CN115160144B - Transition metal substituted heteropolyacid-based ionic liquid flame retardant, preparation method and application thereof - Google Patents

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

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CN115160144B
CN115160144B CN202210684913.4A CN202210684913A CN115160144B CN 115160144 B CN115160144 B CN 115160144B CN 202210684913 A CN202210684913 A CN 202210684913A CN 115160144 B CN115160144 B CN 115160144B
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flame retardant
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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 heteropolyacid based ionic liquid flame retardant, a preparation method and application thereof, and belongs 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 carrying out anion-cation exchange in an aqueous phase or an organic phase. The transition metal substituted heteropolyacid is used as a catalytic flame-retardant active center of the flame retardant, so that the flame retardant performance of the flame-retardant modified composite material can be effectively improved.

Description

Transition metal substituted heteropolyacid-based ionic liquid flame retardant, preparation method and application thereof
Technical Field
The invention relates to a transition metal substituted heteropolyacid based ionic liquid flame retardant, a preparation method and application thereof, and belongs to the technical field of flame retardant materials.
Background
The resin polymer such as epoxy resin has excellent physical properties, chemical properties, adhesive properties, corrosion resistance and the like, so that the resin polymer is widely applied to various fields of national society life and national defense and military construction such as electronics, electrical and mechanical manufacturing, chemical corrosion resistance, aerospace and the like; however, most of 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 usually accompanied by release and fusion dripping of a large amount of toxic smoke, so that the fire safety hidden danger of products in the use process is extremely high, and the personal and property safety of the national is seriously threatened. With the continuous rising of new technologies, the requirements of industries such as electronics, electrics, aerospace and the like on resin materials are increasing, and meanwhile, the requirements on heat resistance and flame retardance of products are also increasing, for example, 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 polymer materials close to the components have certain flame retardance, and the flammability of resin polymers greatly limits the application of the resin polymers in the fields of electronic and electric industries and composite materials with certain requirements on flame retardance. 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 guaranteeing the national economy and social safety, and has very important strategic requirement background in various fields of electronics and electricity, information communication, mechanical manufacturing, aerospace and the like.
At present, common challenges faced by the development of flame retardant modification of resin polymers at home and abroad are: (1) The compatibility of the flame retardant and the resin matrix is poor, so that the irreversible negative influence on the processability, mechanical properties and the like of the material is extremely easy to cause, or the phenomena of flame retardant migration and precipitation, phase separation and the like occur along with the time; (2) Safety problems of flame retardants most high-efficiency flame retardants represented by halogen compounds are extremely harmful to human bodies and the environment, and although the european union has issued related instruction regulations to restrict the use of these flame retardants with 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 performance of a matrix, has high flame retardant efficiency and is environment-friendly is a great difficulty to be solved in the field of flame retardant modification of epoxy resin materials.
The Polyoxometalates (POMs) are metal-oxygen cluster compounds formed by co-angle, co-edge or coplanar bridging of oxygen atoms and high-valence front transition metal atoms such as molybdenum, tungsten, vanadium, niobium, tantalum and the like, and have diversified and controllable structures and redox activities. The preparation of POMs-based ionic liquids (POM-ILs) by modulating the type of POMs counter cations, such as the introduction of ionic liquids (ionic liquids) cations, can be used in the field of flame retardant materials, such as chinese patent applications 201510981817.6 and 201310315174.2, however, the POM-ILs disclosed in the above-mentioned patent applications are used as flame retardant synergists in combination with other conventional flame retardants. The inventor researches and discovers that under the condition that the flame retardant or flame retardant groups such as phosphorus, nitrogen, silicon and the like are not compounded or modified, the effect of directly serving as the flame retardant for carrying out flame retardant modification on a high polymer material is extremely poor, and how to obtain POM-ILs which can be directly used as the flame retardant is not reported in the prior art at present.
Disclosure of Invention
In view of the above, the invention aims to provide a transition metal substituted heteropolyacid-based ionic liquid flame retardant, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the transition metal substituted heteropolyacid-based 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 tetrabutyl quaternary ammonium cation, a tetrapentyl quaternary ammonium cation, a tetraheptyl quaternary ammonium cation, a tetraoctyl quaternary ammonium cation, a trioctylmethyl quaternary ammonium cation, a dodecyl trimethyl 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 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- 。
The invention discloses a preparation method of a transition metal substituted heteropolyacid based 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 higher than that of deionized water; when the organic cationic halogen salt is water insoluble, the solvent is dichloromethane;
(2) Mixing transition metal substituted heteropolyacid 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 heteropolyacid-based ionic liquid flame retardant; and (3) when the solvent in the step (1) is dichloromethane, collecting the organic phase in the mixture in the step (2), removing the dichloromethane, and washing and drying to obtain the transition metal substituted heteropolyacid-based ionic liquid flame retardant.
Preferably, in the step (2), the transition metal substituted heteropolyacid aqueous solution and the organic cation salt solution are mixed according to a stoichiometric ratio of cation-anion exchange.
The invention discloses an application of a transition metal substituted heteropolyacid based ionic liquid flame retardant, which is used for flame-retardant modification of a high-molecular polymer.
Preferably, the flame retardant is used as an additive flame retardant for flame-retardant modification of epoxy resin or used as a surface coating for flame-retardant modification of cellulose.
Preferably, when flame retardant modification is performed on an epoxy resin: firstly, adding the flame retardant into epoxy resin glue, stirring and mixing uniformly to obtain a mixed solution, and heating and dissolving an epoxy resin curing agent to obtain a curing solution; then stirring and mixing the mixed solution and the curing solution uniformly, 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 percent based on 100 percent of the total mass of the flame retardant, the epoxy resin and the epoxy resin curing agent;
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 mg/mL-300 mg/mL, immersing the cellulose cloth strip in the dispersion liquid for 5 min-10 min, and drying after the immersion 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) According to the transition metal substituted heteropolyacid-based ionic liquid flame retardant provided by the invention, the novel halogen-free, smoke-suppressing, low-toxicity and high-efficiency flame retardant is formed by compounding the organic cations and the transition metal substituted polymetallic acid anions, and the transition metal substituted heteropolyacid is used as a catalytic flame-retardant active center in the flame retardant, so that the char formation efficiency of a condensed phase of the flame-retardant modified composite material can be improved, the phenomena of inflammable or toxic smoke overflow and molten drop are inhibited, and the flame retardant performance of the composite material is effectively improved. In addition, the flame-retardant modified composite material has higher thermal stability and non-toxicity and difficult volatility, and can avoid migration and precipitation phenomena, safety and other problems in the processing or using process of the traditional flame retardant.
(2) According to the transition metal substituted heteropolyacid-based ionic liquid flame retardant provided by the invention, the catalytic effect of transition metal can be fully exerted by further optimizing the anionic skeleton structure and the element composition, and the progress of carbon forming reactions such as cyclization, aromatization, crosslinking, graphitization and the like is promoted, so that the carbon forming and flame retarding efficiency of a condensed phase 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 material 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 heteropolyacid based ionic liquid flame retardant provided by the invention can be realized by carrying out anion-cation exchange in an aqueous 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 graph showing the thermal weight loss of the flame-retardant modified epoxy resin described in application example 1-2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following comparative examples, application comparative examples and application examples:
(1) Fourier infrared spectroscopy test: instrument Bruker Tensor II, test range 500-4000cm -1 Resolution of 4cm -1 。
(2) Thermal weight loss test: the test range of the instrument Netzsch STA 449F3 Jupiter is 30-800 ℃, the temperature rising rate is 10 ℃/min, and the nitrogen atmosphere is adopted.
Comparative example 1
3.2g of tetraheptyl ammonium bromide is dissolved in 20mL of dichloromethane at 25+/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; 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 processed by 6 [P 2 W 18 O 62 ]Dripping the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting the organic phase in the mixture, evaporating the dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then sequentially washing with water for three times and diethyl ether for three times, and drying under reduced pressure to constant weight to obtain a heteropolyacid-based ionic liquid (C) 28 H 60 N) 6 [P 2 W 18 O 62 ]。
Fourier infrared spectrum results of the heteropolyacid-based ionic liquid show that the cation is tetraheptyl quaternary ammonium cation and the anion is [ P ] 2 W 18 O 62 ] 6- 。
Example 1
3.5g of 1-ethyl-3-methylimidazole bromide is dissolved in 100mL of distilled water at 25+/-5 ℃ to obtain 1-ethyl-3-methylimidazole bromide solution; 5g (NH) 4 ) 4 [H 6 Ni II Mo 6 O 24 ]Dissolved in 100mL distilled water to give (NH) 4 ) 4 [H 6 Ni II Mo 6 O 24 ]A solution; 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 precipitate in the mixture, washing with water for three times, and drying under reduced pressure to constant weight to obtain transition metal substituted heteropolyacid 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 25+/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; 5g of Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dissolving in 100mL distilled water to obtain Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]A solution; the Na is treated with 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dripping the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting an organic phase in the mixture, evaporating dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then sequentially washing with water for three times and diethyl ether for three times, and then drying under reduced pressure to constant weight to obtain the transition metal substituted heteropolyacid-based 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 of the flame retardant is tetraheptyl quaternary ammonium cation, and the anion is [ H ] 4 Cu II 4 P 2 W 18 O 70 ] 10- 。
Example 3
3.0g of tetrabutyl phosphonium bromide is dissolved in 20mL of dichloromethane at 25+/-5 ℃ to obtain tetrabutyl phosphonium bromide solution; 5g of Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dissolving in 100mL distilled water to obtain Na 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]A solution; the Na is treated with 3 K 7 [H 4 Cu II 4 P 2 W 18 O 70 ]Dripping the solution into the tetrabutyl phosphonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting an organic phase in the mixture, evaporating dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then sequentially washing with water for three times and diethyl ether for three times, and then drying under reduced pressure to constant weight to obtain the transition metal substituted heteropolyacid-based 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 phosphonium cation and the anion is [ 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 25+/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; 5g of Na 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]Dissolving in 100mL distilled water to obtain Na 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]A solution; the Na is treated with 6 K 4 [H 4 Ni II 4 P 2 W 18 O 70 ]Dripping the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting the organic phase in the mixture, evaporating the dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then washing with water for three times and diethyl ether for three times in sequenceDrying under reduced pressure to constant weight after the second time to obtain the transition metal substituted heteropolyacid based 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 of the flame retardant is tetraheptyl quaternary ammonium cation, and the anion is [ H ] 4 Ni II 4 P 2 W 18 O 70 ] 10- 。
Example 5
3.5g of 1-ethyl-3-methylimidazole bromide is dissolved in 100mL of distilled water at 25+/-5 ℃ to obtain 1-ethyl-3-methylimidazole bromide solution; 5g (NH) 4 ) 4 [H 6 Cu II Mo 6 O 24 ]Dissolved in 100mL distilled water to give (NH) 4 ) 4 [H 6 Cu II Mo 6 O 24 ]A solution; 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 precipitate in the mixture, washing with water for three times, and drying under reduced pressure to constant weight to obtain transition metal substituted heteropolyacid based 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; 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 processed by 10 [H 4 Co II 4 P 2 W 18 O 70 ]Dripping the solution into the tetrapentylammonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting an organic phase in the mixture, evaporating dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then sequentially washing with water for three times and diethyl ether for three times, and then drying under reduced pressure to constant weight to obtain the transition metal substituted heteropolyacid-based 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 tetra-amyl 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 25+/-5 ℃ to obtain a tetraheptyl ammonium bromide solution; 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 processed by 10 [H 4 Mn II 4 P 2 W 18 O 70 ]Dripping the solution into the tetraheptyl ammonium bromide solution, and stirring for 0.5h to obtain a mixture; after standing, collecting an organic phase in the mixture, evaporating dichloromethane by a rotary evaporator under reduced pressure at 30 ℃, and then sequentially washing with water for three times and diethyl ether for three times, and then drying under reduced pressure to constant weight to obtain the transition metal substituted heteropolyacid-based 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- 。
Comparative example 1 was used
Taking 100g of epoxy resin glue (D.E.R.332), 5g of heteropolyacid-based ionic liquid described in comparative example 1, and mixing and stirring at 90 ℃ for 1h to obtain a uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the epoxy resin is 25.3% measured according to ISO 4589-2 and ISO 5660 standard, and the peak heat release rate p-HRR is 964.4kW/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The limiting oxygen index LOI of the composite material is 27.9%, 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 glue (D.E.R.332) and 5g of flame retardant described in example 2 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 37.8 percent according to ISO 4589-2 and ISO 5660 standard test, and the peak heat release rate p-HRR is 753.2kW/m 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 is shown in fig. 2, and the result shows that the composite has no obvious decomposition below 300 ℃ (the thermal weight loss is less than 5 wt.%).
Application example 2
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 4 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 31.7% according to ISO 4589-2 and ISO 5660 standard test, and the peak heat release rate p-HRR is 714.4kW/m 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 is shown in fig. 2, and the result shows that the composite has no obvious decomposition below 300 ℃ (the thermal weight loss is less than 5 wt.%).
Application example 3
100g of epoxy resin glue (D.E.R.332) and 1.3g of flame retardant described in example 2 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 31.4% 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 thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 4
100g of epoxy resin glue (D.E.R.332) and 6.7g of flame retardant described in example 2 are taken and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 42.9% and the peak heat release rate p-HRR is 886.2kW/m according to ISO 4589-2 and ISO 5660 standard test 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 5
100g of epoxy resin glue (D.E.R.332) and 9.6g of flame retardant described in example 4 are taken and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 29.6 percent according to ISO 4589-2 and ISO 5660 standard test, and the peak heat release rate p-HRR is 962.6kW/m 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 6
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 1 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring the materials into a preheated (the preheating temperature is 50 ℃); and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 30.1% and the peak heat release rate p-HRR is 606.1kW/m according to ISO 4589-2 and ISO 5660 standard test 2 。
In the composite material, the example 1 is uniformly dispersed in epoxy resin, and the system compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 7
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 3 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring the materials into a preheated (the preheating temperature is 50 ℃); and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 32.2% and the peak heat release rate p-HRR is 864.3kW/m according to ISO 4589-2 and ISO 5660 standard test 2 。
The epoxy resin and the epoxy resin in the embodiment 3 are partially mutually dissolved and uniformly dispersed before the composite material is cured, and the system compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 8
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 5 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring the materials into a preheated (the preheating temperature is 50 ℃); and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 31.8 percent according to ISO 4589-2 and ISO 5660 standard test, and the peak heat release rate p-HRR is 604.4kW/m 2 。
Example 5 was uniformly dispersed in the composite material and the system compatibility was good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 9
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 6 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 32.6% and the peak heat release rate p-HRR is 834.3kW/m according to ISO 4589-2, ISO 5660 standard test 2 。
The epoxy resin and the epoxy resin in the embodiment 6 are partially mutually dissolved and uniformly dispersed before the composite material is cured, and the system compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 10
100g of epoxy resin glue (D.E.R.332) and 5g of flame retardant described in example 7 are taken, and mixed and stirred for 1h at 90 ℃ to obtain uniform mixed solution; heating 27.9g of diaminodiphenyl methane curing agent to 90 ℃ until the diaminodiphenyl methane curing agent is completely dissolved to obtain a curing liquid; mixing the mixed solution and the curing solution, stirring uniformly, decompressing, removing bubbles in the materials, and pouring into a mould preheated to 50 ℃; and (3) putting the loaded mold into an oven for curing, pre-curing for 2 hours at 100 ℃, curing for 2 hours at 150 ℃, and naturally cooling to obtain the flame-retardant modified epoxy resin composite material.
The limiting oxygen index LOI of the composite material is 36.3% and the peak heat release rate p-HRR is 867.2kW/m according to ISO 4589-2 and ISO 5660 standard test 2 。
The components of the composite material are completely mutually soluble before curing, and the compatibility is good.
The thermal weight loss curve results of the composite show that the composite has no significant decomposition below 300 ℃ (thermal weight loss less than 5 wt.%).
Application example 11
6g of the flame retardant described in the example 6 is taken and dissolved in 20mL of acetone, the cellulose cloth strip is placed in the flame retardant acetone solution for soaking for 10min, and the cloth strip is taken out and naturally dried, so that the flame-retardant modified cellulose composite material is obtained.
The limiting oxygen index LOI of the cellulose strips was tested to ISO 4589-2 and was 16.9% and the limiting oxygen index LOI of the cellulose composite was 22.5%.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.

Claims (7)

1. Transition metalBelongs to a substituted heteropolyacid-based ionic liquid flame retardant, which is characterized in that: the flame retardant consists of organic cations and transition metal substituted polyoxometalate anions, wherein the organic cations are 1-ethyl-3-methylimidazole cations, tetrapentyl quaternary ammonium cations, tetraheptyl quaternary ammonium cations or tetrabutyl quaternary phosphonium 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- 。
2. A method for preparing the transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 1, wherein the method comprises the following steps: 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 higher than that of deionized water; when the organic cationic halogen salt is water insoluble, the solvent is dichloromethane;
(2) Mixing transition metal substituted heteropolyacid 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 heteropolyacid-based ionic liquid flame retardant; and (3) when the solvent in the step (1) is dichloromethane, collecting the organic phase in the mixture in the step (2), removing the dichloromethane, and washing and drying to obtain the transition metal substituted heteropolyacid-based ionic liquid flame retardant.
3. The method for preparing the transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 2, which is characterized in that: in the step (2), the transition metal substituted heteropolyacid aqueous solution and the organic cation salt solution are mixed according to stoichiometric ratio of anion-cation exchange.
4. Use of the transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 1, characterized in that: the flame retardant is used for carrying out flame retardant modification on the high-molecular polymer.
5. The use of a transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 4, wherein: the flame retardant is used as an additive flame retardant for flame-retardant modification of epoxy resin or used as a surface coating for flame-retardant modification of cellulose.
6. The use of a transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 5, wherein: when flame retardant modification is performed on epoxy resins: firstly, adding the flame retardant into epoxy resin glue, stirring and mixing uniformly to obtain a mixed solution, and heating and dissolving an epoxy resin curing agent to obtain a curing solution; then stirring and mixing the mixed solution and the curing solution uniformly, 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 percent based on 100 percent of the total mass of the flame retardant, the epoxy resin and the epoxy resin curing agent;
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 mg/mL-300 mg/mL, immersing the cellulose cloth strip in the dispersion liquid for 5 min-10 min, and drying after the immersion is finished to obtain the flame-retardant modified cellulose composite material.
7. The use of a transition metal substituted heteropolyacid-based ionic liquid flame retardant according to claim 6, 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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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435844A (en) * 2013-07-23 2013-12-11 中国科学院宁波材料技术与工程研究所 Flame retardation catalyst and supported flame retardation catalyst composed of same
CN105879912A (en) * 2016-04-17 2016-08-24 东北师范大学 Amphiphilic cobalt-containing sandwich type heteropolyacid and application thereof
WO2019027880A1 (en) * 2017-08-02 2019-02-07 Corning Incorporated Phosphate ionic liquid-polyoxometalate-inorganic additive for low smoking zero halogen flame retardant compounds
CN114011460A (en) * 2021-11-16 2022-02-08 沈阳工业大学 Preparation method and application of titanium heteropolyacid ionic liquid catalyst
CN114225966A (en) * 2021-12-31 2022-03-25 郑州中科新兴产业技术研究院 Preparation method of layered heteropoly acid ionic liquid catalyst and method for accurately catalyzing alcoholysis of PET (polyethylene terephthalate) by using layered heteropoly acid ionic liquid catalyst
CN114985007A (en) * 2022-06-13 2022-09-02 福州大学 Transition metal doped heteropoly acid ionic liquid and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435844A (en) * 2013-07-23 2013-12-11 中国科学院宁波材料技术与工程研究所 Flame retardation catalyst and supported flame retardation catalyst composed of same
CN105879912A (en) * 2016-04-17 2016-08-24 东北师范大学 Amphiphilic cobalt-containing sandwich type heteropolyacid and application thereof
WO2019027880A1 (en) * 2017-08-02 2019-02-07 Corning Incorporated Phosphate ionic liquid-polyoxometalate-inorganic additive for low smoking zero halogen flame retardant compounds
CN114011460A (en) * 2021-11-16 2022-02-08 沈阳工业大学 Preparation method and application of titanium heteropolyacid ionic liquid catalyst
CN114225966A (en) * 2021-12-31 2022-03-25 郑州中科新兴产业技术研究院 Preparation method of layered heteropoly acid ionic liquid catalyst and method for accurately catalyzing alcoholysis of PET (polyethylene terephthalate) by using layered heteropoly acid ionic liquid catalyst
CN114985007A (en) * 2022-06-13 2022-09-02 福州大学 Transition metal doped heteropoly acid ionic liquid and preparation method and application thereof

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