CN110511434B - Preparation method and application of polyphosphazene-containing coated silver-doped halloysite nanotube composite material - Google Patents
Preparation method and application of polyphosphazene-containing coated silver-doped halloysite nanotube composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a polyphosphazene-containing coated silver-doped halloysite nanotube composite material, which comprises the following steps: (1) uniformly dispersing the halloysite nanotube and silver nitrate in an organic mixed solvent; (2) slowly adding octadecenoic acid and oleylamine into the dispersion, and performing ultrasonic dispersion; (3) magnetically stirring the material obtained in the step (2), adding ascorbic acid, and continuing to magnetically stir for reaction; (4) washing with the organic mixed solvent to remove free nano silver particles, and drying in vacuum to constant weight to obtain the silver-loaded halloysite nanotube; (5) ultrasonically dispersing the silver-loaded halloysite nanotube in acetonitrile, and then sequentially adding a double-end amine compound and triethylamine for stirring; (6) slowly adding acetonitrile solution of hexachlorocyclotriphosphazene, and stirring for condensation polymerization reaction; (7) washing with anhydrous ethanol, and vacuum drying to constant weight.
Description
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to a preparation method and application of a polyphosphazene-containing coated silver-doped halloysite nanotube composite material.
Background
Halloysite, as a natural low-valent clay nanotube, is formed by curling kaolinite sheets composed of double-layer 1: 1 type aluminosilicate, wherein the inner layer is an aluminum octahedron, the outer layer is a silicon-oxygen tetrahedron, the lattices of the inner layer and the outer layer are staggered and curled, and crystal water exists between the layers. The molecular formula of which is Al2Si2O5(OH)4·nH2O (n is 0 or 2), and generally has an outer diameter of 40 to 100nm and a length of about 0.2 to 3 um. In addition, the halloysite nanotube with porous property is also used as a flame retardant, is applied to high polymer materials such as polyurethane, nylon 6, epoxy resin and the like, and plays roles of anti-dripping, smoke suppression and carbon formation promotion. Meanwhile, because the halloysite nanotube has a longer length-diameter ratio and the elastic modulus of a single nanotube can reach 140GPa, the force of a polymer material can be effectively improved while the high-performance polymer nanocomposite is preparedThe theory and the like.
Polyphosphazenes are organic-inorganic macromolecules with P, N atoms as main chains by single-double bond conjugation and alternation, and have 2 organic side groups, organic metal or inorganic side groups connected with each phosphorus atom on the main chains. The polycyclic polyphosphazene high polymer composed of the phosphazene compound has extremely high thermal stability and is an important high-temperature-resistant flame-retardant high polymer material.
The poor fire resistance of most polymer materials seriously affects their widespread use in many fields. In order to improve the flame-retardant properties of polymer materials without affecting their mechanical properties. Therefore, it is necessary to design a functional flame retardant which can improve the mechanical properties of the polymer material and simultaneously has a good flame retardant effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a polyphosphazene-containing coated silver-doped halloysite nanotube composite material.
The invention also aims to provide application of the silver-doped halloysite nanotube composite material containing the polyphosphazene coating.
The technical scheme of the invention is as follows:
a preparation method of a polyphosphazene-containing coated silver-doped halloysite nanotube composite material comprises the following steps:
(1) uniformly dispersing halloysite nanotubes and silver nitrate in an organic mixed solvent consisting of any two of toluene, ethanol and methanol to obtain a dispersion liquid;
(2) slowly adding octadecenoic acid and oleylamine into the dispersion, and performing ultrasonic dispersion;
(3) magnetically stirring the material obtained in the step (2) at 50-60 ℃, then adding ascorbic acid, and continuing to magnetically stir for reaction for 30-40 min;
(4) washing the material obtained in the step (3) by using the organic mixed solvent to remove free nano silver particles, and then drying the material in vacuum at the temperature of 40-70 ℃ to constant weight to obtain a silver-loaded halloysite nanotube;
(5) ultrasonically dispersing the silver-loaded halloysite nanotube in acetonitrile, and then sequentially adding a double-end amine compound and triethylamine for stirring; the double-end amine compound is 4, 4' -diamino diphenyl sulfone or 4, 4-diamino diphenyl methane;
(6) slowly adding acetonitrile solution of hexachlorocyclotriphosphazene into the material obtained in the step (5), and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 h;
(7) and (3) washing the material obtained in the step (6) by using absolute ethyl alcohol, and then drying the material at 40-80 ℃ in vacuum to constant weight to obtain the polyphosphazene-containing coated silver-doped halloysite nanotube composite material.
In a preferred embodiment of the invention, the halloysite nanotubes have the formula Al2Si2O5(OH)4·2H2O, diameter of 30-70 nanometers, length of 1-3 microns.
In a preferred embodiment of the present invention, the volume ratio of the two solvents in the organic mixed solvent is 0.8-1.2: 0.8-1.2.
In a preferred embodiment of the present invention, in the step (1), the mass ratio of the halloysite nanotubes to the silver nitrate is 1-2: 2-4.
In a preferred embodiment of the present invention, in the step (2), the volume ratio of octadecenoic acid and oleylamine is 2-5: 2-5.
In a preferred embodiment of the invention, the ratio of halloysite nanotubes, silver nitrate, octadecenoic acid and oleylamine is 0.01-0.02g:0.02-0.04g:0.2-0.5 mL.
The application of the polyphosphazene-containing coated silver-doped halloysite nanotube composite material prepared by the preparation method in preparing a flame-retardant polymer material.
In a preferred embodiment of the present invention, the polymer in the flame retardant polymer material is bisphenol a epoxy resin type E51 or polylactic acid.
The application of the polyphosphazene-containing coated silver-doped halloysite nanotube composite material prepared by the preparation method in improving the mechanical property of a flame-retardant polymer material.
In a preferred embodiment of the present invention, the polymer in the flame retardant polymer material is bisphenol a epoxy resin type E51 or polylactic acid.
The invention has the beneficial effects that:
1. the raw materials of the polyphosphazene-containing coated silver-doped halloysite nanotube composite material are low in price and easy to obtain, and the composite material is easy to synthesize and prepare.
2. The polyphosphazene polymer serving as the shell layer can fully play a role in capturing free radicals, inhibiting combustion and promoting carbon formation and diluting gas during combustion. Meanwhile, the porous clay halloysite nanotube containing crystal water can not only dilute combustible gas during combustion, but also lock part of small-molecular organic volatile gas due to the porous characteristic of the porous clay halloysite nanotube to reduce smoke, and the halloysite nanotube can reduce mass and energy transfer by forming physical barriers when being compounded with polymers, so that the flame-retardant synergistic effect is achieved.
3. In the invention, metal ions are introduced into the tube of the porous HNT through reduction, thereby effectively avoiding the agglomeration of the metal ions outside the tube under high combustion temperature, and playing a role in effectively catalyzing and reducing toxic gas while partially locking smoke, thereby achieving the effect of purifying smoke and releasing.
4. The prepared polyphosphazene-containing coated silver-doped halloysite nanotube composite material can effectively improve the mechanical property of a polymer, and can achieve the double-layer effect of interpenetration of a condensed phase and a gas phase flame retardant by reducing the transfer of substance energy, promoting the catalytic carbonization and purifying toxic gases such as CO gas, thereby having good application prospects in the aspects of flame retardance, reinforcement and the like of high polymer materials.
Drawings
FIG. 1 is a TEM image of a polyphosphazene-coated silver-doped halloysite nanotube composite obtained in example 1 of the present invention.
Fig. 2 is an infrared spectrum (FT-IR) of the silver-doped halloysite nanotube composite containing polyphosphazene coating obtained in example 1 of the present invention.
FIG. 3 is a comparison graph of CO absorption in a thermal red coupling analysis of pure epoxy resin obtained in example 2 of the present invention and 5 wt% of a polyphosphazene-containing coated silver-doped halloysite nanotube composite/epoxy resin.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Preparing silver-loaded halloysite nanotubes: metal Ag is doped into the halloysite nanotube cavity, and the method specifically comprises the following steps: adding halloysite nanotubes 0.015-0.03 g and silver nitrate 0.025-0.05 g into a reaction container, and dispersing in V(ethanol)∶V(toluene)1: 1 organic mixed solvent; slowly adding 0.4-0.8 mL of octadecenoic acid and 0.4-0.8 mL of oleylamine into the dispersion liquid, and performing ultrasonic dispersion for about 10-15 min; thirdly, placing the dispersion liquid to be reacted at 50-60 ℃ and carrying out magnetic stirring at 600rpm, then adding ascorbic acid, and continuing stirring and reacting for 30-40 min; centrifugally washing the reacted product with the organic solvent for multiple times respectively to remove free nano silver particles outside the tubular shape, and then carrying out vacuum drying on the washed product at the temperature of 40-70 ℃ to constant weight to obtain brown solid, namely the silver-loaded halloysite nanotube;
(2) polyphosphazene-coated silver-doped halloysite nanotubes: coating the polyphosphazene polymer with the silver-loaded halloysite nanotube obtained in the step (1), wherein the method specifically comprises the following steps: fifthly, placing 0.1g to 0.2g of silver-loaded halloysite nanotube into 50mL to 100mL of acetonitrile solvent with analytical purity, carrying out ultrasonic dispersion in an ultrasonic machine with the ultrasonic power of 90w for 30min, and sequentially adding 0.03mol to 0.06mol of amine terminated substance and 2mL to 6mL of triethylamine into the solution for stirring; sixthly, slowly dripping acetonitrile solution (0.01g/mL-0.03g/mL) dissolved with hexachlorocyclotriphosphazene into the solution, and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 hours; seventhly, centrifuging and washing the reaction product for multiple times by using absolute ethyl alcohol, and drying the reaction product in vacuum at the temperature of 40-80 ℃ until the weight of the reaction product is constant to obtain a grey brown solid, namely the silver-doped halloysite nanotube composite material containing polyphosphazene coating as shown in figures 1 and 2.
Example 2
The preparation and flame retardant test procedures of the pure epoxy resin and the epoxy resin modified by the polyphosphazene-coated silver-doped halloysite nanotube composite material obtained in example 1 are as follows.
(1) Preparation of pure epoxy resins
Weighing 20g of epoxy resin E-51, heating to 80 ℃, adding 5g of curing agent 4, 4' -diaminodiphenylmethane, stirring uniformly, vacuumizing to remove bubbles, pouring into a preheated mold, and sequentially carrying out temperature programming according to the following temperature and time: 120 ℃/3h, 140 ℃/4h and 180 ℃/5 h.
(2) Preparation of epoxy resin by modification of polyphosphazene-coated silver-doped halloysite nanotube composite graphene obtained in example 1
Weighing 20g of epoxy resin E51, heating to 80 ℃, weighing 0.2g of silver-doped halloysite nanotube coated by polyphosphazene, performing ultrasonic dispersion for 30min by using an acetone solvent, then slowly adding the epoxy resin, removing the solvent acetone in vacuum, adding 5g of curing agent 4, 4' -diaminodiphenylmethane, stirring uniformly, pouring into a mold, performing gradient heating curing for 120 ℃/3h, 140 ℃/4h and 180 ℃/5h, and finally obtaining the silver-doped halloysite nanotube modified epoxy resin containing polyphosphazene reading, wherein the content of the flame retardant is 1 wt% (corresponding to EP-1 wt% in Table 1). According to this method, a modified epoxy resin was prepared by adding 0.6g, 1g, and 1.4g, respectively, of polyphosphazene-coated silver-doped halloysite nanotubes to 20g of an epoxy resin, wherein the reactive flame retardant content was 3 wt%, 5 wt%, and 7 wt%, respectively (corresponding to EP-3 wt%, EP-5 wt%, and EP-7 wt%, respectively, in Table 1).
The obtained sample is tested for oxygen index according to the GB/T2406.2-2009 method
The results of the Limiting Oxygen Index (LOI) tests on the polyphosphazene-coated silver-doped halloysite nanotube-modified epoxy resin of example 2 of the present invention are summarized in table 1.
The flexural modulus and flexural strength of the polyphosphazene-containing coated silver-doped halloysite nanotube-modified epoxy resin of example 2 were measured by three-point bending are shown in table 1.
Thermogravimetry-infrared combined analysis is carried out on pure epoxy resin and 5 wt% of polyphosphazene-containing polymer modified silver-doped halloysite nanotube/epoxy resin to obtain a CO absorption contrast spectrum, as shown in figure 3.
Example 3
The pure polylactic acid and the preparation and flame retardant test procedure of the polyphosphazene-coated silver-doped halloysite nanotube/polylactic acid obtained in example 1 are as follows.
(1) Preparation of pure polylactic acid
And (3) placing 100g of PLA in a forced air drying oven at 80 ℃ for drying for 6h, banburying for 10min at 175 ℃ and 100r/min of rotating speed, and carrying out mould pressing on the banburied sample at 185 ℃ by using a flat vulcanizing machine to form a plate with the thickness of 3.2mm and cutting the plate into standard sample strips for later use.
(2) Modification preparation of polylactic acid by using polyphosphazene-coated silver-doped halloysite nanotube obtained in example 1 of the invention
100g of PLA and 5g of the polyphosphazene-coated silver-doped halloysite nanotube are placed in an air drying oven at 80 ℃ for drying for 6h, the PLA and the polyphosphazene-coated silver-doped halloysite nanotube are mixed according to the proportion, then the mixture is subjected to banburying for 10min at the temperature of 175 ℃ and the rotating speed of 100r/min, a banburied sample is subjected to mould pressing at 185 ℃ by using a flat vulcanizing machine to form a plate with the thickness of 3.2mm, and the plate is cut into standard sample strips for later use, so that the flame-retardant polylactic acid is obtained, wherein the content of the polyphosphazene-coated silver-.
The limiting oxygen indexes of pure polylactic acid and the polylactic acid/polyphosphazene-containing coated silver-doped halloysite nanotubes are respectively 20.7 percent and 31.0 percent according to GB/T2406-2009.
Comparative example 1
Weighing 20g of epoxy resin E51, heating to 80 ℃, respectively weighing 0.2g, 0.6g, 1g and 1.4g of unmodified halloysite nanotubes, using solvent acetone and carrying out ultrasonic dispersion for 30min, then slowly adding the mixture into the epoxy resin, removing the solvent acetone under vacuum, adding 5g of curing agent 4, 4' -diaminodiphenylmethane, uniformly stirring, pouring the mixture into a mold, carrying out gradient heating curing for 120 ℃/3h, 140 ℃/4h and 180 ℃/5h, and finally obtaining the unmodified halloysite nanotube/epoxy resin composite material, wherein the content of the flame retardant unmodified halloysite nanotubes is respectively 1 wt%, 3 wt%, 5 wt% and 7 wt% (corresponding to EP-1HNT, EP-3HNT, EP-5HNT and EP-7HNT in the table 2). The samples of the comparative examples were also tested for their oxygen index as described in example 3, with reference to the method of GB/T2406.2-2009, and the results of the limiting oxygen index testing of the unmodified halloysite nanotube/epoxy composite are also collated in table 2. Also, the flexural modulus of the unmodified halloysite nanotube/epoxy composite for the three-point bending test is also collated in table 2.
Comparative example 2
And (2) placing 100g of PLA and 3g of unmodified halloysite nanotubes in a 80 ℃ forced air drying oven for drying for 6h, mixing the PLA and the unmodified halloysite nanotubes according to the mixture ratio, banburying for 10min at the temperature of 175 ℃ and the rotating speed of 100r/min, molding the banburied sample into a 3.2mm thick plate by using a flat vulcanizing machine at the temperature of 185 ℃, and cutting the plate into standard sample strips for later use to obtain the flame-retardant polylactic acid, wherein the content of the unmodified halloysite nanotubes is 3 wt%.
The limiting oxygen index of the polylactic acid/HNT is 25.4 percent according to GB/T2406-2009
TABLE 1 Limiting Oxygen Index (LOI) and flexural Strength Table for polyphosphazene-containing coated silver-doped halloysite nanotubes/epoxy resins
TABLE 2 Limiting Oxygen Index (LOI) and flexural Strength Table for unmodified halloysite nanotubes/epoxy
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. A preparation method of a polyphosphazene-containing coated silver-doped halloysite nanotube composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly dispersing halloysite nanotubes and silver nitrate in an organic mixed solvent consisting of any two of toluene, ethanol and methanol to obtain a dispersion liquid; the molecular formula of the halloysite nanotube is Al2Si2O5（OH）4·2H2O, diameter of 30-70 nanometers and length of 1-3 microns;
(2) slowly adding octadecenoic acid and oleylamine into the dispersion, and performing ultrasonic dispersion;
(3) magnetically stirring the material obtained in the step (2) at 50-60 ℃, then adding ascorbic acid, and continuing to magnetically stir for reaction for 30-40 min;
(4) washing the material obtained in the step (3) by using the organic mixed solvent to remove free nano silver particles, and then drying the material in vacuum at the temperature of 40-70 ℃ to constant weight to obtain a silver-loaded halloysite nanotube;
(5) ultrasonically dispersing the silver-loaded halloysite nanotube in acetonitrile, and then sequentially adding a double-end amine compound and triethylamine for stirring; the double-end amine compound is 4, 4' -diamino diphenyl sulfone or 4, 4-diamino diphenyl methane;
(6) slowly adding acetonitrile solution of hexachlorocyclotriphosphazene into the material obtained in the step (5), and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 h;
(7) and (3) washing the material obtained in the step (6) by using absolute ethyl alcohol, and then drying the material at 40-80 ℃ in vacuum to constant weight to obtain the polyphosphazene-containing coated silver-doped halloysite nanotube composite material.
2. The method of claim 1, wherein: the volume ratio of the two solvents in the organic mixed solvent is 0.8-1.2: 0.8-1.2.
3. The method of claim 1, wherein: in the step (1), the mass ratio of the halloysite nanotube to the silver nitrate is 1-2: 2-4.
4. The method of claim 1, wherein: in the step (2), the volume ratio of the octadecenoic acid to the oleylamine is 2-5: 2-5.
5. The method of claim 1, wherein: the ratio of the halloysite nanotube to the silver nitrate to the octadecenoic acid to the oleylamine is 0.01-0.02g to 0.02-0.04g to 0.2-0.5 mL.
6. Use of the polyphosphazene-containing coated silver-doped halloysite nanotube composite prepared by the preparation method according to any one of claims 1 to 5 for preparing a flame-retardant polymer material.
7. The use of claim 6, wherein: the polymer in the flame-retardant polymer material is E51 type bisphenol A epoxy resin or polylactic acid.
8. Use of the polyphosphazene-containing coated silver-doped halloysite nanotube composite prepared by the preparation method according to any one of claims 1 to 5 for improving the mechanical properties of flame-retardant polymer materials.
9. The use of claim 8, wherein: the polymer in the flame-retardant polymer material is E51 type bisphenol A epoxy resin or polylactic acid.
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| "聚合物包覆碳纳米管及其对环氧树脂的改性研究";凌杨;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170115;第18，44,50-51页 * |
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