CN114773681A - Cyclotriphosphazene flame retardant with microcapsule core-shell structure and preparation method thereof - Google Patents
Cyclotriphosphazene flame retardant with microcapsule core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of flame retardants, and particularly relates to a cyclotriphosphazene flame retardant with a microcapsule core-shell structure and a preparation method thereof. The flame retardant comprises a flame-retardant core material and an envelope material wrapped outside the flame-retardant core material, wherein the flame-retardant core material is hexa (4-aldehyde phenoxy) cyclotriphosphazene, and the envelope material is melamine urea-formaldehyde resin. According to the invention, the modified cyclotriphosphazene flame retardant is subjected to microcapsule coating by using in-situ polymerization reaction, and the prepared flame retardant not only has high contents of nitrogen element and phosphorus element, but also has good compatibility with a polylactic acid matrix, and the composite material has good thermal stability, excellent mechanical properties and good flame retardant effect.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a cyclotriphosphazene flame retardant with a microcapsule core-shell structure and a preparation method thereof.
Background
The polymer material is easy to process, good in performance and low in price, so that the polymer material is widely applied to the fields of traffic, buildings, electronic appliances, aerospace and the like, replaces traditional materials such as metal and other wood to a certain extent, and becomes an indispensable material in the modern society. However, most of high molecular materials are flammable and have poor combustion behavior, generate a large amount of molten drops during combustion, and generate toxic smoke, thereby bringing great threat to the safety of human life and property.
At present, flame retardant is often added into high molecular materials to carry out flame retardant modification, so that the flame retardant property of the high molecular materials is improved. The flame retardant can be classified into two main types, namely an additive flame retardant and a reactive flame retardant, according to the existence form and the use method of the flame retardant in a polymer matrix, wherein the additive flame retardant is widely used due to the advantages of simple operation, wide selectable range and the like. According to the structure of the flame retardant, the flame retardant can be divided into two categories, namely halogen flame retardant and halogen-free flame retardant, wherein most of the halogen flame retardant is high in efficiency, but generates a large amount of corrosive gas and toxic smoke during thermal decomposition, thereby causing influence on human health, and the halogen flame retardant is banned or restricted for use at home and abroad in recent years. The halogen-free flame retardant comprises a metal hydroxide series, a phosphorus series, a nitrogen series, an organic silicon series, a boron series and the like, and in recent years, the Intumescent Flame Retardant (IFR) with multiple synergistic flame retardant elements is widely concerned, wherein the IFR usually comprises three components of an acid source, a carbon source and a gas source, the carbon source is usually a polyhydroxy compound, the acid source can decompose phosphate when being heated, the phosphoric acid can well promote char formation, the gas source is a substance capable of releasing non-combustible gas when being heated, and the gas enables a carbon layer to fully expand and has a good heat and oxygen isolating effect. The cyclotriphosphazene is a novel organic phosphorus flame retardant framework material, the thermal stability is good due to a stable phosphorus-nitrogen six-membered ring conjugated structure, meanwhile, N, P element has a synergistic effect in flame retardance, but some problems exist in application, and the mechanical property of the composite material is obviously reduced due to small molecular weight and poor compatibility with a matrix, so that the wider application of the composite material is limited.
Through years of experiments and exploration, the microcapsule technology can effectively solve the defects of the flame retardant. The microcapsule technology is to coat solid, liquid or gas with natural or synthetic polymer material to form a core-shell structure or a skin-core structure with the diameter of 1-1000 μm, and the microcapsule has multiple forms such as single core, multiple core, single wall, multiple wall, etc. On one hand, the microencapsulated flame retardant firstly destroys the shell structure to release the flame retardant during combustion, and a flame retardant synergistic effect possibly exists between the core and the shell, so that the flame retardant effect is achieved; on the other hand, the shell structure of the microcapsule flame retardant has the functions of protecting the core material from external factors and improving the compatibility between the flame retardant and the matrix, thereby better playing the flame retardant function of the flame retardant and improving the influence of the flame retardant on the mechanical property of the matrix. However, the microcapsule flame retardant is still problematic for the flame retardance of polymers: whether a coating layer formed on the surface of the flame retardant core material by the shell material is uniform, flat and compact can influence the release of the flame retardant of the core material in the flame retardant process, and further influence the flame retardant effect.
Disclosure of Invention
Aiming at the defects and problems of the existing flame retardant, the invention provides a cyclotriphosphazene flame retardant with a microcapsule core-shell structure and a preparation method thereof.
The scheme adopted by the invention for solving the technical problem is as follows: the cyclotriphosphazene flame retardant with the microcapsule core-shell structure comprises a flame-retardant core material and a shell material wrapped outside the flame-retardant core material, wherein the flame-retardant core material is hexa (4-aldehyde phenoxy) cyclotriphosphazene, and the shell material is melamine urea-formaldehyde resin.
The particle size of the hexa (4-aldehyde phenoxy) cyclotriphosphazene is less than 10 micrometers.
A preparation method of a cyclotriphosphazene flame retardant with a microcapsule core-shell structure comprises the following steps:
step one, preparing a flame-retardant core material: sequentially adding an acid-binding agent, p-hydroxybenzaldehyde and an organic solvent into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, and stirring and reacting for 1h at room temperature; then, 150ml of organic solution in which hexachlorocyclotriphosphazene is dissolved is dropwise added into the solution, the temperature is raised to 65 ℃, stirring and reflux reaction are carried out for 24 hours, then the solution is kept stand, cooled and filtered, and filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing, washing and drying the obtained crystal to obtain a white acicular solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene; wherein the molar ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is 1: 7.4, the molar ratio of the p-hydroxybenzaldehyde to the hexachlorocyclotriphosphazene is 1: 7.2;
step two, preparing a prepolymer mixture: adding melamine, urea, formaldehyde solution and deionized water into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, adding alkaline solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1h, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea;
and step three, crushing the hexa (4-aldehyde phenoxy) cyclotriphosphazene, respectively adding hexa (4-aldehyde phenoxy) cyclotriphosphazene powder, a prepolymer solution and a surfactant solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, adjusting the pH value to 5.5-6, heating to 70 ℃, stirring for reaction for 3 hours, diluting, filtering and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
In the preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure, the acid-binding agent is inorganic base or organic base without active hydrogen, wherein the inorganic base is one or more of potassium carbonate, sodium carbonate or sodium hydroxide, and the organic base without active hydrogen is pyridine or triethylamine.
In the preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure, the organic solvent used in the first step is one or more of acetone, tetrahydrofuran and N, N-dimethylformamide.
In the preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure, the molar ratio of the melamine to the urea to the formaldehyde solution in the step two is 1: 2: 6 or 2: 1: 6.
in the preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure, the addition amount of HAPCP in the step three is 0.005 mol.
The invention has the beneficial effects that:
according to the invention, the modified cyclotriphosphazene flame retardant is subjected to microcapsule coating by using an in-situ polymerization reaction, so that the compatibility between flame retardant particles and a matrix material can be improved.
The coating layer formed on the surface of the flame-retardant core material by the shell material of the flame retardant prepared by the invention is uniform, flat and compact, thereby being beneficial to the release of the core material flame retardant in the flame-retardant process and improving the flame-retardant effect.
The preparation method disclosed by the invention is simple in preparation process, easy to operate, low in cost and high in yield, and the prepared flame retardant has high content of nitrogen and phosphorus elements, is good in thermal stability, has good compatibility with a polylactic acid matrix, and is good in thermal stability, mechanical property and flame retardant effect.
Drawings
FIG. 1 is an FTIR spectrum of a cyclotriphosphazene-based flame retardant (HAPCP) in the preparation process of the present invention.
FIG. 2 is a nuclear magnetic spectrum of a cyclic triphosphazene flame retardant (HAPCP) in the preparation process of the invention.
FIG. 3 is a scanning electron microscope image of a cyclotriphosphazene flame retardant (MHAPCP) with a microcapsule core-shell structure prepared by the invention.
FIG. 4 is a graph showing TG and DTG spectra of a cyclotriphosphazene-based flame retardant (MHAPCP) having a microcapsule core-shell structure prepared by the present invention.
FIG. 5 is a graph of TG and DTG of a flame retardant with microcapsule core-shell structure (MHAPCP) and PLA blended material prepared by the invention.
FIG. 6 is a graph showing the change of elongation at break of a flame retardant (MHAPCP) with a microcapsule core-shell structure blended with PLA prepared by the invention.
FIG. 7 is a graph of the change of the notched impact strength of a flame retardant (MHAPCP) and PLA blended material with a microcapsule core-shell structure prepared by the invention.
FIG. 8 is a scanning electron microscope image of a flame retardant (MHAPCP) and PLA blended material with a microcapsule core-shell structure prepared by the invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1: the embodiment provides a cyclotriphosphazene flame retardant with a microcapsule core-shell structure, and the preparation method comprises the following steps:
step one, 20.45g (0.148 mol) of K was sequentially added to a 500ml three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer2CO317.6g (0.144 mol) of p-hydroxybenzaldehyde and 200ml of THF, and reacting for 1h at room temperature with stirring; then 150ml THF dissolved with 6.95g (0.02 mol) hexachlorocyclotriphosphazene is dripped in, after dripping is finished, the temperature is raised to 65 ℃, stirring reflux reaction is carried out for 24 hours, then the solution is kept stand, cooled and filtered, and the filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing with ethyl acetate, washing the obtained crystal, and drying to obtain white acicular solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene (HAPCP), with the yield of 96.7%; grinding in a freezing grinder until the particle size is less than 10 microns, sieving with a 100-mesh sieve, and placing in a dryer for later use.
Step two, adding 1.26g of melamine, 1.2g of urea and 5.68g of formaldehyde solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, wherein the molar ratio of the melamine to the urea to the formaldehyde solution is 1: 2: 6 and deionized water, adding 10% sodium bicarbonate solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1h, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea.
And step three, adding 4.3g (0.005 mol) of HAPCP powder prepared in the step one and all prepolymer solutions prepared in the step two into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, adding a proper amount of sodium dodecyl sulfate solution, adjusting the pH to 5.5-6 by using 5% potassium hydrogen phthalate solution, heating to 70 ℃, stirring for reaction for 3 hours, diluting by using a large amount of deionized water after the reaction is finished to reduce the viscosity and the filtration resistance, filtering the diluent, washing a filter cake, and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
Example 2: the embodiment provides a cyclotriphosphazene flame retardant with a microcapsule core-shell structure, and a preparation method of the cyclotriphosphazene flame retardant comprises the following steps:
step one, 20.45g (0.148 mol) of K was sequentially added to a 500ml three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer2CO317.6g (0.144 mol) of p-hydroxybenzaldehyde and 200ml of DMF, and stirring for reaction at room temperature for 1 hour; then 150ml of DMF in which 6.95g (0.02 mol) of hexachlorocyclotriphosphazene is dissolved is dripped, the temperature is raised to 65 ℃, the mixture is stirred and refluxed for reaction for 24 hours after dripping, then the solution is kept stand, cooled and filtered, and the filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing with ethyl acetate, washing and drying the obtained crystal to obtain white needle-like solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene (HAPCP), wherein the yield is 85.9%; grinding in a freezing grinder until the particle size is less than 10 microns, sieving with a 100-mesh sieve, and placing in a dryer for later use.
Step two, adding 1.26g of melamine, 1.2g of urea and 5.68g of formaldehyde solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, wherein the molar ratio of the melamine to the urea to the formaldehyde solution is 1: 2: 6 and deionized water, adding 10% sodium bicarbonate solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1h, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea.
And step three, adding 4.3g (0.005 mol) of HAPCP powder prepared in the step one and all prepolymer solutions prepared in the step two into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, adding a proper amount of sodium dodecyl sulfate solution, adjusting the pH to 5.5-6 by using 5% potassium hydrogen phthalate solution, heating to 70 ℃, stirring for reaction for 3 hours, diluting by using a large amount of deionized water after the reaction is finished to reduce the viscosity and the filtration resistance, filtering the diluent, washing a filter cake, and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
Example 3: the embodiment provides a cyclotriphosphazene flame retardant with a microcapsule core-shell structure, and a preparation method of the cyclotriphosphazene flame retardant comprises the following steps:
step one, 20.45g (0.148 mol) K is added into a 500ml three-neck flask which is provided with a thermometer, a condenser and a magnetic stirring bar in sequence2CO317.6g (0.144 mol) of p-hydroxybenzaldehyde and 200ml of DMF, and stirring for reaction at room temperature for 1 hour; then 150ml THF dissolved with 6.95g (0.02 mol) hexachlorocyclotriphosphazene is dripped in, after dripping is finished, the temperature is raised to 65 ℃, stirring reflux reaction is carried out for 24 hours, then the solution is kept stand, cooled and filtered, and the filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing with anhydrous ethanol, washing and drying the obtained crystal to obtain white flocculent solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene (HAPCP), wherein the yield is 90.4%; grinding in a freezing grinder until the particle size is less than 10 microns, sieving with a 100-mesh sieve, and placing in a dryer for later use.
Step two, adding 5.0448g of melamine, 1.2g of urea and 9.74g of formaldehyde solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, wherein the molar ratio of the three is 2: 1: 6 and deionized water, adding 10% NaOH solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1h, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea.
And step three, adding 4.3g (0.005 mol) of HAPCP powder prepared in the step one and all prepolymer solutions prepared in the step two into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, adding a proper amount of sodium dodecyl sulfate solution, adjusting the pH value to 5.5-6 by using a 5% hydrochloric acid solution, heating to 70 ℃, stirring for reaction for 3 hours, diluting by using a large amount of deionized water after the reaction is finished to reduce the viscosity and the filtration resistance, filtering the diluent, washing a filter cake, and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
Example 4: the embodiment provides a cyclotriphosphazene flame retardant with a microcapsule core-shell structure, and a preparation method of the cyclotriphosphazene flame retardant comprises the following steps:
step one, 20.45g (0.148 mol) of K was sequentially added to a 500ml three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer2CO317.6g (0.144 mol) of p-hydroxybenzaldehyde and 200ml of acetone, and stirring and reacting for 1 hour at room temperature; then 150ml of acetone dissolved with 6.95g (0.02 mol) of hexachlorocyclotriphosphazene is dripped, the temperature is raised to 65 ℃, the mixture is stirred and refluxed for 24 hours after dripping, then the solution is kept stand, cooled and filtered, and the filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing with ethyl acetate, washing and drying the obtained crystal to obtain white flocculent solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene (HAPCP), wherein the yield is 56.4%; grinding in a freezing grinder until the particle size is less than 10 microns, sieving with a 100-mesh sieve, and placing in a dryer for later use.
The observation of a scanning electron microscope shows that the surface of the product is uneven, and the yield is greatly reduced because acetone damages substances participating in the reaction process.
Step two, adding 5.0448g of melamine, 1.2g of urea and 9.74g of formaldehyde solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, wherein the molar ratio of the three is 2: 1: 6 and deionized water, adding 10% sodium bicarbonate solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1 hour, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea.
And step three, adding 4.3g (0.005 mol) of HAPCP powder in the step one and all prepolymer solutions prepared in the step two into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, adding a proper amount of sodium dodecyl sulfate solution, adjusting the pH value to 5.5-6 by using 5% potassium hydrogen phthalate solution, heating to 70 ℃, stirring for reaction for 3 hours, diluting with a large amount of deionized water after the reaction is finished to reduce the viscosity and the filtration resistance, filtering the diluent, washing a filter cake, and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
Test example 1, Performance test
(1) Infrared spectroscopic analysis
The functional groups of the cyclotriphosphazene flame retardant HAPCP prepared in the first step of the invention example 1 are analyzed by Fourier infrared spectroscopy, and the details are shown in FIG. 1.
(2) Nuclear magnetic resonance analysis
Nuclear Magnetic Resonance (NMR) of the cyclotriphosphazene flame retardant HAPCP prepared in the first step of the example 1 is shown in figure 2, wherein (a)1HNMR is shown in the figure; (b)31 PNMR; (c)13CNMR。
(3) analysis of element content
The result of analyzing the element content of the cyclotriphosphazene flame retardant HAPCP prepared in the first step of the invention is shown in the following table 1, and the element content basically accords with the expected product.
(4) Scanning Electron microscope analysis (SEM)
The cyclotriphosphazene flame retardant with the microcapsule core-shell structure synthesized by the invention is observed and analyzed by using a desktop scanning electron microscope, and the result is shown in figure 3.
As can be seen from the SEM image, the uncoated cyclotriphosphazene flame retardant prepared in the first step has a smooth surface, the surface of the flame retardant coated by the microcapsule has a compact coating layer, and the particle size of the flame retardant particles is enlarged and is distributed between 10 and 20 microns. The successful preparation of the core-shell structure of the microcapsule is proved.
(5) Thermogravimetric analysis (TG)
Using a thermogravimetric analyzer, the mass and composition of the sample was analyzed as a function of temperature, with the results shown in fig. 4.
As can be seen from the TGA results of FIG. 4 (a), the initial decomposition temperature of HAPCP is 446oC (based on 5% weight loss); the main peak of thermal degradation is around 314 oC, at 800 oThe carbon residue was about 76.5%. From the results of TGA in FIG. 4 (b), it can be seen that the initial decomposition temperature of the flame retardant having a microcapsule core-shell structure (MHAPCP) is 327oC (based on)5% weight loss); the main peak of thermal degradation is about 340 oC, at 800 oThe carbon residue was about 48.87%.
Test example 2: the cyclotriphosphazene flame retardant with the microcapsule core-shell structure prepared in the embodiment 1 is applied as a nitrogen-phosphorus synergistic flame retardant for polylactic acid.
(1) The invention is used for testing the performance of the cyclotriphosphazene flame retardant and polylactic acid (PLA) blended material with the microcapsule core-shell structure.
The content ratio of the flame retardant and the polylactic acid (PLA) is controlled to prepare the composite material, standard sample bars are prepared according to GB/T2406-93 and GB/T2508-1996 test standards respectively, and a limit oxygen index test and a vertical combustion test are carried out, wherein the data are shown in Table 2.
From the data in Table 2, it can be seen that pure PLA has a limiting oxygen index of 18.7%, is a highly flammable material, and cannot be rated in the UL-94 test. Pure PLA can generate a large amount of drops in the combustion process, easily causes secondary combustion, and causes great loss to the safety of lives and properties. With the gradual increase of the content of the flame retardant MHAPCP, the limiting oxygen index and the vertical burning grade of the PLA flame-retardant composite material are improved. When the addition amount of the flame retardant is increased from 15% to 30%, the LOI of the flame-retardant composite material is increased from 20.3% to 29.8%, the flame-retardant rating is achieved, and the vertical burning test also passes the V-0 test rating. This shows that with the increase of the content of the flame retardant MHAPCP, the flame retardance of the PLA/MHAPCP flame-retardant composite material is gradually enhanced, and the combustion behavior is gradually improved.
(2) The flame retardant with microcapsule core-shell structure (MHAPCP) prepared by the invention and the PLA blended material are subjected to a weight loss under heating test.
The change in the mass and chemical composition of the blended material with increasing temperature was analyzed using a thermogravimetric analyzer and the results are shown in figure 5.
It can be seen from the combination of the graphs that the addition of the flame retardant significantly changes the initial decomposition temperature of the composite material compared to pure PLAThe T of pure PLA is determined by taking the temperature at which the material is decomposed by 5% as the initial decomposition temperature5%From 358 ℃ to 370 ℃ because the addition of the flame retardant hinders the degradation of PLA, which in turn increases the initial decomposition temperature of the composite.
Pure PLA has a residual carbon content of about 2.72% at 400 ℃ and a residual mass of about 1.37% at 600 ℃ and is almost negligible, whereas composite materials to which 30% of flame retardant (MHAPCP) has been added have residual carbon contents of 30.9%, 24.7% and 22% at 400 ℃, 500 ℃ and 600 ℃, respectively. The results show that PLA/MHAPCP exhibits better thermal stability, while the carbon residue formed at 600 ℃ is higher than pure PLA.
(3) The tensile and impact resistance tests of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure and the polylactic acid (PLA) blended material are carried out, and the results are shown in FIGS. 6 and 7.
As can be seen from fig. 6 and 7, the elongation at break of the pure PLA is 7.76%, and when the MHAPCP content is 15%, 20%, 25%, 30%, the elongation at break of the corresponding composite materials is 6.41%, 6.13%, 5.72%, 5.45%, respectively. The notched impact strength of pure PLA was 4.41KJ/m2When the MHAPCP content is 15%, 20%, 25% or 30%, the corresponding composite material has a notched impact strength of 4.34KJ/m2、4.2 KJ/m2、4.05 KJ/m2、3.89 KJ/m2. Compared with pure PLA material, generally, the mechanical property of the composite material is reduced due to factors such as nonuniform dispersion of the flame retardant particles in the matrix and incompatibility with the matrix material when the flame retardant is introduced into the matrix, but the mechanical property of the material is maintained at a better level after the flame retardant is added in the invention, and is slightly reduced compared with the pure PLA material. Hydrogen bond combination is formed between the microcapsule structure containing a large number of free hydroxyl groups and the PLA matrix, which is probably an important reason for improving the compatibility between the flame retardant particles and the matrix, and further the mechanical property of the composite material is improved.
(4) The blended material was observed by an electron microscope, and the scanning electron microscope is shown in FIG. 8.
As can be seen from the SEM image of FIG. 8, no significant agglomeration of the flame retardant particles occurs in the matrix, and the flame retardant particles are uniformly dispersed in the PLA matrix, so that it can be concluded that the flame retardant particles have good compatibility with each other, and the trend of the mechanical properties is consistent with the trend of the change of the mechanical properties.
Claims (7)
1. A cyclotriphosphazene flame retardant with a microcapsule core-shell structure is characterized in that: the flame-retardant core material is hexa (4-aldehyde phenoxy) cyclotriphosphazene, and the shell material is melamine urea-formaldehyde resin.
2. The cyclotriphosphazene flame retardant with a microcapsule core-shell structure according to claim 1, wherein: the particle size of the hexa (4-aldehyde phenoxy) cyclotriphosphazene is less than 10 microns.
3. A preparation method of cyclotriphosphazene flame retardant with a microcapsule core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a flame-retardant core material: sequentially adding an acid-binding agent, p-hydroxybenzaldehyde and an organic solvent into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, and stirring and reacting for 1h at room temperature; then, 150ml of organic solution in which hexachlorocyclotriphosphazene is dissolved is dropwise added, the temperature is raised to 65 ℃, stirring and reflux reaction are carried out for 24 hours, then the solution is kept stand, cooled and filtered, and filtrate is collected; dropwise adding ice water into the filtrate to obtain a white precipitate, filtering, collecting and washing a filter cake, and drying at 80 ℃ for 12 hours; drying, recrystallizing, washing and drying the obtained crystal to obtain a white acicular solid, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene; wherein the molar ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is 1: 7.4, the molar ratio of the p-hydroxybenzaldehyde to the hexachlorocyclotriphosphazene is 1: 7.2;
step two, preparing a prepolymer mixture: adding melamine, urea, formaldehyde solution and deionized water into a three-neck flask provided with a thermometer, a condenser pipe and a magnetic stirrer, adding alkaline solution to adjust the pH value to 8.5-9, heating to 70 ℃, reacting for 1h, and cooling to room temperature to obtain a mixed solution of two prepolymers, namely hydroxymethyl melamine and hydroxymethyl urea;
and step three, crushing the hexa (4-aldehyde phenoxy) cyclotriphosphazene, respectively adding hexa (4-aldehyde phenoxy) cyclotriphosphazene powder, a prepolymer solution and a surfactant solution into a three-neck flask provided with a thermometer, a condenser and a magnetic stirrer, adjusting the pH value to 5.5-6, heating to 70 ℃, stirring for reaction for 3 hours, diluting, filtering and drying to obtain the cyclotriphosphazene flame retardant with the microcapsule core-shell structure.
4. The preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure according to claim 3, characterized in that: the acid-binding agent is inorganic base or organic base without active hydrogen, wherein the inorganic base is one or more of potassium carbonate, sodium carbonate or sodium hydroxide, and the organic base without active hydrogen is pyridine or triethylamine.
5. The preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure according to claim 3, characterized in that: the organic solvent used in the first step is one or more of acetone, tetrahydrofuran and N, N-dimethylformamide.
6. The preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure according to claim 3, characterized in that: in the second step, the molar ratio of the melamine to the urea to the formaldehyde solution is 1: 2: 6 or 2: 1: 6.
7. the preparation method of the cyclotriphosphazene flame retardant with the microcapsule core-shell structure according to claim 3, characterized in that: in the third step, the addition amount of HAPCP is 0.005 mol.
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