric chloride and 1-oxygen phospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] Octane monosubstituted, phenyl diamine monosubstituted, and make triazine ring linked polymerization reaction product.

Description

A kind of polymerized macromolecular triazine ring-containing halogen-free expansion flame retardant and its preparation method

technical field

The invention relates to a flame retardant and a preparation method, in particular to a halogen-free expansion type flame retardant containing a polymerized macromolecular triazine ring and a preparation method.

Background technique

The early flame retardants were mainly halogen flame retardants, which occupied most of the polymer flame retardant market due to their advantages of less dosage, high flame retardant efficiency and wide adaptability. However, the disadvantage of halogen flame retardants is that a large amount of smoke and toxic and corrosive gases are generated during combustion, which is harmful to the environment and human body. Therefore, the application of halogen flame retardants is currently limited in many fields.

The use of intumescent flame retardants in polymer materials is a research hotspot in recent years. G.Camino et al. (Camino, G.Martinasso, C.Costal, L.Thermal degradation of pentaerythritol diphosphate, model compound forfire retardant intumescent systems: Part I-Overall thermal degradation. Polymer Degradation Stability, 1990,27(3):285～296 ) research on intumescent flame retardant polypropylene has opened up a new way for the development of polymer flame retardant technology. Intumescent flame retardant polymer with high flame retardancy, no droplet behavior, excellent resistance to prolonged or repeated exposure to flames; halogen-free, antimony oxide-free; low smoke, low toxicity, and non-corrosive gases Etc. Therefore, it is known as a revolution in flame retardant technology. Intumescent flame retardant (Intumescent Flame Retardant, IFR) is a new type of halogen-free flame retardant, because of its harmless gas released during combustion, large amount of char formation and the generated char layer can effectively prevent polymer melting. Drops and other advantages, especially suitable for flame retardant polymers. Therefore, intumescent flame retardants are receiving more and more attention in the field of flame retardancy at home and abroad. The intumescent flame retardant system mainly contains three types of components: acid source, carbon source and gas source. In the traditional intumescent flame retardant system, it is generally composed of ammonium polyphosphate (APP), polyol and cyanuric chloride composite components. Therefore, it is generally believed that the flame retardant mechanism of the intumescent system is: ammonium polyphosphate is decomposed by heat , generate phosphoric acid and pyrophosphoric acid with strong dehydration effect, esterify pentaerythritol (PER), and then dehydrate and carbonize. The water vapor formed by the reaction and the ammonia gas decomposed by the triazine ring make the carbon layer expand, and finally form a layer of microporous carbon layer, thereby isolating air and heat transfer, protecting the polymer body, and achieving the purpose of flame retardancy. Theoretically, the formation of the expanded carbon layer mainly goes through the following steps: (1) at a lower temperature (about 150 °C), the acid source emits an inorganic acid that can esterify polyols and can be used as a dehydrating agent; (2) At a slightly higher temperature, the inorganic acid and the polyol (carbon source) undergo esterification reaction, and the amine in the system acts as a catalyst for the esterification reaction, which accelerates the esterification reaction; (3) the system is before the esterification reaction or Melting during the esterification reaction; (4) The water vapor generated during the reaction and the incombustible gas generated by the gas source make the system in the molten state expand and foam. At the same time, polyols and esters are dehydrated and carbonized to form inorganic substances and carbon residues, and the system further expands and foams; (5) When the reaction is nearly completed, the system gels and solidifies, and finally forms a porous carbon foam layer.

When the polymer is thermally degraded to form a cross-linked structure or aromatic ring with high thermal stability, the amount of char formation will increase. During the combustion process, char formation has a great influence on the flame retardancy of polymers. Therefore, it is of great significance to develop efficient char-forming agents, especially intumescent flame retardants that can promote the polymer itself to participate in char-forming more. Triazine derivatives are a large class of compounds rich in tertiary nitrogen structures, which have excellent carbonization effects. The three chlorine atoms in cyanuric chloride have different reactivity at different temperatures. Utilizing this feature of cyanuric chloride, it is possible to design different carbon forming agents containing hydroxyl groups, phosphorus elements, etc., or monomeric intumescent flame retardants that integrate gas sources, carbon sources, and acid sources. Nitrogen-containing compounds, mainly triazine derivatives, as new char-forming agents in IFR systems, have proved to have a significant synergistic effect on improving the flame retardancy of IFR. The main feature of triazine derivatives is that starting from its starting material, cyanuric chloride, and reacting with compounds containing different groups, a variety of compounds can be synthesized, which mainly has the following advantages: (1) halogen-free and low toxicity; (2) High decomposition temperature; (3) Little influence on physical and mechanical properties of materials; (4) Anti-bleeding; (5) High flame retardant efficiency.

Xuejun Lai et al. (Lai X J, Tang S, Li H Q, et al. Flame-retardant mechanism of a novel polymeric intumescent flame retardant containing caged bicyclic phosphate for polypropylene[J]. Polymer Degradation and Stability, 2015, 113, 22-31. ) is substituted by 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane (PEPA) and cyanuric chloride, and then polymerized with ethylenediamine The macromolecule intumescent flame retardant PETBP is generated, phosphorus is introduced into the triazine ring, and the flame retardant foaming effect of the triazine ring is increased. The introduced PEPA is a cage-shaped phosphorus-containing compound, which improves the thermal stability of the triazine ring and increases its oxygen content. The acid source and gas source are sufficient during the flame-retardant process, and the flame-retardant effect is improved. If the benzene ring diamine is introduced and the triazine ring is connected to synthesize a macromolecular intumescent flame retardant. Compared with ethylenediamine in PETBP as the polymer chain between triazine rings, the introduction of diamines of benzene rings improves the thermal stability of the product and increases its char formation, without the synergistic effect of APP. It can be directly used in various thermoplastic and thermosetting materials, and has a broader application prospect.

Contents of the invention

The object of the present invention is to provide a halogen-free expansion type flame retardant containing a polymerized macromolecular triazine ring, which introduces diamines of benzene rings, improves the thermal stability of the product, and increases its char formation , It is directly used in various thermoplastic and thermosetting materials without the synergistic effect of APP. At the same time, each triazine monocyclic ring contains 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octyl, which contains high phosphorus and hydroxyl groups, and can be used as Reactive intumescent flame retardant.

The present invention also provides a preparation method of the halogen-free intumescent flame retardant containing a polymerized macromolecular triazine ring, mainly through cyanuric chloride and 1-oxyphospha-4-hydroxymethyl-2,6,7- The reaction is carried out with trioxabicyclo[2.2.2]octane and phenyl diamine, and the preparation method is simple and easy.

Technical scheme of the present invention is as follows:

The halogen-free expansion flame retardant containing polymerized macromolecular triazine ring of the present invention is cyanuric chloride and 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] Octane monosubstituted, phenyl diamine monosubstituted, and make triazine ring linked polymerization reaction product.

The above-mentioned polymerized macromolecular triazine ring-containing halogen-free expansion flame retardant of the present invention, its further technical scheme is that the described benzene ring diamine is p-phenylenediamine, p-xylylenediamine, 2,4-diamino Toluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl or 4,4'-diaminodiphenylmethane.

The above-mentioned polymerized macromolecular triazine ring-containing halogen-free intumescent flame retardant of the present invention has a further technical solution that when the phenylenediamine is p-phenylenediamine, the specific structural formula of the flame retardant is:

When the phenylenediamine is p-xylylenediamine, the specific structural formula of the flame retardant is:

When the benzene ring diamine is 2,4-diaminotoluene, the specific structural formula of the flame retardant is:

When the benzene ring diamine is 2,6-diaminotoluene, the specific structural formula of the flame retardant is:

When the benzene ring diamine is 4,4'-diaminobiphenyl, the specific structural formula of the flame retardant is:

When the benzene ring diamine is 4,4'-diaminodiphenylmethane, the specific structural formula of the flame retardant is:

The preparation method of the above-mentioned polymerized macromolecular triazine ring-containing halogen-free intumescent flame retardant of the present invention comprises the following steps:

1) Add cyanuric chloride and solvent into the reaction kettle, stir to disperse the cyanuric chloride evenly, add 1-oxyphospha-4-hydroxymethyl- 2,6,7-trioxabicyclo[2.2.2]octane and acid-binding agent, so that the pH value of the solution is 5-8, and react for 3-4 hours after the addition is completed, and the pH value is stable at 7-8, and the reaction Separation after finishing, obtain intermediate product one;

2) Raise the temperature to 40°C-55°C, stir, so that the intermediate product is evenly distributed in the solvent, and continue to add benzene ring diamine and acid-binding agent dropwise in a controlled manner, so that the pH value is 5-8. After the dropwise addition is completed, After reacting for 6 to 8 hours, the pH value is stable at 7 to 8. After the reaction is completed, it is separated to obtain the intermediate product 2;

3) Raise the temperature to 95°C-105°C, stir, so that the intermediate product 2 is evenly distributed in the solvent, continue to add benzene ring diamine and acid-binding agent dropwise in a controlled manner, so that the pH value is 5-8, after the dropwise addition is completed After reacting for 10 to 12 hours, the pH value is stable at 7 to 8. After the reaction is completed, it is separated to obtain a halogen-free expandable flame retardant containing a polymeric macromolecule triazine ring.

The above-mentioned preparation method of the present invention, its further technical scheme is that described acid-binding agent is sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, triethylenediamine, N-methyl Morpholine, tetramethylethylenediamine, 1,8-diazabicycloundec-7-ene, or 4-dimethylaminopyridine. The acid-binding agent is preferably sodium bicarbonate or triethylamine.

The above-mentioned preparation method of the present invention, its further technical scheme can also be that described phenylenediamine is p-phenylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene , 4,4'-diaminobiphenyl or 4,4'-diaminodiphenylmethane.

In the above-mentioned preparation method of the present invention, its further technical solution can also be that the solvent described in step 1) and step 2) is a mixture of acetone and water, and the volume ratio of acetone and water is 1:1-1.5.

In the above-mentioned preparation method of the present invention, its further technical scheme can also be that the solvent described in step 3) is toluene.

Compared with prior art, the beneficial effects of the present invention are as follows:

Adding the flame retardant obtained in the present invention to polymers can prepare polymers with flame retardant properties. The present invention has no particular limitation on the flame retardant polymer prepared by the method of the present invention. It can be mixed physically according to the conventional formula. It is hereby applicable to various thermoplastic polymers such as polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polycarbonate, polyterephthalate thermoplastic polyester, etc.; also It can be used as curing agent or auxiliary agent in various thermosetting resins, such as epoxy resin and polyurethane.

Add 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octyl to the flame retardant synthesized by the present invention, so that the carbon layer in the flame retardant is formed It is denser and improves the flame retardant effect; phosphorus elements are added, which mainly play a flame retardant role in the condensed phase, especially for oxygen-containing polymer materials. Compared with ethylenediamine as the polymer chain between triazine rings in PETBP, diamines of benzene rings are also introduced, which improves the thermal stability of the product and increases its char formation, without the synergistic effect of APP It is directly used in various thermoplastic and thermosetting materials.

In the preparation method of the present invention, the synthesis reaction process is continuous, the synthesis process is simple, and the synthesis time generally takes 15 to 25 hours. The method can design different feed ratios according to the requirement of adding polymers, so that macromolecular chains with different molecular weights can be obtained. .

detailed description

Example 1

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Make the cyanuric chloride disperse evenly, then under the condition of 0℃, add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition, react at 0°C for 3 hours. Then raise the temperature to 40°C, add 100ml of acetone solution, then evenly and slowly add 5.4g of p-phenylenediamine and _NaHCO3 solution (8.4g of _NaHCO3 dissolved in 100ml of distilled water) dropwise to the reaction flask, keep the temperature at 40°C, After the dropwise addition was completed, the reaction was carried out under this condition for 8 hours. Then suction filter and wash with water to get the reaction product of the second step, put it into a 1L three-neck flask, add 300ml of toluene, then raise the temperature to 95°C, and evenly and slowly add 5.4g of p-phenylenediamine and triethylamine dropwise into the reaction flask Toluene solution (10.4g triethylamine dissolved in 100ml toluene), stirred and refluxed for 10 to 12 hours, after the reaction was finished, the product was evaporated and dried, then washed with toluene, suction filtered, and then the filtrate was evaporated and dried. The halogen-free intumescent flame retardant (I) containing a polymerized macromolecular triazine ring was obtained with a yield of 83.2%. Its structural formula is:

When the macromolecular triazine ring halogen-free intumescent flame retardant (I) is blended with polypropylene at 1:4, its limiting oxygen index (LOI) is determined to be 43.19%, and the flame retardant rating of UL-94 vertical burning test reaches V -Level 0.

Example 2

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1.5) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Disperse cyanuric chloride evenly, and then add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2 .2] Octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition was completed, reacted for 4 hours at -5°C. Then raise the temperature to 50°C, add 100ml of acetone solution, then evenly and slowly add 6.8g of p-xylylenediamine and _NaHCO3 solution (8.4g of _NaHCO3 dissolved in 100ml of distilled water) to the reaction flask, keeping the temperature at 50°C , After the dropwise addition was completed, the reaction was carried out under this condition for 6 hours. Then suction filter and wash with water to obtain the reaction product of the second step, put it into a 1L three-necked flask, add 300ml of toluene, then raise the temperature to 98°C, and evenly and slowly add 6.8g of p-xylylenediamine and triethylamine dropwise into the reaction flask The toluene solution of amine (10.4g triethylamine dissolved in 100ml toluene), stirred and refluxed for 11 to 12 hours, after the reaction, the product was evaporated and dried, then washed with toluene solution, suction filtered, and the filtrate was evaporated and dried. After drying, a halogen-free intumescent flame retardant (II) containing a polymerized macromolecular triazine ring was obtained with a yield of 89.14%. Its structural formula is:

When the macromolecular triazine ring halogen-free intumescent flame retardant (Ⅱ) is blended with polypropylene at 1:4, its limiting oxygen index (LOI) is determined to be 37.01%, and the flame retardant rating of UL-94 vertical burning test reaches V -Level 0.

Example 3

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Make the cyanuric chloride disperse evenly, then under the condition of 5℃, add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition, react at 5°C for 3 hours. Then raise the temperature to 45°C, add 100ml of acetone solution, then evenly and slowly add 6.15g of 2,4-diaminotoluene and _NaHCO3 solution (8.4g of _NaHCO3 dissolved in 100ml of distilled water) dropwise to the reaction flask, keeping the temperature at 45 °C, after the dropwise addition was completed, the reaction was carried out under this condition for 7 hours. Then suction filter and wash with water to obtain the reaction product of the second step, put it into a 1L three-necked flask, add 300ml of toluene, then raise the temperature to 105°C, and evenly and slowly add 6.15g of 2,4-diaminotoluene and The toluene solution of triethylamine (10.4g triethylamine dissolved in 100ml toluene), stirred and refluxed for 11 to 12 hours, after the reaction, the product was evaporated and dried, then washed with toluene solution, suction filtered, and the filtrate was evaporated After drying, the halogen-free intumescent flame retardant containing polymerized macromolecular triazine ring (Ⅲ) was obtained with a yield of 81.55%. Its structural formula is:

When the macromolecular triazine ring halogen-free intumescent flame retardant (Ⅲ) is blended with polypropylene 1:4, its limiting oxygen index (LOI) is determined to be 42.35%, and the flame retardant rating of UL-94 vertical burning test reaches V -Level 0.

Example 4

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Make the cyanuric chloride disperse evenly, then under the condition of 5℃, add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition, react at 5°C for 3 hours. Then raise the temperature to 50°C, add 100ml of acetone solution, and then evenly and slowly add 6.15g of 2,6-diaminotoluene and _NaHCO3 solution (8.4g of _NaHCO3 dissolved in 100ml of distilled water) to the reaction flask, keeping the temperature at 50 °C, after the dropwise addition was completed, the reaction was carried out under this condition for 7 hours. Then suction filter and wash with water to obtain the reaction product of the second step, put it into a 1L three-necked flask, add 300ml of toluene, then raise the temperature to 100°C, and evenly and slowly add 6.15g of 2,6-diaminotoluene and The toluene solution of triethylamine (10.4g triethylamine dissolved in 100ml toluene), stirred and refluxed for 11 to 12 hours, after the reaction, the product was evaporated and dried, then washed with toluene solution, suction filtered, and the filtrate was evaporated After drying, the halogen-free intumescent flame retardant (Ⅳ) containing polymerized macromolecular triazine ring was obtained, and the yield was 87.08%. Its structural formula is:

When the macromolecular triazine ring halogen-free intumescent flame retardant (Ⅳ) is blended with polypropylene 1:4, its limiting oxygen index (LOI) is determined to be 45.64%, and the flame retardant rating of UL-94 vertical burning test reaches V -Level 0.

Example 5

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Make the cyanuric chloride disperse evenly, then under the condition of 5℃, add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition, react at 5°C for 3 hours. Then raise the temperature to 50°C, add 100ml of acetone solution, then evenly and slowly add 9.3g of 4,4'-diaminobiphenyl and _NaHCO3 solution (8.4g _NaHCO3 dissolved in 100ml of distilled water) to the reaction flask, keeping The temperature was 50°C, and after the dropwise addition was completed, the reaction was continued for 7 hours under this condition. Then suction filter and wash with water to obtain the reaction product of the second step, put it into a 1L three-necked flask, add 300ml of toluene, then raise the temperature to 100-105°C, and evenly and slowly add 9.3g of 4,4'-di The toluene solution of aminobiphenyl and triethylamine (10.4g triethylamine dissolved in 100ml toluene), stirred and refluxed for 11 to 12 hours, after the reaction, the product was evaporated and dried, then washed with toluene solution, and suction filtered. Then, the filtrate was evaporated and dried to obtain a halogen-free intumescent flame retardant (Ⅴ) containing a polymerized macromolecular triazine ring, with a yield of 84.27%. Its structural formula is:

When the macromolecular triazine ring halogen-free intumescent flame retardant (Ⅴ) is blended with polypropylene at 1:4, its limiting oxygen index (LOI) is determined to be 43.29%, and the UL-94 vertical burning test flame retardant grade reaches V -Level 0.

Example 6

Add 18.45g of cyanuric chloride and 100ml of acetone solution (the volume ratio of acetone and water is 1:1) in the 1L reaction flask equipped with reflux condenser, constant pressure dropping funnel, stirrer and thermometer, fully stir, Make the cyanuric chloride disperse evenly, then under the condition of 5℃, add 18g of 1-oxyphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2. 2] octane and NaHCO ₃ solution (8.4g NaHCO ₃ dissolved in 100ml distilled water), after the dropwise addition, react at 5°C for 3 hours. Then raise the temperature to 50°C, add 100ml of acetone solution, and then evenly and slowly add 10g of 4,4'-diaminodiphenylmethane and _NaHCO3 solution (8.4g _NaHCO3 dissolved in 100ml of distilled water) dropwise to the reaction flask, Keep the temperature at 50°C. After the dropwise addition is complete, react under this condition for 7 hours. Then suction filter and wash with water to obtain the reaction product of the second step, put it into a 1L three-neck flask, add 300ml of toluene, then raise the temperature to 95-105°C, and evenly and slowly add 10g of 4,4'-diamino The toluene solution of diphenylmethane and triethylamine (10.4g triethylamine is dissolved in 100ml toluene), stirred and refluxed for 11 to 12 hours, after the reaction, the product was evaporated and dried, then washed with toluene solution and suction filtered. The filtrate was then evaporated and dried to obtain a halogen-free intumescent flame retardant (Ⅵ) containing a polymerized macromolecular triazine ring, with a yield of 90.19%. Its structural formula is:

When the macromolecule triazine ring halogen-free intumescent flame retardant (Ⅵ) is blended with polypropylene at 1:4, its limiting oxygen index (LOI) is determined to be 41.82%, and the flame retardant rating of UL-94 vertical burning test reaches V -Level 0.

Claims (9)

1. one kind containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described fire retardant be Cyanuric Chloride respectively with 1-epoxide phospha-4-methylol-2, the replacement of 6,7-trioxa-l-phosphabicyclos [2.2.2] octane one, phenyl class diamidogen one replacement, and make triazine ring The polymeric reaction product being connected.

The most according to claim 1 containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described phenyl ring class Diamidogen is p-phenylenediamine, p dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'-bis- Diaminodiphenylmethane.

The most according to claim 2 containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described phenyl ring class When diamidogen is p-phenylenediamine, fire retardant concrete structure formula is:

When described phenyl ring class diamidogen is p dimethylamine, fire retardant concrete structure formula is:

When described phenyl ring class diamidogen is 2,4 di amino toluene, fire retardant concrete structure formula is:

Described phenyl ring class diamidogen is 2, and during 6-diaminotoluene, fire retardant concrete structure formula is:

Described phenyl ring class diamidogen is 4, and during 4'-benzidine, fire retardant concrete structure formula is:

Described phenyl ring class diamidogen is 4, and during 4'-MDA, fire retardant concrete structure formula is:

4. the preparation method containing polymerization macro molecular triazine ring halogen-free expansion fire retardant as claimed in claim 1, it is characterised in that Comprise the following steps:

1) add Cyanuric Chloride and solvent, stirring in a kettle., make Cyanuric Chloride dispersed, control to drip at-5 DEG C～5 DEG C Add and drip 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane and acid binding agent so that solution ph is 5～8, Reacting 3～4 hours after being added dropwise to complete, pH stable is 7～8, and reaction separates after terminating, and obtains intermediate product one；

2) temperature is increased to 40 DEG C～55 DEG C, stirring so that intermediate product one uniform distribution in a solvent, continues to control dropping benzene Ring class diamidogen and acid binding agent so that pH value is 5～8, react 6～8 hours after being added dropwise to complete, pH stable is 7～8, instead Should separate after terminating, obtain intermediate product two；

3) temperature is increased to 95 DEG C～105 DEG C, stirring so that intermediate product two uniform distribution in a solvent, continues to control dropping Phenyl ring class diamidogen and acid binding agent so that pH value is 5～8, react 10～12 hours after being added dropwise to complete, pH stable 7～8, Reaction separates after terminating, and obtains containing polymerization macro molecular triazine ring halogen-free expansion fire retardant.

Preparation method the most according to claim 4, it is characterised in that described acid binding agent is sodium bicarbonate, sodium carbonate, hydroxide Sodium, potassium hydroxide, triethylamine, pyridine, triethylene diamine, N-methylmorpholine, tetramethylethylenediamine, 1,8-diazabicylo ten One carbon-7-alkene or DMAP.

Preparation method the most according to claim 5, it is characterised in that described acid binding agent is sodium bicarbonate or triethylamine.

Preparation method the most according to claim 4, it is characterised in that described phenyl ring class diamidogen be p-phenylenediamine, p dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'-MDA.

Preparation method the most according to claim 4, it is characterised in that step 1) and step 2) described in solvent be acetone and The volume ratio of the mixture of water, acetone and water is 1:1～1.5.

Preparation method the most according to claim 4, it is characterised in that step 3) described in solvent be toluene.