CN107163289B - Layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant and preparation method thereof - Google Patents
Layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant and preparation method thereof Download PDFInfo
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- CN107163289B CN107163289B CN201710470714.2A CN201710470714A CN107163289B CN 107163289 B CN107163289 B CN 107163289B CN 201710470714 A CN201710470714 A CN 201710470714A CN 107163289 B CN107163289 B CN 107163289B
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Abstract
The invention belongs to the technical field of flame-retardant smoke inhibitors, and particularly relates to a graphene flame-retardant smoke inhibitor modified by layered double hydroxide-molybdate ions and a preparation method thereof; the method is obtained by loading LDH on the surface of graphene and then intercalating molybdate ions between LDH layers; the flame-retardant smoke suppressant provided by the invention can improve the flame retardance and smoke suppression performance of the polymer and can also improve the physical and mechanical properties of the polymer.
Description
Technical Field
The invention belongs to the technical field of flame-retardant smoke inhibitors, and particularly relates to a layered double hydroxide-molybdate ion modified graphene flame-retardant smoke inhibitor and a preparation method thereof.
Background
Graphene is a two-dimensional honeycomb-shaped planar structure formed by close packing of single-layer carbon atoms, and has received extensive attention and research from researchers in many fields in recent years due to its large surface area and excellent electrical, optical, mechanical and thermal properties. In the text "graphene/polymer composite material research progress" in 2016 (volume 44, 2) of plastic industry, China journal states that the flame retardant property of some polymers can be improved by adding graphene. In fact, the improvement of the flame retardant performance of the graphene composite polymer material is mainly due to the physical barrier effect of the graphene sheet layer with large specific surface area in the polymer combustion process, which can inhibit the transfer of energy and substances between a gas phase and a condensed phase in the polymer combustion process, thereby protecting the underlying substrate from further combustion. However, due to strong van der waals force between graphene sheets, graphene is easily agglomerated, so that the dispersibility of graphene in a polymer is poor, the flame retardant efficiency is reduced, a large addition amount is required to achieve a good flame retardant effect, and the increase of the addition amount often causes the reduction of the physical and mechanical properties of the polymer, thereby limiting the application of graphene in flame retardant of the polymer.
Disclosure of Invention
The invention aims to provide a layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant, which can improve the flame retardance and smoke suppression performance of a polymer and improve the physical and mechanical properties of the polymer.
In order to achieve the purpose, the invention adopts the technical scheme that: a layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant is obtained by loading LDH on the surface of graphene and then intercalating molybdate ions between LDH layers.
Another object of the present invention is to provide a method for preparing the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant described above, which comprises the following steps:
(1) dispersing and dissolving divalent metal salt and trivalent metal salt into deionized water to obtain a uniform salt solution;
(2) dispersing graphene into an alkaline solution, adding a salt solution, adjusting the pH of the solution to 8-11 by using a precipitator, stirring and reacting for 12-36h at the temperature of 40-80 ℃, then adding a reducing agent, reacting to obtain a mixture, and performing centrifugal washing treatment on the mixture to obtain RGO-LDH;
(3) dispersing RGO-LDH into deionized water, adding molybdate solution, adjusting the pH of the solution to 4-5, and treating by an ion exchange method to obtain molybdate ion intercalation modified RGO-LDH.
The beneficial effect that above-mentioned technical scheme produced lies in: the graphene is simultaneously modified by the layered double hydroxide and molybdate ions, the prepared molybdate ion intercalation modified RGO-LDH can be uniformly dispersed in a polymer matrix during application, no obvious agglomeration phenomenon exists, and the flame-retardant smoke suppressant can effectively improve the flame-retardant smoke suppressant performance of the polymer.
Detailed Description
The technical scheme disclosed by the invention is further explained by 3 embodiments as follows:
example 1: preparation and application of flame-retardant smoke suppressant
Preparation of flame-retardant smoke suppressant
(1) 7.5g of Al (NO) are weighed out3)3·9H2O and 25.6g Mg (NO)3)2·6H2O, dispersing and dissolving in 150ml of deionized water to obtain a uniform salt solution;
(2) weighing 0.64g of graphene, dispersing into 150ml of alkaline solution (the concentration of NaOH is 0.20M, the concentration of Na2CO3 is 0.05M), and carrying out ultrasonic treatment for 30 minutes to obtain uniformly dispersed graphene dispersion liquid;
dropwise adding the salt solution prepared in the step (1) into the graphene dispersion liquid, and rapidly stirring while dropwise adding; (time, rate)
Adjusting pH of the mixture to 8 with 0.2M NaOH solution, stirring the mixture at 40 deg.C for 36 hr, and adding 0.75ml N2H2·H2Heating to 100 ℃, reacting for 3 hours at constant temperature, washing the product for 2 times by using deionized water and absolute ethyl alcohol in sequence, centrifuging the washed product each time, and freeze-drying to obtain RGO-LDH;
(3) weighing 12g of (NH)4)6Mo7O24·4H2Dissolving O in 100ml of deionized water to obtain an ammonium heptamolybdate aqueous solution;
weighing 10g RGO-LDH, dispersing into 500ml deionized water, carrying out ultrasonic treatment for 5 minutes, adding an ammonium heptamolybdate aqueous solution, adjusting the pH value of the solution to 4, stirring and reacting for 3 hours at 60 ℃, sequentially washing for 3 times by using the deionized water and absolute ethyl alcohol, centrifuging products after washing each time, and carrying out freeze drying to obtain RGO-LDH/Mo.
Second, application of flame-retardant smoke suppressant
The flame-retardant smoke suppressant prepared in example 1 was added into the polyurethane elastomer in an amount of 2 wt% by mass, and then placed in an internal mixer at a temperature of 170 ℃ and a rotation speed of 45r/min for mixing for 6min, and the mixture was discharged and fed to a press vulcanizer for sample preparation, so as to obtain a flame-retardant polyurethane elastomer sample 1.
Example 2: preparation and application of flame-retardant smoke suppressant
Preparation of flame-retardant smoke suppressant
(1) Weighing 37.5g of Al (NO3) 3.9H 2O and 59.4g of Zn (NO3) 2.6H 2O, and dispersing and dissolving in 500ml of deionized water to obtain a uniform salt solution;
(2) 1.2g of graphene was weighed out and dispersed in 150ml of an alkaline solution (NaOH concentration 0.20M, Na)2CO3Concentration of 0.05M), and performing ultrasonic treatment for 20 minutes to obtain uniformly dispersed graphene dispersion liquid;
dropwise adding the salt solution prepared in the step (1) into the graphene dispersion liquid, and rapidly stirring while dropwise adding; (time, rate)
Adjusting pH of the mixture to 11 with 0.5M NaOH solution, stirring the mixture at 60 deg.C for 24 hr, and adding 1.5ml N2H2·H2Heating to 110 ℃, reacting for 2 hours at constant temperature, washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, centrifuging the washed product each time, and freeze-drying to obtain RGO-LDH;
(3) weighing 11g of (NH)4)6Mo7O24·4H2Dissolving O in 100ml of deionized water to obtain an ammonium heptamolybdate aqueous solution;
weighing 10g RGO-LDH, dispersing into 500ml deionized water, carrying out ultrasonic treatment for 10 minutes, adding an ammonium heptamolybdate aqueous solution, adjusting the pH value of the solution to 5, stirring and reacting for 2 hours at 70 ℃, sequentially washing for 3 times by using the deionized water and absolute ethyl alcohol, centrifuging products after washing each time, and carrying out freeze drying to obtain RGO-LDH/Mo.
Second, application of flame-retardant smoke suppressant
And (2) putting the flame-retardant smoke inhibitor prepared in the example 2 into a polyurethane elastomer according to the mass percent of 2 wt%, then placing the polyurethane elastomer into an internal mixer at the temperature of 170 ℃ and the rotating speed of 45r/min for mixing for 6min, discharging, and feeding the mixture to a flat vulcanizing machine for sample preparation to obtain a flame-retardant polyurethane elastomer sample 2.
Example 3: preparation and application of flame-retardant smoke suppressant
Preparation of flame-retardant smoke suppressant
(1) 14.0625g of Al (NO) was weighed out3)3·9H2O and 54.5625g of Co (NO)3)2·6H2O, dispersing and dissolving in 150ml of deionized water to obtain a uniform salt solution;
(2) weighing 0.82g of graphene, dispersing into 150ml of alkaline solution (the concentration of NaOH is 0.20M, the concentration of Na2CO3 is 0.05M), and carrying out ultrasonic treatment for 30 minutes to obtain uniformly dispersed graphene dispersion liquid;
dropwise adding the salt solution prepared in the step (1) into the graphene dispersion liquid, and rapidly stirring while dropwise adding; (time, rate)
Adjusting pH of the mixture to 10 with 0.4M NaOH solution, stirring the mixture at 80 deg.C for 12 hr, and adding 0.75ml N2H2·H2Heating to 120 ℃, reacting for 1h at constant temperature, washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, centrifuging the washed product each time, and freeze-drying to obtain RGO-LDH;
(3) 13g of Na were weighed2MoO4·2H2Dissolving O in 100ml of deionized water to obtain a sodium molybdate aqueous solution;
weighing 10g RGO-LDH, dispersing into 500ml deionized water, carrying out ultrasonic treatment for 5 minutes, adding a sodium molybdate aqueous solution, adjusting the pH value of the solution to 5, stirring and reacting for 1 hour at 80 ℃, sequentially washing for 3 times by using the deionized water and absolute ethyl alcohol, centrifuging products after washing each time, and carrying out freeze drying to obtain RGO-LDH/Mo.
Second, application of flame-retardant smoke suppressant
The flame-retardant smoke suppressant prepared in the example 3 is added into the ethylene-vinyl acetate copolymer according to the mass percent of 2 wt%, then the mixture is placed into an internal mixer with the temperature of 110 ℃ and the rotating speed of 45r/min for mixing for 10min, and the discharged material is sent to a flat vulcanizing machine for sample preparation, so that the flame-retardant ethylene-vinyl acetate copolymer sample 3 is obtained.
Performance test:
the flame retardant samples 1 to 3 prepared above were respectively tested for flame retardant performance, smoke suppression performance and physical and mechanical properties, and the test standards and test results are shown in tables 1 to 3 below. Wherein the percent decrease in the maximum heat release rate and the percent decrease in the maximum smoke density reported in tables 1 and 2 are the percent decrease compared to the polyurethane elastomer/ethylene vinyl acetate copolymer without the flame retardant.
It is apparent from tables 1 and 2 that the maximum heat release rate and the maximum smoke density of samples 1 and 2 can be reduced by more than 60% and 50% by using the flame retardant smoke suppressant disclosed in the present invention, as compared with the polyurethane elastomer without the flame retardant. Compared with ethylene-vinyl acetate copolymer without flame retardant, the flame-retardant smoke suppressant disclosed by the invention can reduce the maximum heat release rate of a sample by 54.9% and reduce the maximum smoke density by 51.8%.
As is evident from the data in Table 3, the tensile strength and elongation at break of samples 1-3 are significantly improved by using the flame retardant and smoke suppressant of the present invention as compared to polyurethane elastomers and ethylene-vinyl acetate copolymers without flame retardants.
Table 1 flame retardant testing of samples
TABLE 2 Smoke suppression Performance test of the samples
Mechanical testing of the samples in Table 3
The data analysis shows that the flame-retardant smoke suppressant disclosed by the invention can effectively improve the flame retardance, smoke suppression and mechanical properties of the polyurethane elastomer and the ethylene-vinyl acetate copolymer in the practical application process.
Claims (7)
1. A layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant is characterized in that LDH is loaded on the surface of graphene, and molybdate ions are intercalated between LDH layers to obtain the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant;
the preparation method of the flame-retardant smoke suppressant comprises the following steps:
(1) dispersing and dissolving divalent metal salt and trivalent metal salt into deionized water to obtain salt solution;
(2) dispersing graphene into an alkaline solution, adding a salt solution, adjusting the pH of the solution to 8-11 by using a precipitator, stirring and reacting for 12-36h at the temperature of 40-80 ℃, then adding a reducing agent to obtain a mixture, and treating the mixture by a coprecipitation method to obtain RGO-LDH;
(3) dispersing RGO-LDH into deionized water, adding molybdate solution, adjusting the pH of the solution to 4-5, and treating by an ion exchange method to obtain molybdate ion intercalation modified RGO-LDH;
the coprecipitation method treatment in the step (2) comprises the following steps: reacting for 1-3h at the temperature of 100-120 ℃, washing for 2-3 times by sequentially adopting deionized water and absolute ethyl alcohol, centrifuging products after washing each time, and freeze-drying;
the ion exchange treatment in the step (3) comprises the following steps: stirring and reacting for 1-3h at 60-80 deg.C, sequentially washing with deionized water and anhydrous ethanol for 3 times, centrifuging the product after each washing, and freeze drying.
2. The layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant of claim 1, wherein said LDH is selected from one of MgAl-LDH, ZnAl-LDH, CoAl-LDH, and said molybdate ion is Mo7O24 6-Or MoO4 2-。
3. The method for preparing the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant according to claim 1, wherein the total metal ion concentration in the deionized water in the step (1) is 0.6-1.5M, and the divalent metal ion M in the deionized waterⅡAnd a trivalent metal salt MⅢIn a molar ratio of 2-5: 1.
4. The layered double hydroxide-molybdate ion of claim 1The preparation method of the modified graphene flame-retardant smoke suppressant is characterized in that in the step (2), the alkaline solution is NaOH and Na2CO3The concentration of NaOH in the mixed solution is 0.20M and Na2CO3The concentration of (3) was 0.05M.
5. The preparation method of the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant according to claim 1, wherein the addition amount of the graphene in the step (2) is 4-8g/L, and the volume ratio of the graphene dispersion liquid to the salt solution is 0.3-1: 1.
6. The method for preparing the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant according to claim 1, wherein the precipitating agent in the step (2) is sodium hydroxide, the reducing agent is hydrazine hydrate, and the addition amount of the hydrazine hydrate is 0.2-0.25 vt%.
7. The method for preparing the layered double hydroxide-molybdate ion modified graphene flame-retardant smoke suppressant according to claim 1, wherein the molybdate in the step (3) is an aqueous ammonium molybdate tetrahydrate solution or an aqueous sodium molybdate dihydrate solution; trivalent metal ion M in the RGO-LDHⅢThe mol ratio of/Mo is 1: 4-6.
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| CN107987316A (en) * | 2017-11-22 | 2018-05-04 | 宁国市飞扬新材料科技有限公司 | A kind of anti-flaming smoke-inhibiting agent, its preparation method and PVC flame-retardant smoke inhibitions material prepared therefrom |
| CN109880254B (en) * | 2019-02-19 | 2021-04-20 | 山东盛瑞科华新材料有限公司 | Halogen-free flame retardant, preparation method thereof and cable bridge containing halogen-free flame retardant |
| CN110669246B (en) * | 2019-09-05 | 2022-05-20 | 中南林业科技大学 | Phosphomolybdic acid intercalation hydrotalcite-like light foam heat-insulating material and preparation method thereof |
| CN114957963A (en) * | 2022-06-11 | 2022-08-30 | 彭宗健 | Preparation method of modified thermoplastic polyurethane resin |
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