CN112225945A - Magnesium hydroxide-microcapsule flame retardant and preparation method thereof - Google Patents
Magnesium hydroxide-microcapsule flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of magnesium hydroxide flame retardants, and discloses a magnesium hydroxide-microcapsule flame retardant which comprises a surface modification layer, a DOPO layer and a polymerization layer, wherein the surface modification layer, the DOPO layer and the polymerization layer are sequentially coated outside a flame-retardant core; magnesium hydroxide and a multi-component flame retardant are subjected to in-situ construction to form a magnesium hydroxide-microcapsule flame retardant with a multilayer structure by a chemical method, on one hand, the surface grafting of the magnesium hydroxide forms ethylene magnesium hydroxide particles with reaction activity; on the other hand, an intermediate DOPO with better flame-retardant efficiency is selected, and a layer of DOPO is wrapped on the surface of the magnesium hydroxide through the characteristic that a P-H bond has activity on double bonds; then coating a thin polymer layer on the surface of the magnesium hydroxide-DOPO capsule through in-situ polymerization; is used for solving the problems of poor flame retardant effect, high addition amount and poor compatibility with other materials of the magnesium hydroxide flame retardant.
Description
Technical Field
The invention relates to the technical field of magnesium hydroxide flame retardants, and more particularly relates to a magnesium hydroxide-microcapsule flame retardant and a preparation method thereof.
Background
The organic polymer material has the characteristics of chain network structure, easy processing and forming property, multiple functionality, low cost, high cost performance and the like, and is applied to the wide fields of electronic information, industry, agriculture, transportation, aerospace and the like. However, most organic polymer materials are flammable or combustible, and pose a great threat to the safety of human life and property when applied to provide rich and colorful material conditions and benefits for human beings. In actual use, the organic polymer material is particularly easy to burn under the action of open fire, heat and the like, releases a large amount of heat, strong smog or toxic gas and even can cause people to be poisoned or suffocated to die.
In recent years, halogen flame retardants generate toxic smoke when heated, and pose a great threat to the safety of human life and property, and therefore some of these products have been restricted or banned by the regulations such as RoHS directive and stockholm convention. With the annual improvement of the environmental protection standard and the improvement of the environmental legislation in China, the demand of the environmental protection type green flame retardant is increased continuously, and the market demand of the green inorganic flame retardant such as magnesium hydroxide and the like is expected to be increased remarkably. Magnesium hydroxide has received increasing attention in recent years as a typical inorganic flame retardant due to its acid-free, low cost and good smoke suppression properties. Since magnesium hydroxide functions to generate oxidation residue by endothermic decomposition and release of water exceeding 300 ℃, it can prevent heat from being fed back into the interior of the flame material, showing the advantage of complete environmental protection. However, there are some problems with magnesium hydroxide in practical commercial applications, the greatest disadvantage being relatively low flame retardant efficiency, requiring high addition levels; however, too high an amount of addition leads to poor system compatibility, difficulty in dispersing the inorganic flame retardant in the polymer matrix, and thus significant deterioration of processability.
Chinese patent 'an ultrafine modified magnesium hydroxide flame retardant and a preparation method thereof' discloses an ultrafine modified magnesium hydroxide flame retardant, which comprises the following preparation raw materials in parts by weight: 30-50 parts of alkaline precipitator, 20-30 parts of magnesium salt, 6-8 parts of activating agent, 8-12 parts of surfactant and 1-3 parts of dispersing agent. The superfine modified magnesium hydroxide flame retardant prepared by the invention has the advantages of higher flame retardant efficiency, good compatibility with materials, higher cost performance, environmental protection and no toxicity.
In the invention, the compatibility of the magnesium hydroxide flame retardant and materials is effectively solved, but the superfine modified magnesium hydroxide flame retardant has micron-sized particles and a common flame retardant effect, and the addition amount of the prepared superfine modified magnesium hydroxide is still high when the superfine modified magnesium hydroxide is compounded with other materials to prepare the flame retardant material.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art and provides a magnesium hydroxide-microcapsule flame retardant which is used for solving the problems of poor flame retardant effect, high addition amount and poor compatibility with other materials of the magnesium hydroxide flame retardant.
Another object of the present invention is to provide a method for preparing a magnesium hydroxide-microencapsulated flame retardant.
The invention adopts the technical scheme that the magnesium hydroxide-microcapsule flame retardant comprises a flame-retardant core, and a surface modification layer, a DOPO layer and a polymerization layer which are sequentially coated outside the flame-retardant core. The magnesium hydroxide-microcapsule flame retardant takes magnesium hydroxide particles as a flame retardant core, and a plurality of layers of different shells are coated on the outer layer, so that the defect of low efficiency of the single-component flame retardant can be effectively overcome, and the dispersibility and the compatibility with high polymer materials can be improved.
Further, the magnesium hydroxide is of a lamellar structure, and the particle size is 300-400 nm. The magnesium hydroxide is of a lamellar structure, the particle size of the magnesium hydroxide is in a nanometer level, the compactness among particles is better, and the flame retardant effect is also better.
Further, the surface modification layer is formed by vinylating the surface of the magnesium hydroxide particles.
Further, the polymerization layer is a high molecular layer formed by in-situ polymerization of the active monomer on the DOPO layer.
The preparation method of the magnesium hydroxide-microcapsule flame retardant comprises the steps of vinylating the surface of the nano-lamellar magnesium hydroxide particles, reacting the nano-lamellar magnesium hydroxide particles with DOPO, and finally coating the nano-lamellar magnesium hydroxide particles by in-situ polymerization to form the magnesium hydroxide-microcapsule flame retardant.
Further, the method comprises the following steps:
preparation of S1 nano-lamellar magnesium hydroxide particles: mixing anhydrous magnesium chloride, a composite dispersant A and distilled water, strongly stirring uniformly at a low temperature, slowly dropwise adding 20% ammonia water, continuously and slowly dropwise adding a sodium hydroxide solution with the mass concentration of 8%, uniformly stirring, heating to continue reacting, cooling to room temperature after the reaction is finished, filtering, washing and drying in vacuum;
preparation of S2 DOPO-coated magnesium hydroxide particles: adding a modifier and distilled water into the magnesium hydroxide prepared by S1, adjusting the pH value to acidity by using glacial acetic acid, uniformly stirring, heating for reaction, adding a DOPO mixed solution dissolved in absolute ethyl alcohol in advance after the reaction is completed, heating, refluxing at constant temperature, performing centrifugal separation, washing with absolute ethyl alcohol and distilled water for multiple times in sequence, and freeze-drying to constant weight;
preparation of S3 multilayer coated magnesium hydroxide particles: adding the composite dispersant B and distilled water into the DOPO-coated magnesium hydroxide particles prepared by S2, stirring and dispersing, adding the prepolymer, stirring and dispersing uniformly, cooling to room temperature, adjusting the pH value to acidity with acetic acid, heating, slowly heating, keeping the temperature, stirring and reacting, cooling, adjusting the pH value to alkalinity with dilute sodium carbonate, washing and drying.
Further, the method comprises the following steps:
preparation of S1 nano-lamellar magnesium hydroxide particles: mixing 30-60 parts of anhydrous magnesium chloride, 1-5 parts of composite dispersant A and 50-150 parts of distilled water, maintaining the temperature at 5-10 ℃, intensively stirring and mixing for 30-60 minutes, slowly dropwise adding 10-25 parts of 20% ammonia water in percentage by mass, continuously and slowly dropwise adding 20-65 parts of sodium hydroxide solution with the mass concentration of 8%, uniformly stirring for 30-60 minutes, heating to 35-45 ℃, continuously reacting for 120-150 minutes, cooling to room temperature, filtering, washing, and vacuum drying at 70-90 ℃;
preparation of S2 DOPO-coated magnesium hydroxide particles: weighing 10-60 parts of magnesium hydroxide prepared in S1, adding 3-25 parts of modifier and 100-300 ml of distilled water, adjusting the pH value to 3-4 with glacial acetic acid, stirring for 10-30 minutes, and heating to 60-70 ℃ for reaction for 120-150 minutes; then, adding a mixed solution of 5-20 parts of DOPO pre-dissolved in 50-100 ml of absolute ethyl alcohol, heating to 85-95 ℃, refluxing at constant temperature for 3-6 hours, then performing centrifugal separation, washing with absolute ethyl alcohol and distilled water for three times in sequence, and freeze-drying to constant weight;
preparation of S3 multilayer coated magnesium hydroxide particles: weighing 30-90 parts of DOPO-coated magnesium hydroxide particles prepared in S2, adding 0.15-1.0 part of composite dispersant B and 100-500 parts of distilled water, dispersing in a reactor, adding 40-100 parts of prepolymer, stirring and dispersing at 60-75 ℃, cooling to room temperature after 30-45 minutes, adjusting the pH value to 4-5.5 with acetic acid, heating, slowly heating to 60-80 ℃, keeping the temperature, stirring for 120-150 minutes, and cooling; and (4) adjusting the pH value to 8-9 by using dilute sodium carbonate, filtering, washing and drying.
Further, the composite dispersant A is two of sodium dodecyl sulfate, polyvinyl alcohol, ethylene glycol, fructose, glucose, cetyl trimethyl ammonium bromide and gelatin.
Preferably, the composite powder A is prepared from sodium dodecyl sulfate and polyvinyl alcohol in a mass ratio of 1: 0.5-3, or is prepared from sodium dodecyl sulfate and gelatin in a mass ratio of 1: 0.5-3, or is prepared from fructose and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 0.5-3, or is prepared from glucose and gelatin in a mass ratio of 1: 0.5-3, or is prepared from glycol and fructose in a mass ratio of 1: 0.5-3. The single dispersant is easy to separate out in a salt solution with stronger polarity, the dispersion effect is not good, the compounding and dispersion effects according to the method are good, and the particle size distribution of the prepared magnesium hydroxide lamellar structure particles is narrow.
Further, the modifier is one of a silane coupling agent, monounsaturated fatty acid and polyunsaturated fatty acid.
Further, the silane coupling agent is one of 3-triethoxysilyl-1-propylamine, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
Further, the monounsaturated fatty acid is oleic acid; the polyunsaturated fatty acid is one of linolenic acid, arachidonic acid, docosahexaenoic acid, docosapentadilute acid, and docosapentadilute acid.
Further, the composite dispersant B is two of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, an emulsifier OP-10 and stearic acid.
Preferably, the composite dispersant B is prepared from polyethylene glycol and stearic acid in a mass ratio of 1: 1-2, or sodium dodecyl benzene sulfonate and an emulsifier OP-10 in a mass ratio of 1: 1-2, or sodium dodecyl sulfate and an emulsifier OP-10 in a mass ratio of 1: 1-2, or polyethylene glycol and sodium dodecyl sulfate in a mass ratio of 1: 1-2.
Further, the prepolymer is one of melamine-formaldehyde resin prepolymer, urea-formaldehyde prepolymer and phenol-formaldehyde prepolymer.
The technical scheme of the invention provides an integrated construction idea, magnesium hydroxide and a multi-component flame retardant are subjected to in-situ construction by a chemical method to obtain the magnesium hydroxide-microcapsule flame retardant with a multilayer structure, so that the defect of low efficiency of the single-component flame retardant is overcome, and the deterioration degree of the multi-component flame retardant on resin performance is reduced. On one hand, the surface grafting of the magnesium hydroxide forms ethylene magnesium hydroxide particles with reaction activity; on the other hand, an intermediate DOPO with better flame-retardant efficiency is selected, and a layer of DOPO is wrapped on the surface of the magnesium hydroxide through the characteristic that a P-H bond has activity on double bonds; then a thin polymer layer is coated on the surface of the magnesium hydroxide-DOPO capsule through in-situ polymerization, so that the dispersity and the compatibility with polymer materials are improved, the P-Si flame-retardant effect is formed, the flame-retardant efficiency of the magnesium hydroxide flame retardant is improved, and the magnesium hydroxide-DOPO capsule has good applicability.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the magnesium hydroxide flame retardant prepared by the method, the surface of the magnesium hydroxide flame retardant is vinylated by using a modifier, and the DOPO structure containing P-H bonds and surface-vinylated magnesium hydroxide C ═ C are subjected to chemical reaction under the stirring effect, so that the magnesium hydroxide-microcapsule flame retardant with the P-Si synergistic effect is synthesized, and the defect of low flame retardant efficiency of magnesium hydroxide is effectively overcome.
(2) The DOPO modified magnesium hydroxide is coated by adopting an in-situ polymerization method, so that the effects of good compatibility and uniform dispersion between the magnesium hydroxide and the matrix of the high polymer material can be realized.
Detailed Description
The examples of the present invention are provided for illustrative purposes only and are not to be construed as limiting the invention.
Example 1
A preparation method of a magnesium hydroxide-microcapsule flame retardant comprises the following steps:
s1: weighing 30 parts of anhydrous magnesium chloride, 2.5 parts of sodium dodecyl sulfate, 1.5 parts of polyvinyl alcohol and 100 parts of distilled water, maintaining the temperature at 10 ℃, intensively stirring and mixing for 30 minutes, slowly dropwise adding 15 parts of ammonia water with the mass percentage of 20%, continuously and slowly dropwise adding 40 parts of sodium hydroxide solution with the mass concentration of 8%, and uniformly stirring for 30 minutes. The temperature is increased to 40 ℃ and the reaction is continued for 120 minutes, and the reaction is cooled to room temperature. Then filtering, washing and vacuum drying at 70 ℃ to obtain the magnesium hydroxide powder.
S2: 30 parts of magnesium hydroxide, 3 parts of gamma-aminopropyltriethoxysilane, 100 ml of distilled water and glacial acetic acid, adjusting the pH value to 3.5, stirring for 10 minutes, and heating to 65 ℃ for reaction for 120 minutes; then, 2 parts of DOPO are weighed, dissolved in 60 ml of absolute ethyl alcohol in advance, added into the solution, refluxed for 4 hours at the constant temperature of 85 ℃, centrifuged, washed by the absolute ethyl alcohol and distilled water for three times in sequence, and freeze-dried to constant weight.
S3, weighing a proper amount of 30 parts of DOPO coated magnesium hydroxide powder, 0.1 part of sodium dodecyl sulfate, 0.05 part of emulsifier (OP-10) and 100 parts of distilled water, dispersing in a reactor, adding 40 parts of melamine-formaldehyde resin prepolymer solution, stirring and dispersing at 60 ℃, cooling to room temperature after 30 minutes, adjusting the pH value to 4 with acetic acid, heating, slowly heating to 60 ℃, keeping the temperature, stirring for 120 minutes, and cooling; and (4) adjusting the pH value to 8.5 by using dilute sodium carbonate, filtering, washing and drying to obtain the multilayer coated magnesium hydroxide flame retardant.
Example 2
A preparation method of a magnesium hydroxide-microcapsule flame retardant comprises the following steps:
s1: weighing 35 parts of anhydrous magnesium chloride, 2.25 parts of sodium dodecyl sulfate, 2.25 parts of gelatin and 120 parts of distilled water, maintaining the temperature at 8 ℃, intensively stirring and mixing for 30 minutes, slowly dropwise adding 20 parts of 20% ammonia water in mass percent, continuously and slowly dropwise adding 45 parts of 8% sodium hydroxide solution in mass percent, and uniformly stirring for 30 minutes. The temperature is increased to 45 ℃ and the reaction is continued for 120 minutes, and the reaction is cooled to room temperature. Then filtering, washing and vacuum drying at 80 ℃ to obtain the magnesium hydroxide powder.
S2: 40 parts of magnesium hydroxide, 5.5 parts of oleic acid, 150 ml of distilled water and glacial acetic acid are used for adjusting the pH value to 4.0, stirring is carried out for 30 minutes, and the temperature is increased to 70 ℃ for reaction for 120 minutes; then, 15 parts of DOPO are weighed, dissolved in 70 ml of absolute ethyl alcohol in advance, added into the solution, refluxed for 4 hours at the constant temperature of 95 ℃, centrifuged, washed by the absolute ethyl alcohol and distilled water for three times in sequence, and freeze-dried to constant weight.
S3, weighing a proper amount of 50 parts of DOPO-coated magnesium hydroxide powder, 0.2 part of sodium dodecyl sulfate, 0.2 part of emulsifier (OP-10) and 200 parts of distilled water, dispersing in a reactor, adding 60 parts of melamine-formaldehyde resin prepolymer solution, stirring and dispersing at 70 ℃, cooling to room temperature after 30 minutes, adjusting the pH value to 4.5 with acetic acid, heating, slowly heating to 65 ℃, keeping the temperature, stirring for 120 minutes, and cooling; and (4) adjusting the pH value to 8.5 by using dilute sodium carbonate, filtering, washing and drying to obtain the multilayer coated magnesium hydroxide flame retardant.
Example 3
A preparation method of a magnesium hydroxide-microcapsule flame retardant comprises the following steps:
s1: weighing 60 parts of anhydrous magnesium chloride, 2 parts of fructose, 3 parts of hexadecyl trimethyl ammonium bromide and 150 parts of distilled water, maintaining the temperature at 7 ℃, intensively stirring and mixing for 60 minutes, slowly dropwise adding 25 parts of 20% ammonia water in percentage by mass, continuously and slowly dropwise adding 65 parts of sodium hydroxide solution with the mass concentration of 8%, and uniformly stirring for 60 minutes. The temperature is increased to 45 ℃ and the reaction is continued for 150 minutes, and the reaction is cooled to room temperature. Then filtering, washing and vacuum drying at 80 ℃ to obtain the magnesium hydroxide powder.
S2: regulating the pH value to 4 by using 60 parts of magnesium hydroxide, 15 parts of linolenic acid, 300 ml of distilled water and glacial acetic acid, stirring for 30 minutes, and heating to 70 ℃ for reaction for 150 minutes; then, 15 parts of DOPO are weighed, dissolved in 100 ml of absolute ethyl alcohol in advance, added into the solution, refluxed for 6 hours at the constant temperature of 95 ℃, centrifuged, washed by the absolute ethyl alcohol and distilled water for three times in sequence, and freeze-dried to constant weight.
S3, weighing a proper amount of 90 parts of DOPO coated magnesium hydroxide powder, 0.4 part of polyethylene glycol, 0.6 part of sodium dodecyl sulfate and 500 parts of distilled water, dispersing in a reactor, adding 100 parts of melamine-formaldehyde resin prepolymer solution, stirring and dispersing at 60 ℃, cooling to room temperature after 30 minutes, adjusting the pH value to 5.0 with acetic acid, heating, slowly heating to 60 ℃, keeping the temperature, stirring for 150 minutes, and cooling; and (4) adjusting the pH value to 9 by using dilute sodium carbonate, filtering, washing and drying to obtain the multilayer coated magnesium hydroxide flame retardant.
Example 4
A preparation method of a magnesium hydroxide-microcapsule flame retardant comprises the following steps:
s1: weighing 50 parts of anhydrous magnesium chloride, 1 part of glucose, 3 parts of gelatin and 50 parts of distilled water, maintaining the temperature at 5 ℃, intensively stirring and mixing for 42 minutes, slowly dropwise adding 10 parts of ammonia water with the mass percentage of 20%, continuously and slowly dropwise adding 20 parts of sodium hydroxide solution with the mass concentration of 8%, and uniformly stirring for 60 minutes. The temperature is increased to 35 ℃ to continue the reaction for 120 minutes, and the reaction is cooled to room temperature. Then filtering, washing and vacuum drying at 80 ℃ to obtain the magnesium hydroxide powder.
S2: 10 parts of magnesium hydroxide, 25 parts of docosapentaenoic acid, dissolved in ethanol solution and 100 ml of distilled water, adjusting the pH value to 3 by glacial acetic acid, stirring for 15 minutes, and heating to 60 ℃ for reaction for 120 minutes; then, 20 parts of DOPO is weighed, dissolved in 50 ml of absolute ethyl alcohol in advance, added into the solution, refluxed for 3 hours at the constant temperature of 90 ℃, centrifuged, washed by the absolute ethyl alcohol and distilled water for three times in sequence, and freeze-dried to constant weight.
S3, weighing a proper amount of 70 parts of DOPO coated magnesium hydroxide powder, 0.3 part of polyethylene glycol, 0.45 part of stearic acid and 300 parts of distilled water, dispersing in a reactor, adding 80 parts of melamine-formaldehyde resin prepolymer solution, stirring and dispersing at 75 ℃, cooling to room temperature after 30 minutes, adjusting the pH value to 5.0 with acetic acid, heating, slowly heating to 80 ℃, keeping the temperature, stirring for 120 minutes, and cooling; and (4) adjusting the pH value to 8 by using dilute sodium carbonate, filtering, washing and drying to obtain the multilayer coated magnesium hydroxide flame retardant.
Comparative example 1
The difference from example 1 is that commercially available flame retardant grade magnesium hydroxide was used directly and the S2 and S3 steps were identical to example 1.
Comparative example 2
The difference from example 1 is that 2.5 parts of sodium lauryl sulfate of example 1 were also replaced with polyvinyl alcohol, and other conditions were the same as in example 1.
Comparative example 3
The difference from example 1 is that 0.05 part of emulsifier OP-10 of example 1 is replaced by sodium lauryl sulfate and the other conditions are the same as in example 1.
The flame retardants obtained in examples 1 to 4 and comparative examples 1 to 3 were added to HMEVAC8-7 manufactured by DuPont (DuPont, USA), 150 manufactured by Mitsui Chemicals (Mitsui Chemical, Japan), and VA910 ethylene-vinyl acetate copolymer (EVA) manufactured by Korea Lotte Chemical (Korea Letian Chemical) at a ratio of 15.0 wt%, respectively, and prepared into a plurality of test specimens, and the corresponding indices were measured according to the following measurement methods:
(1) test for flammability Limit Oxygen Index (LOI) measured according to ASTM D2863, bars obtained by pressing from a pressure Forming machine and having dimensions of 100X 6.5X 3mm3The data are shown in table 1:
| oxygen index/% | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | EVA |
| HMEVAC8-7 | 30.4 | 31.65 | 34.71 | 36.14 | 22.0 | 26.7 | 24.3 | 21.8 |
| 150 | 29.4 | 33.44 | 31.54 | 32.23 | 21.4 | 25.1 | 23.9 | 22.1 |
| VA910 | 27.8 | 35.85 | 32.80 | 31.87 | 21.5 | 24.8 | 23.4 | 21.7 |
TABLE 1 Ethylene Vinyl Acetate (EVA) test limiting oxygen index
From table 1, it can be found that the flame retardants of examples 1 to 4 are used in methyl vinyl silicone rubber raw materials of three types of HMEVAC8-7, 150 and VA910, the oxygen index of the flame retardants of examples 1 to 4 is significantly higher than that of the flame retardants of comparative examples 1 to 3, the flame retardants of examples 1 to 4 can better realize flame retardance on ethylene-vinyl acetate copolymers (EVA) of three types of HMEVAC8-7, 150 and VA910, and the inorganic magnesium hydroxide is uniformly dispersed in an ethylene-vinyl acetate copolymer (EVA) substrate and has good compatibility; particularly, the flame retardant of example 3 has excellent flame retardant effect on HMEVAC8-7 and the flame retardant of example 2 on VA 910.
(2) The vertical burning test (UL-94) is rated according to the American national standard UL-94, and the sample size is 130 x 13 x 3mm3The cotton wool is vertically placed, absorbent cotton is placed under the cotton wool, 10 seconds of flame is applied twice respectively to record the combustion phenomenon, and the combustion evaluation is carried out on the material. Each set of samples was run in parallel five times to ensure reliability and reproducibility of the data. The data are shown in table 2:
TABLE 2 Ethylene Vinyl Acetate (EVA) test horizontal burn Rate
| Horizontal combustion rate | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | EVA |
| HMEVAC8-7 | HB | HB | HB | HB | HB75 | HB75 | HB75 | HB75 |
| 150 | HB | HB | HB | HB | HB75 | HB75 | HB75 | HB75 |
| VA910 | HB | HB | HB | HB | HB75 | HB75 | HB75 | HB75 |
TABLE 3 Ethylene Vinyl Acetate (EVA) testing vertical burn rate
| Vertical combustion rate | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | EVA |
| HMEVAC8-7 | V-1 | V-1 | V-0 | V-0 | V-2 | V-1 | V-2 | V-2 |
| 150 | V-1 | V-1 | V-1 | V-1 | V-2 | V-2 | V-2 | V-2 |
| VA910 | V-1 | V-0 | V-1 | V-1 | V-2 | V-2 | V-2 | V-2 |
TABLE 4 ethylene vinyl acetate copolymer (EVA) test melt drops
| Molten drop | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | EVA |
| HMEVAC8-7 | Without dripping | Without dripping | Without dripping | Without dripping | Is very violent | Without dripping | Is very violent | Is very violent |
| 150 | Without dripping | Without dripping | Without dripping | Without dripping | Is very violent | Is very violent | Is very violent | Is very violent |
| VA910 | Without dripping | Without dripping | Without dripping | Without dripping | Is very violent | Is very violent | Is very violent | Is very violent |
As can be found from tables 2-4, the flame retardants of examples 1-4 are used in ethylene-vinyl acetate copolymer (EVA) raw materials of HMEVAC8-7, 150 and VA910, and the flame retardant effect of the flame retardants is obviously better than that of the flame retardants of comparative examples 1-3 in ethylene-vinyl acetate copolymer (EVA) raw materials of HMEVAC8-7, 150 and VA 910. The flame retardants of embodiments 1-4 can better realize flame retardance on ethylene-vinyl acetate copolymers (EVA) of HMEVAC8-7, 150 and VA910, and the flame retardance efficiency of inorganic magnesium hydroxide on ethylene-vinyl acetate copolymer (EVA) substrates is better; the flame retardant of example 3 has excellent flame retardant effect on HMEVAC8-7 and the flame retardant of example 2 on VA 910.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. The magnesium hydroxide-microcapsule flame retardant is characterized by comprising a flame-retardant core made of magnesium hydroxide, and a surface modification layer, a DOPO layer and a polymerization layer which are sequentially coated outside the flame-retardant core.
2. The magnesium hydroxide-microcapsule flame retardant according to claim 1, wherein the magnesium hydroxide has a lamellar structure and a particle size of 300 to 400 nm; or the surface modification layer is formed by vinylation on the surface of the magnesium hydroxide particles; or the polymerization layer is a high molecular layer formed by in-situ polymerization of the active monomer on the DOPO layer.
3. The method for preparing a magnesium hydroxide-microcapsule flame retardant according to claim 1 or 2, wherein the magnesium hydroxide-microcapsule flame retardant is formed by vinylating the surface of the nanosheet layer magnesium hydroxide particles, reacting the surface with DOPO, and finally coating the magnesium hydroxide-microcapsule flame retardant by in-situ polymerization.
4. The method for preparing a magnesium hydroxide-microcapsule flame retardant according to claim 3, characterized by comprising the steps of:
preparation of S1 nano-lamellar magnesium hydroxide particles: uniformly mixing anhydrous magnesium chloride, a composite dispersant A and distilled water, slowly dripping 20 mass percent of ammonia water and 8 mass percent of sodium hydroxide solution in sequence, uniformly stirring, heating for continuous reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying in vacuum;
preparation of S2 DOPO-coated magnesium hydroxide particles: adding a modifier and distilled water into the nanosheet layer magnesium hydroxide particles prepared in S1, adjusting the pH value to acidity, adding a DOPO mixed solution dissolved in absolute ethyl alcohol in advance after complete heating reaction, heating, refluxing at constant temperature, performing centrifugal separation again, washing with absolute ethyl alcohol and distilled water for multiple times in sequence, and freeze-drying to constant weight;
preparation of S3 multilayer coated magnesium hydroxide flame retardant: adding the composite dispersant B and distilled water into the DOPO-coated magnesium hydroxide particles prepared by S2, stirring and dispersing, adding the prepolymer, stirring and dispersing uniformly, cooling to room temperature, adjusting the pH value to acidity, heating, slowly heating, keeping the temperature, stirring and reacting, cooling, adjusting the pH value to alkalinity, washing and drying.
5. The method for preparing magnesium hydroxide-microcapsule flame retardant according to claim 4, wherein the composite dispersant A is two of sodium dodecyl sulfate, polyvinyl alcohol, ethylene glycol, fructose, glucose, cetyl trimethyl ammonium bromide and gelatin.
6. The preparation method of the magnesium hydroxide-microcapsule flame retardant according to claim 5, wherein the composite dispersant A is composed of sodium dodecyl sulfate and polyvinyl alcohol in a mass ratio of 1: 0.5-3, sodium dodecyl sulfate and gelatin in a mass ratio of 1: 0.5-3, fructose and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 0.5-3, glucose and gelatin in a mass ratio of 1: 0.5-3, or ethylene glycol and fructose in a mass ratio of 1: 0.5-3.
7. The method for preparing magnesium hydroxide-microcapsule flame retardant according to claim 4, wherein the modifier is one of silane coupling agent, monounsaturated fatty acid and polyunsaturated fatty acid.
8. The method for preparing magnesium hydroxide-microcapsule flame retardant according to claim 4, wherein the composite dispersant B is two of polyethylene glycol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, emulsifier OP-10 and stearic acid.
9. The preparation method of the magnesium hydroxide-microcapsule flame retardant according to claim 4, wherein the composite dispersant B is polyethylene glycol and stearic acid in a mass ratio of 1: 1-2, sodium dodecyl benzene sulfonate and emulsifier OP-10 in a mass ratio of 1: 1-2, sodium dodecyl sulfate and emulsifier OP-10 in a mass ratio of 1: 1-2, or polyethylene glycol and sodium dodecyl sulfate in a mass ratio of 1: 1-2.
10. The method of claim 4, wherein the prepolymer is one of melamine-formaldehyde resin prepolymer, urea-formaldehyde prepolymer, and phenol-formaldehyde prepolymer.
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