CN115160144A - Transition metal substituted heteropoly acid based ionic liquid flame retardant, preparation method and application thereof - Google Patents

Transition metal substituted heteropoly acid based ionic liquid flame retardant, preparation method and application thereof Download PDF

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CN115160144A
CN115160144A CN202210684913.4A CN202210684913A CN115160144A CN 115160144 A CN115160144 A CN 115160144A CN 202210684913 A CN202210684913 A CN 202210684913A CN 115160144 A CN115160144 A CN 115160144A
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flame retardant
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transition metal
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ionic liquid
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吕红金
曾影
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Beijing Institute of Technology BIT
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Abstract

The invention relates to a transition metal substituted heteropoly acid based ionic liquid flame retardant, a preparation method and application thereof, belonging to the technical field of flame retardant materials. The flame retardant consists of organic cations and transition metal substituted polyoxometalate anions, wherein the organic cations are imidazole organic cations, pyridine organic cations, quaternary ammonium organic cations or quaternary phosphonium organic cations; the transition metal is iron, cobalt, nickel, copper, zinc or manganese. The flame retardant is prepared by anion and cation exchange in a water phase or an organic phase. The flame retardant takes transition metal substituted heteropoly acid as a catalytic flame-retardant active center, and can effectively improve the flame-retardant property of the flame-retardant modified composite material.

Description

Transition metal substituted heteropoly acid based ionic liquid flame retardant, preparation method and application thereof
Technical Field
The invention relates to a transition metal substituted heteropoly acid based ionic liquid flame retardant, a preparation method and application thereof, belonging to the technical field of flame retardant materials.
Background
The resin polymer such as epoxy resin has excellent physical properties, chemical properties, bonding properties, corrosion resistance and the like, so the resin polymer is widely applied to various fields of national social life and national defense and military construction such as electronics, electricity, mechanical manufacturing, chemical industry anticorrosion, aerospace and the like; however, most resin polymers belong to combustible and inflammable materials, and have the advantages of high heat release rate, high heat value and high flame propagation speed during combustion, and are generally accompanied with the release and melting and dripping of a large amount of toxic smoke, so that fire hazard potential of products in the using process is great, and the personal and property safety of the people is seriously threatened. With the continuous development of new technologies, the demand of industries such as electronics, electrical and aerospace is increasing, and meanwhile, the requirements for heat resistance and flame retardancy of products are also increasing, and common electronic components such as capacitors, radiators, power supply units and the like are easy to become ignition sources when short circuits occur, so that high molecular materials close to the components must have certain flame retardant properties, and the flammability of resin polymers greatly limits the application of the resin polymers in the fields of electronic and electrical industries and composite materials with certain requirements for flame retardant properties. Therefore, the improvement of the flame retardant property of the resin polymer is a key measure for solving the fire safety hidden trouble of the material and ensuring national economy and social safety, and has an extremely important strategic demand background in various fields of electronics and electricity, information communication, mechanical manufacturing, aerospace and the like.
At present, the common challenges for the development of flame-retardant modification of resin polymers at home and abroad are as follows: (1) The compatibility problem of the flame retardant and a resin matrix, and the compatibility of most additive flame retardants and the resin matrix is poor, so that irreversible negative effects on the processing performance, the mechanical property and the like of the material are easily caused, or phenomena of migration precipitation, phase separation and the like of the flame retardant appear over time; (2) The safety problem of the flame retardant, most of high-efficiency flame retardants represented by halogen compounds are extremely harmful to human bodies and the environment, and although relevant instruction and regulations have been issued by the european union to limit the use of the flame retardants with potential safety hazards, alternative environment-friendly high-efficiency flame retardants are lacking. Therefore, research and development of a novel flame retardant which has good compatibility with materials, does not deteriorate inherent properties of a matrix, has high flame retardant efficiency and is environment-friendly are important problems to be solved urgently in the field of flame retardant modification of epoxy resin materials.
Polyoxometalate (POMs) is a metal-oxygen cluster compound which is generated by the joint angle, the common edge or the coplanar bridging of coordination polyhedrons formed by oxygen atoms and high-valence early transition metal atoms such as molybdenum, tungsten, vanadium, niobium, tantalum and the like, and has diversified and controllable structures and redox activity. POMs-based ionic liquids (POM-ILs) prepared by regulating the type of counter cation of POMs such as introducing the cation of ionic liquid (ionic liquids) can be used in the field of flame retardant materials, such as Chinese patent applications 201510981817.6 and 201310315174.2, however, POM-ILs disclosed in the above patent applications are used as flame retardant synergists in combination with other traditional flame retardants. The inventor researches and discovers that the POM-ILs have extremely poor effect of being directly used as flame retardants for flame retardant modification of high polymer materials under the condition of not compounding or modifying phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants and other flame retardant groups, and how to obtain the POM-ILs which can be directly used as the flame retardants is not reported in the prior art at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a transition metal-substituted heteropoly acid-based ionic liquid flame retardant, a preparation method and an application thereof.
In order to realize the purpose, the technical scheme of the invention is as follows:
a transition metal substituted heteropoly acid group ionic liquid flame retardant consists of organic cations and transition metal substituted polyoxometalate anions, wherein the organic cations are imidazole organic cations, pyridine organic cations, quaternary ammonium organic cations or quaternary phosphonium organic cations; the transition metal is iron, cobalt, nickel, copper, zinc or manganese.
Preferably, the organic cation is a 1-ethyl-3-methylimidazole cation, a 1-butyl-3-methylimidazole cation, a 1-hexyl-3-methylimidazole cation, a 1-octyl-3-methylimidazole cation, a 1-dodecyl-3-methylimidazole cation, an N-ethylpyridine cation, an N-butylpyridine cation, an N-hexylpyridine cation, an N-octylpyridine cation, a tetrabutylquaternary ammonium cation, a tetrapentyl quaternary ammonium cation, a tetraheptyl quaternary ammonium cation, a tetraoctyl quaternary ammonium cation, a trioctylmethyl quaternary ammonium cation, a dodecyltrimethyl quaternary ammonium cation, a tributylethyl quaternary phosphonium cation, a tributylhexyl quaternary phosphonium cation or a tetrabutyl quaternary phosphonium cation.
Preferably, the transition metal-substituted polyoxometalate anion is [ Mn IV Mo 9 O 32 ] 6- 、 [Ni IV Mo 9 O 32 ] 6- 、[H 6 Co III Mo 6 O 24 ] 3- 、[H 6 Fe II Mo 6 O 24 ] 4- 、[H 6 Ni II Mo 6 O 24 ] 4- 、 [H 6 Cu II Mo 6 O 24 ] 4- 、[H 6 Zn II Mo 6 O 24 ] 4- 、[H 6 Ni II W 6 O 24 ] 4- 、[H 6 Mn II W 6 O 24 ] 4- 、 [H 4 Co II 4 P 2 W 18 O 70 ] 10- 、[H 4 Cu II 4 P 2 W 18 O 70 ] 10- 、[H 4 Zn II 4 P 2 W 18 O 70 ] 10- 、 [H 4 Ni II 4 P 2 W 18 O 70 ] 10- Or [ H ] 4 Mn II 4 P 2 W 18 O 70 ] 10- 。
Preferably, the organic cation is 1-ethyl-3-methylimidazolium cation, tetrapentaneQuaternary alkylammonium cations, quaternary tetraheptyl quaternary ammonium cations, or quaternary tetrabutylphosphonium cations; the transition metal substituted polyoxometalate anion is [ H ] 6 Ni II Mo 6 O 24 ] 4- 、[H 4 Ni II 4 P 2 W 18 O 70 ] 10- 、[H 4 Mn II 4 P 2 W 18 O 70 ] 10- 、[H 6 Cu II Mo 6 O 24 ] 4- 、 [H 4 Cu II 4 P 2 W 18 O 70 ] 10- Or [ H ] 4 Co II 4 P 2 W 18 O 70 ] 10- 。
The invention relates to a preparation method of a transition metal substituted heteropoly acid group ionic liquid flame retardant, which comprises the following steps:
(1) Dissolving organic cation halogen salt in a solvent to obtain an organic cation salt solution; when the organic cation halogen salt is water-soluble, the solvent is water with the purity of deionized water or higher; when the organic cationic halogen salt is water insoluble, the solvent is dichloromethane;
(2) Mixing a transition metal substituted heteropoly acid aqueous solution with the organic cation salt solution, and stirring for more than 0.5h to fully exchange anions and cations to obtain a mixture;
(3) When the solvent in the step (1) is water, collecting the precipitate in the mixture in the step (2), and washing and drying to obtain the transition metal substituted heteropoly acid based ionic liquid flame retardant; and (2) when the solvent in the step (1) is dichloromethane, collecting an organic phase in the mixture in the step (2), removing the dichloromethane, washing and drying to obtain the transition metal substituted heteropoly acid based ionic liquid flame retardant.
Preferably, in the step (2), the transition metal-substituted heteropoly acid aqueous solution and the organic cation salt solution are mixed according to a stoichiometric ratio of anion-cation exchange.
The invention relates to an application of a transition metal substituted heteropoly acid based ionic liquid flame retardant, which is used for carrying out flame retardant modification on a high molecular polymer.
Preferably, the flame retardant is used for flame-retardant modification of epoxy resin as an additive flame retardant or used for flame-retardant modification of cellulose as a surface coating.
Preferably, when the epoxy resin is flame retardant modified: firstly, adding the flame retardant into epoxy resin glue, stirring and mixing uniformly to obtain a mixed solution, and heating and melting an epoxy resin curing agent to obtain a curing solution; then uniformly stirring and mixing the mixed solution and the curing solution, removing bubbles, and curing to obtain the flame-retardant modified epoxy resin composite material; wherein the addition amount of the flame retardant is 0.5-10% by taking the total mass of the flame retardant, the epoxy resin and the epoxy resin curing agent as 100%;
when flame retardant modification is performed on cellulose: dispersing the flame retardant in acetone, stirring and dispersing uniformly to obtain a dispersion liquid, wherein the concentration of the flame retardant in the dispersion liquid is 100-300 mg/mL, soaking the cellulose cloth strip in the dispersion liquid for 5-10 min, and drying after the soaking is finished to obtain the flame-retardant modified cellulose composite material.
Preferably, when the epoxy resin is subjected to flame retardant modification, the addition amount of the flame retardant is 1-7%.
Advantageous effects
(1) In the transition metal substituted heteropoly acid based ionic liquid flame retardant provided by the invention, a novel halogen-free, smoke-inhibiting, low-toxicity and high-efficiency flame retardant is formed by compounding organic cations and transition metal substituted polyoxometalate anions, and the flame retardant takes transition metal substituted heteropoly acid as a catalytic flame-retardant active center, so that the char formation efficiency of a condensed phase of a flame-retardant modified composite material can be improved, the overflow of inflammable or toxic smoke is inhibited, the phenomena of melting and dripping and the like are avoided, and the flame retardant performance of the composite material is effectively improved. In addition, the composite material after flame retardant modification has high thermal stability, is non-toxic and difficult to volatilize, and can avoid the problems of migration and precipitation, safety and the like existing in the processing or using process of the traditional flame retardant.
(2) In the transition metal substituted heteropoly acid based ionic liquid flame retardant provided by the invention, the catalytic effect of transition metal can be fully exerted by further optimizing the anion framework structure and the element composition, and the carbonization reactions such as ring structuring, aromatization, crosslinking, graphitization and the like are promoted, so that the condensed phase carbonization flame retardant efficiency of the flame retardant is improved; meanwhile, the organic cation can be used as a surfactant to adjust the interfacial tension between the flame retardant and the substance to be modified by further optimizing the type of the organic cation, so that the compatibility between the flame retardant and the material to be modified is optimized.
(3) The preparation method of the transition metal substituted heteropoly acid based ionic liquid flame retardant provided by the invention can be realized by carrying out anion and cation exchange in a water phase or an organic phase, and the synthesis process is simple.
Drawings
FIG. 1 is a Fourier infrared spectrum of the flame retardant described in examples 2-4.
FIG. 2 is a thermogravimetric plot of the flame retardant modified epoxy resin described in application examples 1-2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following comparative examples, comparative application examples and examples of application:
(1) Fourier infrared spectrum test: the instrument Bruker sensor II tests the range of 500-4000cm -1 Resolution of 4cm -1 。
(2) Thermal weight loss test: the apparatus Netzsch STA 449F3 Jupiter, the test range is 30-800 ℃, the heating rate is 10 ℃/min, and the nitrogen atmosphere is adopted.
Comparative example 1
Dissolving 3.2g of tetraheptyl ammonium bromide in 20mL of dichloromethane at the temperature of 25 +/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; mixing 5g of K 6 [P 2 W 18 O 62 ]Dissolving in 100mL distilled water to obtain K 6 [P 2 W 18 O 62 ]A solution; the K is added 6 [P 2 W 18 O 62 ]Solution is dropwise added to theStirring for 0.5h in a tetraheptyl ammonium bromide solution to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain heteropoly acid group ionic liquid (C) 28 H 60 N) 6 [P 2 W 18 O 62 ]。
The Fourier infrared spectrum result of the heteropoly acid radical ionic liquid shows that the cation is tetraheptyl quaternary ammonium cation and the anion is [ P ] 2 W 18 O 62 ] 6- 。
Example 1
Dissolving 3.5g of 1-ethyl-3-methylimidazole bromine salt in 100mL of distilled water at the temperature of 25 +/-5 ℃ to obtain a 1-ethyl-3-methylimidazole bromine salt solution; adding 5g of (NH) 4 ) 4 [H 6 Ni II Mo 6 O 24 ]Dissolved in 100mL of distilled water to obtain (NH) 4 ) 4 [H 6 Ni II Mo 6 O 24 ]A solution; adding the (NH) 4 ) 4 [H 6 Ni II Mo 6 O 24 ]Dropwise adding the solution into the 1-ethyl-3-methylimidazole bromine salt solution, and stirring for 1h to obtain a mixture; collecting the precipitate in the mixture, washing with water for three times, and drying under reduced pressure to constant weight to obtain a transition metal-substituted heteropoly acid-based ionic liquid flame retardant (C) 6 H 11 N 2 ) 4 [H 6 Ni II Mo 6 O 24 ]。
The Fourier infrared spectrum result of the flame retardant shows that the cation is 1-ethyl-3-methylimidazole cation and the anion is [ H ] 6 Ni II Mo 6 O 24 ] 4- 。
Example 2
Dissolving 4.3g of tetraheptyl ammonium bromide in 20mL of dichloromethane at the temperature of 25 +/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; adding 5g of Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dissolving in 100mL of distilled water to obtain Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]A solution; mixing the Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dropwise adding the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with a rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain transition metal-substituted heteropoly acid group ionic liquid flame retardant (C) 28 H 60 N) 10 [H 4 Cu II 4 P 2 W 18 O 70 ]。
The Fourier infrared spectrum of the flame retardant is shown in figure 1, and the result shows that the cation is tetraheptyl quaternary ammonium cation and the anion is [ H ] 4 Cu II 4 P 2 W 18 O 70 ] 10- 。
Example 3
Dissolving 3.0g of tetrabutyl phosphonium bromide in 20mL of dichloromethane at 25 +/-5 ℃ to obtain tetrabutyl phosphonium bromide solution; adding 5g of Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dissolving in 100mL of distilled water to obtain Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]A solution; mixing the Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dropwise adding the solution into the tetrabutyl phosphonium bromide solution, and stirring for 0.5h to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with a rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain transition metal-substituted heteropoly acid group ionic liquid flame retardant (C) 16 H 36 P) 10 [H 4 Cu II 4 P 2 W 18 O 70 ]。
The Fourier infrared spectrum of the flame retardant is shown in figure 1, and the result shows that the cation is tetrabutyl quaternary phosphoniumThe cation and the anion are [ H ] 4 Cu II 4 P 2 W 18 O 70 ] 10- 。
Example 4
Dissolving 4.4g of tetraheptyl ammonium bromide in 20mL of dichloromethane at the temperature of 25 +/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; adding 5g of Na 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]Dissolving in 100mL of distilled water to obtain Na 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]A solution; adding the Na 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]Dropwise adding the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with a rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain transition metal-substituted heteropoly acid group ionic liquid flame retardant (C) 28 H 60 N) 10 [H 4 Ni II 4 P 2 W 18 O 70 ]。
The Fourier infrared spectrum of the flame retardant is shown in figure 1, and the result shows that the cation is tetraheptyl quaternary ammonium cation and the anion is [ H ] 4 Ni II 4 P 2 W 18 O 70 ] 10- 。
Example 5
Dissolving 3.5g of 1-ethyl-3-methylimidazole bromine salt in 100mL of distilled water at 25 +/-5 ℃ to obtain a 1-ethyl-3-methylimidazole bromine salt solution; adding 5g of (NH) 4 ) 4 [H 6 Cu II Mo 6 O 24 ]Dissolved in 100mL of distilled water to obtain (NH) 4 ) 4 [H 6 Cu II Mo 6 O 24 ]A solution; adding the (NH) 4 ) 4 [H 6 Cu II Mo 6 O 24 ]Dropwise adding the solution into the 1-ethyl-3-methylimidazole bromine salt solution, and stirring for 1h to obtain a mixture; collecting the precipitate and water in the mixtureWashing for three times, drying under reduced pressure to constant weight to obtain a transition metal substituted heteropoly acid radical ionic liquid flame retardant (C) 6 H 11 N 2 ) 4 [H 6 Cu II Mo 6 O 24 ]。
The Fourier infrared spectrum result of the flame retardant shows that the cation is 1-ethyl-3-methylimidazole cation and the anion is [ H ] 6 Cu II Mo 6 O 24 ] 4- 。
Example 6
Dissolving 3.5g of tetrapentylammonium bromide in 20mL of dichloromethane at 25 +/-5 ℃ to obtain a tetrapentylammonium bromide solution; mixing 5g of K 10 [H 4 Co II 4 P 2 W 18 O 70 ]Dissolving in 100mL distilled water to obtain K 10 [H 4 Co II 4 P 2 W 18 O 70 ]A solution; the K is added 10 [H 4 Co II 4 P 2 W 18 O 70 ]Dropwise adding the solution into the tetrapentyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with a rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain transition metal-substituted heteropoly acid group ionic liquid flame retardant (C) 20 H 44 N) 10 [H 4 Co II 4 P 2 W 18 O 70 ]。
The Fourier infrared spectrum result of the flame retardant shows that the cation is tetrapentyl quaternary ammonium cation and the anion is [ H ] 4 Co II 4 P 2 W 18 O 70 ] 10- 。
Example 7
Dissolving 4.5g of tetraheptyl ammonium bromide in 20mL of dichloromethane at the temperature of 25 +/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; mixing 5g of K 10 [H 4 Mn II 4 P 2 W 18 O 70 ]Dissolving in 100mL distilled water to obtain K 10 [H 4 Mn II 4 P 2 W 18 O 70 ]A solution; the K is added 10 [H 4 Mn II 4 P 2 W 18 O 70 ]Dropwise adding the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; standing, collecting organic phase in the mixture, evaporating dichloromethane at 30 deg.C under reduced pressure with a rotary evaporator, washing with water for three times, washing with diethyl ether for three times, and drying under reduced pressure to constant weight to obtain transition metal-substituted heteropoly acid group ionic liquid flame retardant (C) 28 H 60 N) 10 [H 4 Mn II 4 P 2 W 18 O 70 ]。
The Fourier infrared spectrum result of the flame retardant shows that the cation is tetraheptyl quaternary ammonium cation and the anion is [ H ] 4 Mn II 4 P 2 W 18 O 70 ] 10- 。
Application comparative example 1
100g of epoxy resin adhesive (D.E.R.332) and 5g of heteropoly acid-based ionic liquid described in comparative example 1 are taken and mixed for 1 hour at 90 ℃ to obtain uniform mixed liquid; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain a curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the epoxy resin is 25.3 percent according to ISO 4589-2 and ISO 5660 standards, and the peak heat release rate p-HRR is 964.4kW/m 2 (ii) a The limiting oxygen index LOI of the composite material is 27.9 percent, and the peak heat release rate p-HRR is 965.8kW/m 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
Application example 1
100g of epoxy resin adhesive (D.E.R.332) and 5g of flame retardant described in example 2 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 37.8 percent and the peak heat release rate p-HRR is 753.2kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The thermal weight loss curve of the composite material is shown in fig. 2, and the result shows that the composite material has no obvious decomposition (the thermal weight loss is less than 5 wt.%) below 300 ℃.
Application example 2
100g of epoxy resin adhesive (D.E.R.332) and 5g of flame retardant described in example 4 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 31.7 percent and the peak heat release rate p-HRR is 714.4kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The thermal weight loss curve of the composite material is shown in fig. 2, and the result shows that the composite material has no obvious decomposition (the thermal weight loss is less than 5 wt.%) below 300 ℃.
Application example 3
100g of epoxy resin adhesive (D.E.R.332) and 1.3g of the flame retardant described in example 2 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain a curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 31.4 percent and the peak heat release rate p-HRR is 788.2kW/m according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 4
100g of epoxy resin adhesive (D.E.R.332) and 6.7g of flame retardant described in example 2 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and (3) putting the loaded mould into an oven for curing, namely pre-curing at 100 ℃ for 2h, curing at 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 42.9 percent and the peak heat release rate p-HRR is 886.2kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 5
100g of epoxy resin adhesive (D.E.R.332) and 9.6g of flame retardant described in example 4 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and (3) putting the loaded mould into an oven for curing, namely pre-curing at 100 ℃ for 2h, curing at 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 29.6 percent and the peak heat release rate p-HRR is 962.6kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 6
100g of epoxy resin adhesive (D.E.R.332) and 5g of the flame retardant described in example 1 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; uniformly mixing and stirring the mixed solution and the curing solution, decompressing to remove bubbles in the material, and pouring the material into a preheated (preheating temperature is 50 ℃) mold; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 30.1 percent and the peak heat release rate p-HRR is 606.1kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
In the composite material, the embodiment 1 is uniformly dispersed in the epoxy resin, and the system compatibility is good.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 7
100g of epoxy resin adhesive (D.E.R.332) and 5g of the flame retardant described in example 3 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain a curing liquid; uniformly mixing and stirring the mixed solution and the curing solution, decompressing to remove bubbles in the material, and pouring the material into a preheated (preheating temperature is 50 ℃) mold; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 32.2 percent and the peak heat release rate p-HRR is 864.3kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
Before the composite material is cured, the epoxy resin is partially miscible with the embodiment 3, and the composite material is uniformly dispersed and has good system compatibility.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 8
100g of epoxy resin adhesive (D.E.R.332) and 5g of flame retardant described in example 5 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; uniformly mixing and stirring the mixed solution and the curing solution, decompressing to remove bubbles in the material, and pouring the material into a preheated (preheating temperature is 50 ℃) mold; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 31.8 percent and the peak heat release rate p-HRR is 604.4kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The composite material of example 5 has uniform dispersion and good system compatibility.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 9
100g of epoxy resin adhesive (D.E.R.332) and 5g of the flame retardant described in example 6 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The composite material has a limiting oxygen index LOI of 32.6% and a peak heat release rate p-HRR of 834.3kW/m measured according to ISO 4589-2, ISO 5660 standard 2 。
Before the composite material is cured, the epoxy resin is partially soluble with the embodiment 6, and the composite material is uniformly dispersed and has good system compatibility.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 10
100g of epoxy resin adhesive (D.E.R.332) and 5g of the flame retardant described in example 7 were mixed and stirred at 90 ℃ for 1 hour to obtain a uniform mixed solution; heating 27.9g of diaminodiphenylmethane curing agent to 90 ℃ until the diaminodiphenylmethane curing agent is completely dissolved to obtain curing liquid; mixing and stirring the mixed solution and the curing solution uniformly, decompressing to remove bubbles in the material, and pouring the material into a mold preheated to 50 ℃; and putting the loaded mould into an oven for curing, firstly pre-curing at 100 ℃ for 2h, then curing at 150 ℃ for 2h, and then naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limit oxygen index LOI of the composite material is 36.3 percent and the peak heat release rate p-HRR is 867.2kW/m as tested according to ISO 4589-2 and ISO 5660 standards 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The results of the thermogravimetric curves of the composites show that the composites do not significantly decompose below 300 ℃ (thermogravimetric less than 5 wt.%).
Application example 11
6g of the flame retardant described in example 6 is dissolved in 20mL of acetone, the cellulose cloth strip is placed in the acetone solution of the flame retardant for dipping for 10min, and the cloth strip is taken out and naturally dried to obtain the flame-retardant modified cellulose composite material.
The limit oxygen index LOI of the cellulose cloth strip is 16.9 percent according to the ISO 4589-2 standard, and the limit oxygen index LOI of the cellulose composite material is 22.5 percent.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.

Claims (10)

1. A transition metal substituted heteropoly acid group ionic liquid flame retardant is characterized in that: the flame retardant consists of organic cations and transition metal substituted polyoxometalate anions, wherein the organic cations are imidazole organic cations, pyridine organic cations, quaternary ammonium organic cations or quaternary phosphonium organic cations; the transition metal is iron, cobalt, nickel, copper, zinc or manganese.
2. The transition metal-substituted heteropoly acid-based ionic liquid flame retardant of claim 1, wherein: the organic cation is a 1-ethyl-3-methylimidazole cation, a 1-butyl-3-methylimidazole cation, a 1-hexyl-3-methylimidazole cation, a 1-octyl-3-methylimidazole cation, a 1-dodecyl-3-methylimidazole cation, an N-ethylpyridine cation, an N-butylpyridine cation, an N-hexylpyridine cation, an N-octylpyridine cation, a tetrabutylquaternary ammonium cation, a tetrapentyl quaternary ammonium cation, a tetraheptyl quaternary ammonium cation, a tetraoctyl quaternary ammonium cation, a trioctylmethyl quaternary ammonium cation, a dodecyltrimethyl quaternary ammonium cation, a tributylethyl quaternary phosphonium cation, a tributylhexyl quaternary phosphonium cation or a tetrabutylquaternary phosphonium cation.
3. The transition metal-substituted heteropoly acid-based ionic liquid flame retardant of claim 1, wherein: the transition metal-substituted polyoxometalate anion is [ Mn IV Mo 9 O 32 ] 6- 、[Ni IV Mo 9 O 32 ] 6- 、[H 6 Co III Mo 6 O 24 ] 3- 、[H 6 Fe II Mo 6 O 24 ] 4- 、[H 6 Ni II Mo 6 O 24 ] 4- 、[H 6 Cu II Mo 6 O 24 ] 4- 、[H 6 Zn II Mo 6 O 24 ] 4- 、[H 6 Ni II W 6 O 24 ] 4- 、[H 6 Mn II W 6 O 24 ] 4- 、[H 4 Co II 4 P 2 W 18 O 70 ] 10- 、[H 4 Cu II 4 P 2 W 18 O 70 ] 10- 、[H 4 Zn II 4 P 2 W 18 O 70 ] 10- 、[H 4 Ni II 4 P 2 W 18 O 70 ] 10- Or [ H ] 4 Mn II 4 P 2 W 18 O 70 ] 10- 。
4. The transition metal-substituted heteropoly acid-based ionic liquid flame retardant of claim 1, wherein: the organic cation is a 1-ethyl-3-methylimidazole cation, a tetrapentyl quaternary ammonium cation, a tetraheptyl quaternary ammonium cation or a tetrabutyl quaternary phosphonium cation; the transition metal substituted polyoxometalate anion is [ H ] 6 Ni II Mo 6 O 24 ] 4- 、[H 4 Ni II 4 P 2 W 18 O 70 ] 10- 、[H 4 Mn II 4 P 2 W 18 O 70 ] 10- 、[H 6 Cu II Mo 6 O 24 ] 4- 、[H 4 Cu II 4 P 2 W 18 O 70 ] 10- Or [ H ] 4 Co II 4 P 2 W 18 O 70 ] 10- 。
5. A method for preparing the transition metal substituted heteropoly acid based ionic liquid flame retardant of any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
(1) Dissolving organic cation halogen salt in a solvent to obtain an organic cation salt solution; when the organic cation halogen salt is water-soluble, the solvent is water with the purity of deionized water or higher; when the organic cationic halogen salt is water insoluble, the solvent is dichloromethane;
(2) Mixing a transition metal substituted heteropoly acid aqueous solution with the organic cation salt solution, and stirring for more than 0.5h to fully exchange anions and cations to obtain a mixture;
(3) When the solvent in the step (1) is water, collecting the precipitate in the mixture in the step (2), and washing and drying to obtain the transition metal substituted heteropoly acid based ionic liquid flame retardant; and (2) when the solvent in the step (1) is dichloromethane, collecting an organic phase in the mixture in the step (2), removing the dichloromethane, washing and drying to obtain the transition metal substituted heteropoly acid based ionic liquid flame retardant.
6. The method for preparing a transition metal substituted heteropoly acid based ionic liquid flame retardant as claimed in claim 5, wherein: in the step (2), the transition metal substituted heteropoly acid aqueous solution and the organic cation salt solution are mixed according to the stoichiometric ratio of anion-cation exchange.
7. Use of a transition metal-substituted heteropolyacid-based ionic liquid flame retardant according to any one of claims 1 to 4, characterized in that: the flame retardant is used for carrying out flame-retardant modification on a high-molecular polymer.
8. The use of the transition metal-substituted heteropoly acid-based ionic liquid flame retardant according to claim 7, wherein: the flame retardant is used as an additive flame retardant for carrying out flame retardant modification on epoxy resin, or is used as a surface coating for carrying out flame retardant modification on cellulose.
9. The use of a transition metal-substituted heteropoly acid-based ionic liquid flame retardant according to claim 8, wherein: when the epoxy resin is flame retardant modified: firstly, adding the flame retardant into epoxy resin adhesive, stirring and mixing uniformly to obtain a mixed solution, and heating and melting an epoxy resin curing agent to obtain a curing solution; then uniformly stirring and mixing the mixed solution and the curing solution, removing bubbles, and curing to obtain the flame-retardant modified epoxy resin composite material; wherein the addition amount of the flame retardant is 0.5-10% by taking the total mass of the flame retardant, the epoxy resin and the epoxy resin curing agent as 100%;
when flame retardant modification is performed on cellulose: dispersing the flame retardant in acetone, stirring and dispersing uniformly to obtain a dispersion liquid, wherein the concentration of the flame retardant in the dispersion liquid is 100-300 mg/mL, soaking the cellulose cloth strip in the dispersion liquid for 5-10 min, and drying after the soaking is finished to obtain the flame-retardant modified cellulose composite material.
10. The use of a transition metal-substituted heteropoly acid-based ionic liquid flame retardant according to claim 9, wherein: when the epoxy resin is subjected to flame retardant modification, the addition amount of the flame retardant is 1-7%.
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