CN111848681A - Metal coordination intumescent flame retardant and preparation method thereof - Google Patents
Metal coordination intumescent flame retardant and preparation method thereof Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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Abstract
A metal coordination intumescent flame retardant and a preparation method thereof are characterized in that: the structure of the flame retardant is shown as the following general formula (I):
in the general formula (I), M is Zn2+，Cu2+，Mn2+，Co3+N is 1 to 5; has the advantages of good thermal stability, high decomposition temperature, easy processing and recovery, and no need of compounding with montmorillonite or molecular sieve.
Description
Technical Field
The invention belongs to the field of environment-friendly flame retardant additives, and particularly relates to a metal coordination intumescent flame retardant and a preparation method thereof.
Background
In recent years, research and development of flame retardant materials are actively conducted in countries around the world, and various flame retardant products are continuously made. Although the halogen flame retardant has a good flame retardant effect, toxic and corrosive gases are released during combustion, and great hidden danger exists for human beings and the environment. Therefore, in the two commands of 'scrap electronic and electric equipment command' (WEEE) and 'RoHS command for forbidding harmful substances in electronic and electric appliances' (RoHS) issued in 2003 by the European Union, the addition of harmful halogen flame retardants such as polybrominated diphenyl ethers to the electronic and electric appliances is strictly forbidden. Compared with halogen flame retardants, inorganic flame retardants and Intumescent Flame Retardants (IFR) are currently recognized as environment-friendly 'green' flame retardants in the scientific and industrial circles, but the flame retardants have poor thermal stability and low decomposition temperature, which causes difficulties in processing and recycling of flame-retardant high polymers.
Patent application documents with publication numbers of CN101168607A, CN101186828A, CN101230275A, CN1018641112A and the like all disclose preparation methods of flame retardants with high thermal stability, and phosphorus-nitrogen expansion type flame retardants with different structures are compounded with montmorillonite or molecular sieves, so that char formation crosslinking is promoted, and the thermal stability and flame retardant property of the flame retardants are improved. However, the method related to the above patent application technology requires that the intumescent flame retardant is compounded with the montmorillonite or the molecular sieve to have higher thermal stability, and the compatibility problem exists in the compounding process; moreover, the dispersion problem of the montmorillonite or molecular sieve structure is also considered, and the process requirement on experimental operation is higher.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the metal coordination intumescent flame retardant which has good thermal stability, high decomposition temperature and easy processing and recovery and does not need to be compounded with montmorillonite or molecular sieve.
In order to solve the technical problems, the invention adopts the technical scheme that: a metal coordination intumescent flame retardant has a structure shown as a general formula (I):
in the general formula (I), M is Zn2+，Cu2+，Mn2+，Co3+Wherein n is 1 to 5.
The metal coordination intumescent flame retardant of the invention is a single substance or a mixture of a plurality of substances satisfying the general formula, such as any mixture of a plurality of corresponding substances obtained from the following steps of n ═ 1,2,3, 4 and 5.
The invention also provides a preparation method of the metal coordination intumescent flame retardant, and the specific synthesis route diagram is as follows:
specifically, the invention also provides a detailed preparation step of the preparation method of the metal coordination intumescent flame retardant, which comprises the following steps:
(1) carrying out amination reaction on salicylaldehyde and an o-phenylenediamine compound in an ethanol solvent for 5-10 hours in a reflux state at normal pressure, wherein the molar ratio of the salicylaldehyde to the o-phenylenediamine compound is 1:2, so as to obtain a product (II), and the structure of the product is as follows:
(2) putting the product (II) obtained in the step (1) in an alkaline solution, wherein the mass ratio of alkaline substances in the alkaline solution to the product (II) is 0.26:1, and carrying out condensation reaction under the oxidation action of an oxidant, the reaction temperature is 50-80 ℃, the reaction time is 5-24 hours, and then neutralizing the product (III) by using concentrated hydrochloric acid to be neutral to obtain a product (III), and the structure of the product is as follows:
(3) pentaerythritol and concentrated phosphoric acid react for 3-6 hours at the temperature of 100 ℃ and 150 ℃ according to the molar ratio of phosphoric acid/pentaerythritol of 2:1 to obtain a phosphorus-containing product (IV), and the structure is as follows:
(4) the dimethyl formamide solution of the product (III) obtained in the step (2) and metal acetic acidSalt (M (OOCCH)3)2) The dimethyl formamide solution and the product (IV) react for 5 to 10 hours at the temperature of between 80 and 110 ℃ to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I).
The alkaline solution in step (2) of the present invention is a 10 wt% potassium hydroxide aqueous solution, and the oxidizing agent is one or a mixture of more of perchloric acid, hypobromous acid, hypochlorous acid, sodium hypochlorite, chlorous acid, permanganic acid, perbromic acid, hydrogen peroxide, oxygen, and the like.
The concentrated phosphoric acid in the step (3) of the invention has a mass percentage concentration of 85% and a mass concentration of 4 mol/L.
The metal acetate in the step (4) of the invention is any one or a mixture of a plurality of zinc acetate, manganese acetate, nickel acetate and cobalt acetate; the molar concentration of the metal acetate (M (OOCCH3)2) in the dimethylformamide is 0.25-0.75mol/L (namely 1L of dimethylformamide contains 0.25-0.75mol of metal acetate).
The concentration of the product (III) in the dimethylformamide solution in the step (4) of the present invention is 75 to 80g/L, preferably 78.5 g/L; in step (4), the molar ratio of the product (iii) to the product (iv) to the metal acetate is 0.05:1: 1.
The invention has the advantages and beneficial effects that:
1. the invention combines metal ions and the intumescent flame retardant by a coordination mode, so that the whole flame retardant structure tends to be stabilized. On the other hand, the catalytic flame-retardant effect of the metal element can improve the flame-retardant effect of the intumescent flame retardant, and the environment-friendly intumescent flame retardant with high thermal stability can be obtained. The flame retardant with a specific structure provided by the invention has very important influence on the final performance due to the positions of metal ions and the functional groups in coordination and overlapping with the metal ions; the flame retardants of the prior art, if not coordinated with metals, result in poor thermal stability; the phosphorus structure of the prior art, if not provided with a cyclic structure, also causes poor thermal stability; meanwhile, if the phosphorus structures in the prior art are still connected in a covalent bond mode, nitrogen protection is needed in the operation process, the control requirement on the operation process conditions is high, and the operation is complex. The flame retardant structure of the invention does not have the condition of the prior art, and the metal coordination and phosphorus-containing structure in the invention are cyclic structures, so that the thermal stability can be improved; the flame retardant of the specific structure of the present application, compared to the prior art, has the difference that 1) the coordination position of the metal ion has essential difference: the metal ions are coordinated between unsaturated amine of a benzene ring side group, N-, hydroxyl oxygen-OH of the benzene ring and a phosphoric acid structure of the annular phosphorus flame retardant; the metal ions in the prior art are coordinated between the saturated amino and the hydroxyl of the benzene ring; 2) the coordination structure of the metal ions in the application is superior in that double bonds of unsaturated amino groups and double bonds on a benzene ring exist in the same coordination six-membered ring, so that a more stable conjugated structure is formed, and the thermal stability of the structure is improved; 3) the phosphorus element in the phosphorus flame retardant used in the application is positioned in two connected five-membered ring structures, and the five-membered ring structures are more stable, so that the structural system of the application has higher thermal stability; 4) in the prior art, phosphorus-containing groups are combined into a metal type flame retardant in a covalent bond mode, sodium ethoxide is used as a catalyst in a synthesis process, as is well known, sodium ethoxide is generally prepared at any time, and needs to be reacted by metal sodium and ethanol, and the metal sodium is extremely easy to catch fire when meeting water and is an extremely dangerous chemical; meanwhile, the sodium ethoxide is stronger in alkalinity than the sodium hydroxide, so that the danger of the operation process is increased; the phosphorus-containing group is combined into the flame retardant in a coordination bond mode, and sodium ethoxide is not needed in the process, so that the phosphorus-containing group has better operation safety; 5) the flame retardant related in the prior art is a micromolecule, and is added into a macromolecular matrix, so that the migration effect is easy to generate, and the flame retardant effect has timeliness; the flame retardant is of a polymer structure with a certain long chain, is added into a high molecular substrate needing flame retardance, and is not easy to migrate, so that the flame retardant effect is superior to that of a small molecular structure flame retardant in aging.
2. The method has the advantages of simple and convenient operation, mild reaction conditions, high yield, cheap and easily-obtained raw materials, and the obtained metal coordination intumescent flame retardant has high thermal stability and flame retardant property. The preparation method combines the methods of amination, condensation, metal organic coordination and the like, can combine elements such as phosphorus, nitrogen and the like with the expansion flame-retardant function with metal ions with the catalytic flame-retardant function, and the obtained product has a certain molecular chain length, can have good compatibility with an organic polymer system, and endows a certain flame-retardant effect. The method has simple operation and high yield. The obtained flame retardant has longer molecular chain and better compatibility with a polymer matrix; the obtained flame retardant structure is a complex of metal ions and an intumescent flame retardant, the stable metal coordination structure can effectively improve the thermal stability of the flame retardant, the flame retardant has excellent char formation, and the residual char content of the flame retardant after degradation at 700 ℃ in a nitrogen atmosphere can reach over 64 percent.
Drawings
FIG. 1 shows the comparison spectrum of the infrared test of the product structure (III) of the recondensation of the product of the reaction of the product (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant and the product of the reaction of salicylaldehyde and o-phenylenediamine.
FIG. 2 shows a nuclear magnetic hydrogen spectrum comparison of the product structure (II) after the reaction of salicylaldehyde with o-phenylenediamine with the product structure (III) after the recondensation of the product structure (II).
FIG. 3 shows comparative chart of thermogravimetric test of product structure (I) of intumescent flame retardant coordinated by metal cobalt, manganese, nickel and zinc.
Detailed Description
The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples.
The technical effects to be realized by the invention are as follows: the thermal stability is good, the decomposition temperature is high, and the expansion type flame retardant is not required to be compounded with montmorillonite or molecular sieve, so that the flame retardant property of the organic polymer matrix can be effectively ensured.
Example 1
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10 wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24 h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) with the concentration of 78.5g/L and 200ml of DMF solution of 0.5mol/L zinc acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I).
30g of the flame retardant obtained in the embodiment example is added into 70g of low-density polyethylene, the oxygen index of the obtained flame retardant material can reach 28.5%, and the vertical burning reaches UL 94V 0 level.
Example 2
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10 wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24 h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of nickel acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of low-density polyethylene, the oxygen index of the obtained flame retardant material can reach 27.9%, and the vertical burning can pass UL 94V 0 grade.
Example 3
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10 wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, introducing oxygen for reaction for 24 hours, neutralizing the solution to be neutral by using hydrochloric acid after the reaction is finished to obtain a brown solid, washing the brown solid with deionized water for 3 times, and drying the brown solid in a vacuum drying oven at 50 ℃ under reduced pressure for 24 hours to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 65%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of zinc acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of polypropylene, the oxygen index of the obtained flame retardant material can reach 29.1%, and the vertical burning can pass UL 94V 0 grade.
Example 4
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10 wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dropwise adding 25ml of 27.5% hydrogen peroxide aqueous solution within 20min, neutralizing the solution to be neutral by using hydrochloric acid after the reaction is finished, obtaining brown solid, washing the brown solid for 3 times by using deionized water, and drying the brown solid in a vacuum drying oven at 50 ℃ under reduced pressure for 24 hours to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 78%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of manganese acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of PC/ABS alloy (wherein the mass ratio of PC to ABS in the alloy is 70/30), the oxygen index of the obtained flame retardant material can reach 31.2%, and the vertical combustion can pass UL 94V 0 grade.
Example 5
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10 wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24 h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) and 200ml of 0.3mol/L DMF solution of cobalt acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 4h to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of polypropylene, the oxygen index of the obtained flame retardant material can reach 28.3%, and the vertical combustion can pass UL 94V 0 grade.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications and equivalents which do not depart from the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Test results
The comparative spectrum analysis of the infrared test of the product structure (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant shown in the figure 1, the example 2, the example 4 and the example 5 respectively shows that: it is evident from FIG. 1 that 1590-1700cm before and after coordination-1All have absorption peaks for the group C ═ N; after the coordination of metal and phosphate, the concentration is 1000-1200cm-1A very distinct characteristic peak of phosphate ester appears; at 521--1The peaks appeared are the peaks of chemical bonds Co-O, Mn-O, Ni-O and Zn-O generated after coordination of metal cobalt, manganese, nickel and zinc, and the above shows that the metal coordination intumescent flame retardant is successfully synthesized.
The nuclear magnetic hydrogen spectrum comparison of the product structure (II) after the reaction of salicylaldehyde and o-phenylenediamine and the product structure (III) after the recondensation of the product structure (II) shown in FIG. 2 shows that: the nuclear magnetic peak position of the product structure (II) is basically similar to that of the product structure (III) obtained after condensation, because the condensation position occurs on the benzene ring of salicylaldehyde, except for adding the same chain unit, no new group structure appears, and therefore the positions of hydrogen are relatively similar, and no new displacement appears. The nuclear magnetic hydrogen spectrum of the product structure (III) has larger noise between 6 ppm and 9ppm, because the polymerized product has poor solubility in a deuterated reagent used for testing, and the nuclear magnetic spectrum has larger noise. Wherein a is the peak shift of the hydrogen atom on the hydroxyl group on the benzene ring, b is the peak shift of the hydrogen atom on the carbon atom in the C ═ N bond, C is the peak shift of the hydrogen atom on the carbon atom in the meta position of the hydroxyl group on the benzene ring, d is the peak shift of the hydrogen atom on the carbon atom on the benzene ring to which the bis-N bond is attached, and e is the peak shift of the hydrogen atom on the carbon atoms in the ortho position and the para position of the hydroxyl group on the benzene ring.
FIG. 3 shows the comparative spectrogram analysis of the thermal weight loss test of the product structure (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant: the metal-coordinated intumescent flame retardants are degraded smoothly during the whole temperature scanning process, and their carbon residue amounts are 77.6%, 72.1%, 64.5%, and 89.4%, respectively. This shows that the structural combination of metal, phosphorus and nitrogen elements can obtain higher thermal stability organic-inorganic hybrid products.
Claims (10)
1. A metal coordination intumescent flame retardant is characterized in that: the structure of the flame retardant is shown as the following general formula (I):
in the general formula (I), M is Zn2+，Cu2+，Mn2+，Co3+Wherein n is 1 to 5.
2. The metal-coordinated intumescent flame retardant of claim 1, characterized in that: the flame retardant is any one of corresponding substances corresponding to the general formula (I) when n is 1, 2, 3, 4 and 5 or a mixture comprising a plurality of substances.
3. A preparation method of a metal coordination intumescent flame retardant is characterized by comprising the following steps: the specific synthetic route diagram is:
4. a process for the preparation of a metal-coordinated intumescent flame retardant as claimed in claim 3, characterized in that: the preparation method comprises the following steps:
(1) carrying out amination reaction on salicylaldehyde and an o-phenylenediamine compound in an ethanol solvent for 5-10 hours in a reflux state at normal pressure, wherein the molar ratio of the salicylaldehyde to the o-phenylenediamine compound is 1:2, so as to obtain a product (II), and the structure of the product is as follows:
(2) Putting the product (II) obtained in the step (1) in an alkaline solution, wherein the mass ratio of alkaline substances to the product (II) is 0.26:1, and the condensation reaction is carried out under the oxidation action of an oxidant, the reaction temperature is 50-80 ℃, the reaction time is 5-24 hours, and then neutralizing the product to be neutral by concentrated hydrochloric acid to obtain a product (III), and the structure of the product is as follows:
(3) pentaerythritol and concentrated phosphoric acid react for 3-6 hours at the temperature of 100 ℃ and 150 ℃ according to the molar ratio of phosphoric acid/pentaerythritol of 2:1 to obtain a phosphorus-containing product (IV), and the structure is as follows:
(4) dimethyl formamide solution of the product (III) obtained in the step (2) and metal acetate (M (OOCCH)3)2) The dimethyl formamide solution and the product (IV) react for 5 to 10 hours at the temperature of between 80 and 110 ℃ to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I).
5. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the alkaline solution in the step (2) is a 10 wt% potassium hydroxide aqueous solution, and the oxidant is any one or more of perchloric acid, hypobromous acid, hypochlorous acid, sodium hypochlorite, chlorous acid, permanganic acid, perbromic acid, hydrogen peroxide and oxygen.
6. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the concentrated phosphoric acid in the step (3) is concentrated phosphoric acid with the mass percentage concentration of 85% and the mass concentration of 4 mol/L.
7. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the metal acetate in the step (4) is any one or more of zinc acetate, manganese acetate, nickel acetate and cobalt acetate.
8. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the molar concentration of the dimethylformamide solution of the metal acetate is 0.25-0.75 mol/L.
9. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the concentration of the product (III) in the dimethylformamide solution in the step (4) is 75-80 g/L.
10. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 9, characterized in that: the concentration of the product (III) in the dimethylformamide solution in the step (4) is 78.5 g/L; in step (4), the molar ratio of the product (iii) to the product (iv) to the metal acetate is 0.05:1: 1.
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