CN112175242A - Microcapsule intumescent flame retardant and preparation method and application thereof - Google Patents
Microcapsule intumescent flame retardant and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a microcapsule intumescent flame retardant and a preparation method and application thereof, the flame retardant is prepared from a core material and a capsule material coated on the core material, the core material is prepared from an acid source and a carbon source, the capsule material is prepared from an air source, the flame retardant has a microcapsule structure and multi-component synergistic flame retardance, the flame retardant efficiency is higher, the flame retardant effect is better, the obtained flame retardant can be blended with polylactic acid to prepare flame-retardant polylactic acid, and the flame retardant property of the obtained flame-retardant polylactic acid is excellent.
Description
Technical Field
The invention relates to the technical field of flame retardants, and particularly relates to a microcapsule intumescent flame retardant and a preparation method and application thereof.
Background
The flame retardant can endow flammable polymers with flame-retardant property, and has wide application in the flame-retardant and fireproof performances of the polymers. At present, the commonly used flame retardants include single-component nitrogen-based flame retardants, phosphorus-based flame retardants, and the like, multi-component nitrogen-phosphorus synergistic flame retardants, phosphorus-silicon synergistic flame retardants, and intumescent flame retardants.
Compared with a single-component flame retardant, the multi-component flame retardant synergistic flame retardant can improve the flame retardant performance through multiple ways. However, the multi-component synergistic flame retardant has the defects that the synergistic elements are not concentrated and the processing temperature is influenced by the lowest processing temperature of the components, so that the flame retardant efficiency of the flame retardant is influenced. And when applied to polymers, multicomponent flame retardants such as intumescent flame retardants are used in relatively large amounts, typically up to 15% and even more, which is detrimental to post processing and other properties of the polymer.
Disclosure of Invention
In order to overcome the problems, the inventor of the present invention has made intensive studies to develop a microcapsule intumescent flame retardant, which is prepared from a core material and a capsule material coated on the core material, wherein the core material is prepared from an acid source and a carbon source, the capsule material is prepared from an air source, the flame retardant has a microcapsule structure and multi-component synergistic flame retardance, and has the advantages of higher flame retardance efficiency, better flame retardance effect, simple preparation method and simple process, the obtained flame retardant can be blended with polylactic acid to prepare flame-retardant polylactic acid, the flame retardance of the obtained flame-retardant polylactic acid is excellent, and the application range of the polylactic acid is widened, thereby completing the present invention.
The invention aims to provide a microcapsule intumescent flame retardant which is prepared from a core material and a capsule material coated on the core material, wherein the core material is prepared from an acid source and a carbon source, and the capsule material is prepared from a gas source.
Another aspect of the present invention provides a method for preparing the microencapsulated intumescent flame retardant of the first aspect of the present invention, the method comprising: mixing an acid source and a carbon source to prepare a core material; and coating a capsule material formed by an air source on the surface of the core material to obtain the microcapsule intumescent flame retardant.
In a further aspect of the present invention, there is provided a use of the microcapsule intumescent flame retardant described in the first aspect of the present invention or prepared by the method described in the second aspect of the present invention in polylactic acid, wherein the microcapsule intumescent flame retardant is mixed with polylactic acid, and the mixture is extruded by a twin-screw extruder to obtain flame retardant polylactic acid.
The invention has the following beneficial effects:
(1) according to the invention, the core material is prepared from an acid source and a carbon source, and the core material is coated with the capsule material formed by an air source to obtain the microcapsule intumescent flame retardant, the microcapsule structure enables flame-retardant elements such as phosphorus, carbon and nitrogen to be more concentrated, a better flame-retardant synergistic effect is achieved, the flame-retardant efficiency is high, and the residual carbon rate of the microcapsule intumescent flame retardant is high, preferably more than 30%, preferably more than 35%, even 37.63%;
(2) according to the invention, the surface of the core material is coated with the capsule material in an in-situ polymerization manner, so that the flame-retardant elements in the gas source are distributed on the surface of the core material more uniformly, and the gas source is decomposed to generate inert gases such as nitrogen and ammonia when heated, so that the oxygen-insulating and heat-insulating effects are achieved, and the flame-retardant effect is realized;
(3) when the core material formed in the microcapsule intumescent flame retardant is heated, an acid source (such as APP) releases inorganic acid to react with a carbon source (such as MCC) for dehydration and crosslinking, so that a compact and fluffy carbon layer is formed, oxygen and heat are isolated, and a flame retardant effect is achieved;
(4) the microcapsule intumescent flame retardant is applied to polylactic acid to prepare flame-retardant polylactic acid, the flame-retardant property of the flame-retardant polylactic acid is excellent, and the application range of the polylactic acid is expanded, for example, the carbon residue rate of the flame-retardant polylactic acid is more than 12%; the limiting oxygen index is higher than 30 percent, for example, reaches 31.5 percent, the ignition time in a vertical burning test experiment is short, no molten drop is generated, and the rating is V-0.
(5) The preparation method of the microcapsule intumescent flame retardant provided by the invention has the advantages of simple process, easily obtained raw materials and easy realization.
Drawings
FIG. 1 shows an SEM photograph in Experimental example 1 of the present invention;
FIG. 2 shows an infrared spectrum in Experimental example 2 of the present invention;
FIG. 3 shows a TG curve in Experimental example 3 of the present invention.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the invention, the microcapsule intumescent flame retardant is prepared from a core material and a capsule material coated on the core material, wherein the core material is prepared from an acid source and a carbon source, and the capsule material is prepared from an air source.
According to the invention, the preparation method of the microcapsule intumescent flame retardant comprises the following steps: preparing a core material by adopting an acid source and a carbon source, and then coating the core material with a capsule material prepared by an air source to obtain the microcapsule intumescent flame retardant.
In the invention, the microcapsule intumescent flame retardant is embodied in a microcapsule form by an intumescent flame retardant, and the intumescent has the characteristics of a microcapsule structure and the synergy of a multi-component flame retardant, and has the advantages of high flame retardant efficiency and good flame retardant effect.
According to a preferred embodiment of the invention, the core material is prepared by mixing an acid source and a carbon source, wherein the mass ratio of the acid source to the carbon source is (2-8): 1, preferably (3-6): 1.
according to a preferred embodiment of the present invention, the acid source is selected from one or more of melamine polyphosphate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid (DDP), ammonium polyphosphate (APP), preferably DDP or APP, more preferably APP.
According to a preferred embodiment of the present invention, the carbon source is selected from one or a mixture of several of microcrystalline cellulose (MCC), pentaerythritol, dipentaerythritol, chitosan and starch, preferably microcrystalline cellulose.
According to a preferred embodiment of the present invention, when the acid source is DDP and the preferred carbon source is MCC, the specific steps of mixing the acid source and the carbon source to prepare the core material are as follows: and mixing the solution containing the DDP and the solution containing the MCC, stirring for a certain time, cooling, continuing stirring, and centrifugally drying to obtain the core material.
According to a further preferred embodiment of the present invention, the solution containing DDP is prepared by dissolving DDP in a solvent, which is a non-polar solvent, preferably one or more of acetone, water, methanol and ethanol, preferably a mixture of acetone and water.
According to a preferred embodiment of the present invention, the volume ratio of acetone to water is (1-4): 1, preferably 2: 1.
According to the present invention, DDP is added to a solvent and mixed to obtain a DDP-containing solution having a volume of 60 to 120ml, preferably 90ml, based on 10g of DDP.
According to the invention, the temperature for mixing the DDP and the solvent is 55-75 ℃, preferably 60-70 ℃, and more preferably 65 ℃.
According to the present invention, the DDP is completely dissolved in the solvent by mixing with stirring. The stirring time and the stirring speed are not particularly set so as to ensure that the DDP is completely dissolved, preferably, the stirring time is 1-3 h, the stirring speed is 100-300 r/min, more preferably, the stirring time is 2h, and the stirring speed is 100 r/min.
According to the invention, the MCC-containing solution is a dispersion liquid containing MCC and is prepared by dispersing the MCC in a solvent by ultrasonic waves, wherein the solvent is water, preferably deionized water, and the volume of the solvent is 3-8 ml, preferably 5ml, based on 1g of the MCC.
According to the invention, the mass ratio of the acid source to the carbon source is (2-8): 1.
according to a further preferred embodiment of the present invention, the mass ratio of DDP to MCC is (2-4): 1, preferably 3: 1.
According to the invention, the MCC-containing dispersion is added into the DDP-containing solution, preferably in a dropwise manner, preferably the MCC-containing solution is added within 5-15 min, and more preferably within 10 min. The dropwise addition method can make MCC easier to disperse in the solution containing DDP, so as to avoid the agglomeration of the MCC in the solution.
According to the invention, after the dispersion liquid containing MCC is added into the solution containing DDP, the dispersion liquid containing MCC and the solution containing DDP are stirred and mixed to obtain a mixed solution, wherein the stirring speed is 100-300 rmin, and preferably 200 r/min; the stirring time is 60-150 min, preferably 120 min.
According to the invention, after stirring is finished, the mixed solution is cooled to a certain temperature, preferably to 10-30 ℃, more preferably to 20 ℃, and is continuously stirred for 5-20 hours, preferably 10 hours, at the temperature, and then the mixed solution is centrifugally dried to obtain the core material, wherein the core material is composed of DDP and MCC, and preferably the core material is formed by coating the MCC with DDP.
In the invention, DDP is supersaturated in a solution containing DDP, the solution containing MCC is added and mixed, the mixed solution is cooled, the DDP is precipitated from the mixed solution under cooling and is adsorbed on the MCC for crystallization, so that the DDP forms a coating structure on the surface of the MCC to obtain the core material. The core material is prepared from an acid source and a carbon source, and the flame retardant efficiency of the core material is improved by the flame retardant synergistic effect of the acid source and the carbon source.
According to the invention, the core material is prepared from the acid source and the carbon source, so that the flame-retardant elements are more concentrated, the phosphorus and the carbon elements have a synergistic flame-retardant effect, the synergistic efficiency is improved, when the core material is combusted and heated, the acid source (such as APP) releases inorganic acid to react with the carbon source (such as MCC) for dehydration and crosslinking, a compact and fluffy carbon layer is formed, oxygen and heat are isolated, and the flame-retardant effect is achieved.
According to another preferred embodiment of the present invention, when the acid source is APP and the carbon source is MCC, the specific steps of mixing the acid source and the carbon source to prepare the core material are as follows: and dispersing the APP and the MCC in a solvent, performing ball milling to obtain ball-milled mixed liquid, and performing centrifugal drying to obtain the core material.
According to the present invention, the solvent is preferably a non-polar solvent, preferably water, more preferably deionized water. Adding APP and MCC into a solvent, controlling the temperature, and then adding the mixture into a ball mill for ball milling to obtain a mixed solution.
According to the invention, the temperature is controlled to be 20-30 ℃, preferably 25 ℃, the blending of the acid source and the carbon source is facilitated at the temperature, and the agglomeration of the carbon source MCC can be prevented.
According to the invention, zirconia microspheres are adopted for ball milling, and the rotating speed of the ball mill is set to be 1000-4000 r/min, preferably 2000-3500 r/min, and more preferably 3000 r/min; the ball milling time is 1-5 h, preferably 2-4 h, and more preferably 3 h.
In the invention, MCC is refined by ball milling, and the contact area of APP and MCC is increased, so that APP and MCC are mixed more uniformly, the flame-retardant elements are distributed more intensively, and the flame-retardant effect is better.
According to the invention, the mass ratio of APP to MCC is (4-8): 1, preferably 6: 1. The volume of the solvent is 80-120 ml, preferably 100ml, based on the total mass of APP and MCC being 7 g.
According to the invention, after the core material is obtained, the core material is coated with the capsule material prepared by the air source, and the microcapsule intumescent flame retardant is obtained.
According to the invention, the core material is coated with the capsule material by an in-situ polymerization method to obtain the microcapsule structure.
According to the invention, the gas source is selected from one or more of Melamine Cyanurate (MCA), melamine, dicyandiamide and urea, wherein the MCA is polymerized from Melamine (ME) and Cyanuric Acid (CA).
In the present invention, the gas source is capable of generating an inert gas by thermal decomposition, such as N in which MCA is decomposed to generate nitrogen by thermal decomposition2And NH3O which dilutes the combustion atmosphere2And takes away heat, hinders the heat and substance transfer of combustion, separates oxygen and insulates against heat, has excellent fire behaviour.
According to the invention, the mass ratio of the gas source to the carbon source is (1-6): 1.
according to the invention, the core material is dispersed in a nonpolar solvent to obtain a solution containing the core material, then cyanuric acid is added, the temperature is raised and the mixture is stirred, and the melamine dispersion liquid is added for reaction to obtain the microcapsule intumescent flame retardant.
According to the invention, the molar ratio of cyanuric acid to melamine is 1: 1.
According to the invention, after cyanuric acid is added, heating and stirring are carried out, specifically, the temperature is raised to 70-100 ℃, preferably 80-90 ℃, and stirring is carried out simultaneously, wherein the stirring speed is 100-300 r/min, preferably 200 r/min; the stirring time is 1-5 h, preferably 2-4 h, and more preferably 2 h.
According to the invention, the melamine dispersion is obtained by dispersing melamine in a solvent, wherein the solvent is a non-polar solvent, preferably absolute ethyl alcohol, and the volume of the absolute ethyl alcohol is 10-30 ml, preferably 20ml, based on 2g of melamine.
According to the invention, the melamine dispersion is added into the reaction system in a dropwise manner, and the dropwise addition is completed within 10-50 min, preferably within 30 min.
According to the invention, after the melamine dispersion liquid is dripped, stirring is carried out for 6-10 h, preferably 8h, and centrifugal drying is carried out after the stirring is finished to obtain the microcapsule intumescent flame retardant.
In the invention, in a reaction system, melamine and cyanuric acid are subjected to in-situ polymerization to generate Melamine Cyanurate (MCA), and the generated MCA is insoluble in the system, so that the MCA is used as a capsule material to coat the surface of a core material, and the microcapsule intumescent flame retardant is obtained.
In the invention, when the microcapsule intumescent flame retardant is heated, an acid source (such as APP) releases inorganic acid to react with a carbon source (such as MCC) for dehydration and crosslinking to form a compact and fluffy carbon layer to isolate oxygen and heat, and meanwhile, an air source (such as MCA) decomposes to generate inert gas (such as ammonia and nitrogen), so that oxygen in a combustion atmosphere can be diluted and heat is taken away, the carbon layer expands, a better heat insulation and oxygen isolation effect is achieved, and the flame retardant property is improved.
According to the invention, the carbon residue rate of the microcapsule intumescent flame retardant is more than 30%, preferably more than 35%, even 37.63%.
The microcapsule intumescent flame retardant disclosed by the invention adopts a composite component of an acid source and a carbon source as a core material, and then a capsule material formed by coating a gas source on the surface of the core material by an in-situ polymerization method is used for forming the trinity microcapsule intumescent flame retardant, the synergistic effect of phosphorus, carbon and nitrogen elements is realized, the core material and the capsule material generate a good flame-retardant synergistic effect, the structural form of the microcapsule also leads flame-retardant elements to be more concentrated, the synergistic efficiency is better improved, and the flame-retardant efficiency of the flame retardant can be obviously improved.
The invention provides an application of a microcapsule intumescent flame retardant in polylactic acid.
According to the invention, the application is that the polylactic acid is mixed with the microcapsule intumescent flame retardant and is extruded by a double-screw extruder to obtain the flame-retardant polylactic acid.
Specifically, the preparation method of the flame-retardant polylactic acid comprises the following steps: the method comprises the following steps of carrying out vacuum drying treatment on the microcapsule intumescent flame retardant, mixing the microcapsule intumescent flame retardant with polylactic acid, adding the mixture into a double-screw extruder, carrying out melt blending extrusion by the double-screw extruder to obtain a flame-retardant polylactic acid material, further carrying out shearing granulation to obtain flame-retardant polylactic acid material granules, and pressing the flame-retardant polylactic acid granules into required test sample strips with various specifications by a film pressing machine to carry out performance test.
According to a preferred embodiment of the present invention, the mass ratio of the microcapsule intumescent flame retardant to the polylactic acid is (80-98): (2-20), preferably (85-95): (5-15), more preferably 10: 90. The microcapsule intumescent flame retardant has good flame retardant effect, and the flame retardant polylactic acid with excellent flame retardant property can be obtained by adding a small amount of flame retardant into the polylactic acid.
According to the invention, the temperature of the vacuum drying treatment is 80-110 ℃, preferably 100 ℃, and the vacuum drying time is 12-24 hours, preferably 12 hours.
According to the invention, the melt blending temperature of the polylactic acid and the microcapsule intumescent flame retardant is 180-200 ℃, preferably 190 ℃, and the rotating speed of the double-screw extruder is 40-80 r/min, preferably 60 r/min.
In the invention, the microcapsule intumescent flame retardant and the flame-retardant polylactic acid prepared from polylactic acid have excellent flame-retardant performance, and the residual carbon rate of the flame-retardant polylactic acid is more than 12%, preferably more than 14%, even reaches 16.1%; the limiting oxygen index of the flame-retardant polylactic acid is higher than 30%, for example, 31.5%, the ignition time in a vertical combustion test experiment is short, no molten drop is generated, the ignition time is not higher than 1.5s, preferably the first ignition time is not higher than 1.4s, the second ignition time is not higher than 1.0s, for example, the first ignition time is 1.3s, and the second ignition time is 0.9s, which shows that the flame retardant can better promote the carbon formation performance of PLA, a compact and fluffy carbon layer is formed on the surface of PLA, oxygen and heat are isolated, gas generated by the decomposition of a capsule material on the surface can dilute oxygen and take away heat, the transfer of heat and substances during combustion is hindered, and an organism is protected, so that the flame-retardant polylactic acid has excellent flame retardant performance.
Examples
In the following examples: DDP feedstock was purchased from Zhengzhou alpha chemical Co., Ltd; the APP raw material is purchased from Shandong Shian chemical Co., Ltd; MCC from Zhengzhou alpha chemical Co., Ltd; melamine and cyanuric acid were purchased from Shanghai Meclin chemical Co., Ltd; polylactic acid was purchased from Zhejiang Haizhen biomaterial GmbH.
Example 1
Mixing 60ml of acetone and 30ml of water to prepare a solvent, adding 10g of DDP into the solvent, and stirring at 65 ℃ to obtain a DDP-containing solution; dispersing 2g of MCC in deionized water to obtain a solution containing MCC;
after DDP is dissolved, adding the solution containing MCC dropwise into the solution containing DDP, obtaining a mixed solution after finishing adding dropwise within 10min, and stirring the mixed solution for 2 h; after stirring, cooling the mixed solution to 20 ℃, and placing the mixed solution in a water bath at 20 ℃ to continue stirring for 10 hours; after stirring is finished, carrying out centrifugal drying on the mixed solution to obtain a core material;
adding 0.99g of melamine into 10ml of deionized water, and performing ultrasonic dispersion to obtain melamine dispersion liquid;
adding 8g of core material into deionized water, performing ultrasonic dispersion, heating to 90 ℃, stirring for 2h, adding 1.01g of cyanuric acid, adding a melamine dispersion liquid in a dropwise manner after the cyanuric acid is dissolved so as to avoid agglomeration of melamine, continuing stirring for 10h within 30min after the dropwise addition is completed, reacting, and performing centrifugal drying after the stirring is completed to obtain the microcapsule intumescent flame retardant.
Example 2
The procedure of example 1 was repeated except that 2.97g of melamine and 3.03g of cyanuric acid were used and the other procedures were the same as in example 1 to obtain a microencapsulated intumescent flame retardant.
Example 3
Dispersing 6g of APP and 1g of MCC in deionized water, controlling the temperature to be 25 ℃, putting the mixture into a ball mill at the rotating speed of 3000r/min, and carrying out centrifugal drying after 3 hours of ball milling to obtain a core material;
dispersing 1.49g of melamine in 15ml of absolute ethyl alcohol to obtain melamine dispersion liquid;
dispersing the core material in 100ml of absolute ethyl alcohol, stirring, adding 1.51g of cyanuric acid, heating to 80 ℃, keeping the temperature for 2 hours, dropwise adding the melamine dispersion, stirring for reacting for 8 hours, and centrifugally drying to obtain the microcapsule type intumescent flame retardant.
Example 4
The procedure in example 3 was repeated except that 2.24g of melamine and 2.26g of cyanuric acid were used and the other procedures were the same as in example 3 to obtain a microencapsulated intumescent flame retardant.
Comparative example 1
APP raw material is used as the flame retardant of comparative example 1.
Comparative example 2
And (3) physically blending 6g of APP and 1g of MCC, uniformly grinding by using a mortar to obtain a blend of the APP and the MCC, and taking the blend as the flame retardant of the comparative example 2.
Comparative example 3
Dispersing 6g of APP and 1g of MCC in deionized water, controlling the temperature to be 25 ℃, putting the mixture into a ball mill at the rotating speed of 3000r/min, carrying out ball milling for 3 hours, and then carrying out centrifugal drying to obtain a core material, wherein the obtained core material is used as the flame retardant of the comparative example 3.
Comparative example 4
Adding 1.49g of melamine into 15ml of deionized water, and performing ultrasonic dispersion to obtain melamine dispersion liquid;
adding 1.51g of cyanuric acid into deionized water at 90 ℃, stirring at constant temperature, adding the melamine dispersion in a dropwise manner after the cyanuric acid is dissolved, continuing stirring for 10h within 30min, reacting, and centrifugally drying after stirring to obtain MCA, wherein the MCA is used as the flame retardant of the comparative example 4.
Comparative example 5
To the product obtained in comparative example 2, 3g of MCA was added and mixed to obtain a blend of the three, and the resulting blend was used as the flame retardant in comparative example 5.
Examples of the experiments
Experimental example 1SEM test
Scanning electron microscope tests were performed on the flame retardant obtained in example 3, and the flame retardants obtained in comparative example 1, comparative example 2 and comparative example 3, and the obtained SEM pictures are shown in FIG. 1, FIG. 1(a) is a SEM picture of the APP raw material obtained in comparative example 1, FIG. 1(b) is a SEM picture of the flame retardant obtained in comparative example 2, FIG. 1(c) is a SEM picture of the flame retardant obtained in comparative example 3, and FIG. 1(d) is a SEM picture of the microencapsulated intumescent flame retardant obtained in example 3.
As can be seen from the figure, the APP raw material particles in the comparative example 1 have clear edges and corners and smooth surface texture, the particles in the comparative example 2 have smooth surfaces and clear edges and corners, are not greatly different from the APP raw material particles in appearance, and are only the simple mixture of the APP and the MCC, and the core material obtained in the comparative example 3 has small particle size and presents a certain agglomeration phenomenon, the particle surface is rough, and the edges and corners are fuzzy. The product particles obtained in example 3 reappeared significant edges and the surface remained rough, indicating successful MCA coating of the core material.
Experimental example 2 Infrared test
The flame retardant obtained in example 3, the flame retardants obtained in comparative examples 1, 4 and 5 were subjected to an infrared test, and the obtained infrared spectrum was as shown in FIG. 2, A is the infrared curve of the APP raw material of comparative example 1, B is the infrared curve of MCA obtained in comparative example 4, C is the infrared curve of the flame retardant of comparative example 5, and D is the infrared curve of the flame retardant obtained in example 3.
As can be seen in FIG. 2, 3012cm in APP-1Is NH4 +Asymmetric absorption peak of ion, 1421cm-1Is NH+Bending vibration peak of ion, 1061, 1002, 884cm-1Is located at the stretching vibration peak of P-O-P, 1244cm-1And P is the expansion vibration peak of O. 3378cm in MCA-1、3227cm-1The peak is N-H symmetric contraction vibration peak and asymmetric expansion vibration peak, 1658cm-1Is represented by-NH2Bending vibration peak of (1), 1530cm-1、1442cm-1Characteristic absorption peak of C-N, C-N at triazine ring, 1781cm-1、1728cm-1C-O, C ═ O absorption peak at carbonyl group, 768cm-1The absorption peak at (a) is due to the out-of-plane bending vibration peak of the ring.
The infrared spectrum of the flame retardant obtained in example 3 and pure APP is 1500cm-1～2000㎝-1Has different characteristic peaks and is 1500cm-1The following characteristic peak patterns were consistent with those of pure APP. The IR spectrum of the flame retardant obtained in example 3 was compared with that of pure MCA, and the IR spectrum of the flame retardant obtained in example 3 remained 3204cm-1、1782cm-1、1730cm-1、1662cm-1、1535cm-1The characteristic peak of MCA in (A) but the peak patterns are not consistent. From this, it was found that MCA was indeed successfully coated on a core material formed of APP and MCC.
Experimental example 3 thermogravimetric testing
The flame retardants obtained in example 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 5 were subjected to thermogravimetric analysis using a thermogravimetric analyzer model NETZSCH TG209F1 of NETZSCH, germany, and the resulting thermogravimetric curves (TG curves) are shown in fig. 3, and in fig. 3, curves A, B, C, D, E are the TG curves of the products obtained in comparative examples 1-3, comparative example 5 and example 3, respectively, and the results of the data analysis are shown in table 1.
TABLE 1
As can be seen from fig. 3 and table 1, the initial decomposition temperature of the APP raw material is 327 ℃, the maximum decomposition efficiency temperature is 619.16 ℃, and the amount of carbon residue (carbon residue rate) is 24.85%, and the thermal degradation thereof in air can be divided into two stages. The first stage begins at about 327 deg.C and ends at about 570 deg.C, which is mainly due to the thermal decomposition of APP into H2O，NH3And cross-linked phosphoric acid, etc., cause mass loss. The second stage occurs above 570 c, which is mainly a further decomposition of phosphoric acid, producing oxides of phosphorus.
The thermal degradation process of the flame retardants obtained in comparative examples 2 and 3 can also be divided into twoAt this stage, but the flame retardants of comparative examples 2 and 3 had thermal stabilities inferior to that of APP, and the amount of carbon residue was also lower than that of APP, probably because of the reduction in the final residual amount due to the decomposition of MCC. After addition of MCA, the amount of carbon residue of comparative example 5 is 26.57%, and the amount of carbon residue of example 3 is 37.63%, both exceeding APP, because APP releases inorganic acid to react with MCC and dehydrates and crosslinks to form a carbon layer when heated, and MCA decomposes to generate NH, which is an inert gas3The carbon layer is expanded, so that the carbon layer has better heat insulation and oxygen isolation effects, and the carbon residue is increased.
The carbon residue of the flame retardant obtained in the example 3 is 11.06% higher than that of the product obtained in the comparative example 5, because the flame retardant of the example 3 is a three-in-one microcapsule intumescent flame retardant, three elements of phosphorus, carbon and nitrogen act synergistically, and the form of microcapsules also leads to more concentrated flame retardant elements, so that the synergistic efficiency is better improved, and the flame retardant performance is improved.
Experimental example 4
Respectively carrying out vacuum drying on the flame retardants obtained in comparative examples 1-3, 5 and 3 at 100 ℃ for 12 hours, then respectively taking 10g of the flame retardant and 90g of polylactic acid to simply mix, carrying out melt blending extrusion and granulation on a double-screw extruder, then carrying out compression molding on the granules on a film pressing machine to prepare test strips of various specifications, respectively recording the samples prepared from the flame retardants obtained in comparative examples 1-3 and 5 and the polylactic acid as sample 1, sample 2, sample 3 and sample 4, respectively recording the sample prepared from example 3 and the polylactic acid as sample 5, and recording pure polylactic acid (PLA) as sample 0.
The cone calorimeter of FTT company in England is used to carry out cone calorimetric test on samples 0-4, the test sample bar specification is 100mm x 3mm, the obtained test results are shown in Table 2,
TABLE 2
As can be seen from Table 2, the peak heat release rate (pHRR) of pure PLA was 437kW/m2Total Heat Release amount (THR) was 73.2MJ/m2. Compared with pure PLA, the total heat release amount of the PLA composite material of sample 1 added with APP only is obviously reduced, but the heat release rate is slightly improved, and the carbon residue rate is increased by 6.9%. After sample 2 was introduced with another flame retardant component MCA, the amount of carbon residue was reduced in sample 2 compared to sample 1, probably due to thermal decomposition of MCA, but the peak heat release rate and the total heat release were both somewhat reduced, with a peak heat release rate drop of 17.61%. The flame retardant performance of sample 4 was not greatly improved, and the peak heat release rate and the decrease in the total heat release amount were not high. The flame retardant property of the flame retardant PLA composite of sample 5 was greatly improved. The peak value of the heat release rate of the sample 5 reaches 313kW/m2The total heat release amount reaches 54MJ/m2. Compared with pure PLA, the peak value of the heat release rate is reduced by 28.38%, the total heat release amount is reduced by 26.23%, and the carbon residue rate reaches 16.1%.
In conclusion, the synergistic flame retardant effect among MCA, APP and MCC in the microcapsule flame retardant is good, and the flame retardant property of the flame-retardant PLA composite material is greatly improved.
Experimental example 5
The samples 0 to 5 in Experimental example 4 were subjected to a limiting oxygen index test using a limiting oxygen index apparatus manufactured by Dynisco of America, and the test bars were 80 mm. times.6.5 mm. times.3 mm in size, and the standard was GB/T2406.2-2009. The Limiting Oxygen Index (LOI) test results obtained are shown in table 3.
TABLE 3
As can be seen from Table 3, the limiting oxygen index of pure PLA is only 19%, the limiting oxygen index of polylactic acid after adding the flame retardant component is improved, and the limiting oxygen index of the flame retardant polylactic acid obtained after adding the microcapsule intumescent flame retardant in sample 5 is improved to 31.5%. The microcapsule intumescent flame retardant can obviously improve the flame retardant property of polylactic acid, although the flame retardant property of polylactic acid can be improved by adding other APP and MCC blending modes, the flame retardant effect is obviously lower than that of the microcapsule intumescent flame retardant, so that the synergistic flame retardant effect of various components of the microcapsule intumescent flame retardant is shown, the flame retardant efficiency is greatly improved, and the flame retardant effect of polylactic acid is obviously improved.
Experimental example 6 vertical Combustion test
The samples 0, 1, 2, 4 and 5 in the experimental example 4 were subjected to a vertical combustion test, respectively, to measure the combustion performance thereof, and the test specimen was subjected to a UL94 test with a standard of GB/T2408-2008 using an CZF-3 type vertical combustion meter of the analytical instrument factory. The test data results are shown in table 4.
TABLE 4
After the pure PLA is ignited for the first time, the pure PLA is ignited rapidly and burns violently, the situation of the drop of the molten drops is serious in the burning process, the drop of the molten drops is connected into a piece, and the absorbent cotton at the lower part is ignited rapidly. When the flame drops along with the molten drops and is separated from the PLA, the flame on the PLA is extinguished, and the second ignition is carried out. After the second ignition, the flame burns violently, the molten droplets drip seriously, and the flame does not extinguish until the PLA is completely burnt out, and is not rated in the vertical burning test.
After the first ignition of sample 1, the sample strips extinguished after 6.9s, the dripping of the molten droplets was improved but still more serious, and the dropped molten droplets ignited the cotton wool. After the second ignition, the bars quickly extinguished after 3.9s, a significant improvement over pure PLA, rated V-2 in the vertical burn test. After the first ignition of sample 2, the bars extinguished after 5.6s, the droplet was improved but still severe compared to sample 1, and the cotton wool at the bottom was ignited. After the second ignition, the bars extinguish after 3.1s, rating V-2 in the vertical burn test.
Sample 4, t of the sample bar after MCA was introduced into the system to form an intumescent flame retardant system1Is 6.3s, t21.7s, the condition of molten drops is further improved, the absorbent cotton at the bottom can still be ignited, the flame retardant property of the polylactic acid composite material is further improved, and the flame retardant property of the polylactic acid composite material is V-2 grade in a vertical burning test.
Sample 5, t of sample bar after addition of microencapsulated intumescent flame retardant1Is 1.3s, t2The flame retardant property of the polylactic acid composite material is remarkably improved, the flame retardant property is 0.9s, after ignition, the sample strips are self-extinguished, the molten drops are slightly dropped and almost not dropped, absorbent cotton at the bottom is not ignited, and the flame retardant property is V-0 grade in a vertical combustion test.
From the above, the microcapsule intumescent flame retardant can better promote the carbon forming performance of PLA, a compact and fluffy carbon layer is formed on the surface of the substrate to isolate oxygen and heat, and N generated by MCA decomposition2And NH3O which dilutes the combustion atmosphere2And the heat is taken away, the heat and substance transfer of combustion is hindered, the polylactic acid matrix is better protected, and the flame retardant property of the polylactic acid matrix is improved.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The microcapsule intumescent flame retardant is characterized in that the flame retardant is prepared from a core material and a capsule material coated on the core material, the core material is prepared from an acid source and a carbon source, and the capsule material is prepared from an air source.
2. The microencapsulated intumescent flame retardant of claim 1,
the acid source is selected from one or more of ammonium polyphosphate, melamine polyphosphate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid and melamine cyanurate;
the carbon source is one or a mixture of more of microcrystalline cellulose, pentaerythritol, dipentaerythritol, chitosan and starch;
the gas source is one or more selected from melamine cyanurate, melamine, dicyandiamide and urea.
3. The microcapsule intumescent flame retardant of claim 1, wherein the mass ratio of the acid source to the carbon source is (2-8): 1, the mass ratio of the gas source to the carbon source is (1-6): 1.
4. the microencapsulated intumescent flame retardant of claim 2, wherein the acid source is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-succinic acid and/or ammonium polyphosphate,
the carbon source is microcrystalline cellulose,
the gas source is melamine cyanurate.
5. A preparation method of a microcapsule intumescent flame retardant is characterized by comprising the following steps: mixing an acid source and a carbon source to prepare a core material; and coating a capsule material formed by an air source on the surface of the core material to obtain the microcapsule intumescent flame retardant.
6. The method of claim 5, wherein the acid source is DDP and the mixing of the acid source and the carbon source to produce the core material comprises: dissolving an acid source in a solvent to obtain a solution I, dispersing a carbon source in the solvent to obtain a solution II, adding the solution II into the solution I to obtain a mixed solution, cooling, stirring, and centrifugally drying to obtain the core material with the carbon source coated by the acid source.
7. The method of claim 5, wherein the acid source is ammonium polyphosphate, and the mixing of the acid source and the carbon source to prepare the core material comprises: and mixing and dispersing the acid source and the carbon source in a solvent, ball-milling and mixing, and centrifugally drying to obtain the core material with the carbon source coated by the acid source.
8. The method of claim 5, wherein the gas source is melamine cyanurate, which is prepared from melamine and cyanuric acid,
the process of coating the surface of the core material with the capsule material formed by the air source comprises the following steps: dispersing the core material in a solvent, adding cyanuric acid, then adding melamine dispersion liquid, reacting, and centrifugally drying to obtain the microcapsule-coated flame retardant.
9. The method according to claim 8, wherein the reaction time is 4-12 h, preferably 8 h; the reaction temperature is 70-100 ℃, and preferably 80-90 ℃.
10. Use of the microencapsulated intumescent flame retardant prepared according to any one of claims 1 to 4 or according to any one of claims 5 to 9 in polylactic acid, characterized in that the microencapsulated intumescent flame retardant is mixed with polylactic acid and extruded through a twin-screw extruder to obtain flame-retardant polylactic acid.
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