CN110218508B - Epoxy acrylate flame-retardant material containing phosphate intercalation layered hydroxide of zinc, aluminum and tin and preparation method thereof - Google Patents
Epoxy acrylate flame-retardant material containing phosphate intercalation layered hydroxide of zinc, aluminum and tin and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses an epoxy acrylate flame retardant material of phosphate intercalation layered hydroxide containing zinc, aluminum and tin and a preparation method thereof, wherein the phosphate intercalation layered hydroxide containing zinc, aluminum and tin is prepared and is used as a char forming catalyst and a flame retardant to be compounded with zinc chloride, acrylamide, acrylic acid and epoxy acrylate to prepare the epoxy acrylate intumescent flame retardant material containing phosphorus, nitrogen, zinc, aluminum and tin, the epoxy acrylate intumescent flame retardant material is a low-addition high-flame retardant acrylate transparent material, and is combined with phosphorus and metal Lewis acid to synergistically catalyze EA coating to generate a uniform porous carbon foam layer when burning so as to play roles of oxygen isolation, heat insulation, smoke suppression, molten drop prevention and the like, thereby not only improving the flame retardant property of the epoxy acrylate flame retardant material, but also improving the mechanical property of the epoxy acrylate flame retardant material, and the preparation method is simple and low in cost, and can be used in the field of decorative type fireproof flame retardant coatings of wooden furniture and ancient wood buildings, has wide market prospect.
Description
Technical Field
The invention belongs to the technical field of epoxy acrylate flame-retardant materials, and particularly relates to an epoxy acrylate flame-retardant material containing phosphate intercalation layered hydroxide of zinc, aluminum and tin and a preparation method thereof.
Background
The transparent fireproof coating is a decorative fireproof coating which is developed according to the requirement of fire prevention and can keep the appearance of a base material, and can be used for protecting the surfaces of ancient buildings, living furniture and cloth ornaments without changing the appearance and the color of the ancient buildings, living furniture and cloth ornaments, can expand when encountering fire and form a uniform and compact cellular or spongy carbon foam layer, has good protection effect on combustible substances, prevents the combustible substances from being damaged by the fire, has important effect in fire prevention safety measures, and has huge market prospect. Because the acrylate resin has the advantages of environmental protection, excellent mechanical property and the like compared with urea formaldehyde and melamine resin, especially the UV curing acrylate resin has the characteristics of excellent weather resistance, good heat resistance, good chemical contamination resistance, environmental protection, energy conservation, fast curing, light color, water white, high transparency and the like, the research of the UV curing flame retardant acrylate transparent coating becomes a hotspot. But the acrylic resin is extremely easy to burn and has a poor fireproof effect. Therefore, the development of a novel transparent acrylate fireproof coating which is environment-friendly, weather-resistant and excellent in mechanical and physical properties is urgently needed. Due to the poor stability of the coating systems, no product with a service life of more than 3 years is currently on the market. Although the UV-cured EA coating has high transparency, the flame-retardant effect is poor, and the application of the UV-cured EA coating is limited, so that the research on a new preparation method or a new preparation process for improving the flame-retardant property of the UV-cured EA coating becomes one of the research hotspots of the coating at present. The existing method for improving the flame retardant property of the UV curing EA coating comprises a flame retardant adding method and an active flame retardant monomer adding method, and the latter method can avoid the adverse effects of short flame retardant timeliness, easy migration of the flame retardant and the like brought by the former method and improve the material property to a certain extent, so that the method is the main method for improving the flame retardant property of the UV curing EA coating at present.
At present, a P or Si-containing flame-retardant active monomer (or oligomer) is synthesized on the market and copolymerized with acrylate to prepare a UV-cured transparent flame-retardant coating, so that the flame-retardant property of the coating is improved to a certain extent, and the defects of poor compatibility with a polymer base material, negative influence on the physical and mechanical properties of a material, easy migration loss of an additive, poor flame-retardant long-acting property and the like existing in an additive type flame-retardant method are overcome. However, when the phosphorus content is high, the material is internally plasticized, and the mechanical properties are reduced. On the other hand, from the research report of artificially synthesized hydrotalcite flame retardant, most researches are limited to single interlayer intercalation, so that the obtained flame-retardant hydrotalcite is not enough in flame-retardant and smoke-eliminating effects when being singly used as the flame retardant, and the practical use requirements can be met only by mixing the flame-retardant hydrotalcite with other flame retardants. Therefore, there is a need for continued research and improvement thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an epoxy acrylate flame retardant material containing phosphate intercalation layered hydroxide of zinc, aluminum and tin and a preparation method thereof.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a preparation method of phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin is characterized by simultaneously dropwise adding a mixed aqueous solution of sodium hydroxide and sodium metaaluminate and a mixed aqueous solution of tin chloride and zinc chloride into a disodium hydrogen phosphate aqueous solution, stirring at normal temperature for 20-40 min after dropwise adding is completed, adjusting the pH value to 10-12, aging at 75-85 ℃ for 10-14 h, carrying out solid-liquid separation, washing the solid part until the pH value of a washing solution is 7-8, and drying to obtain the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin.
In one embodiment: in the phosphate group insertion layer type layered hydroxide containing zinc, aluminum and tin, the molar ratio of Zn, Al, Sn and PO 4 is 7-8: 1.5-2.5: 0.8-1.2.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin prepared by the preparation method.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
an application of the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin in a flame retardant material.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows:
the epoxy acrylate flame retardant material applying the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin comprises the following components in parts by weight: the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin is not more than 12 parts, zinc chloride is 2.5-15 parts, acrylamide is 18-22 parts, acrylic acid is 13-17 parts, and epoxy acrylate is 30-65 parts.
In one embodiment: the method comprises the following steps of: 9-11 parts of phosphate intercalation layered hydroxide containing zinc, aluminum and tin, 9-11 parts of zinc chloride, 19-21 parts of acrylamide, 14-16 parts of acrylic acid and 40-42 parts of epoxy acrylate.
In one embodiment: further comprising: 3-5 parts of an initiator.
In one embodiment: the initiator is a photoinitiator 1173.
The fifth technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the epoxy acrylate flame-retardant material comprises the following steps: and dispersing and dissolving the acrylamide in the acrylic acid, and then uniformly dispersing the zinc chloride, the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin and the epoxy acrylate in sequence.
Compared with the background technology, the technical scheme has the following advantages:
in order to improve the thermal stability and the flame retardance of an Epoxy Acrylate (EA) coating, the invention organically combines the design of a transparent fireproof coating, molecular design, nano flame retardance, catalytic carbonization of metal acid radical ions, expansion flame retardance and the like to prepare a layered hydroxide nanorod with a phosphate radical intercalation and containing metal ions such as Zn, Al, Sn and the like, uses the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin as a carbonization catalyst and a flame retardant, is compounded with zinc chloride, acrylamide and acrylic acid, is assisted with a proper acid source and a proper gas source to design a synergistic expansion flame retardant system, then compounds the synergistic flame retardant system with epoxy acrylate to prepare the epoxy acrylate expansion flame retardant material containing phosphorus, nitrogen, zinc, aluminum and tin through ultraviolet curing, is a low-addition high-flame-retardant acrylate transparent material, and combines phosphorus and metal Lewis acid to synergistically catalyze the combustion of the EA coating to generate a uniform porous carbon foam layer, the zinc-aluminum-tin-containing phosphate radical intercalation layered hydroxide, the compound synergistic expansion flame-retardant system thereof and the epoxy acrylic acid expansion flame-retardant material containing phosphorus, nitrogen, zinc, aluminum and tin have the advantages of simple preparation method, low cost, good flame retardance and mechanical property, can be used in the field of decorative type fireproof flame-retardant coatings of wooden furniture and ancient wood buildings, and has wide market prospect.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is Zn7.5Al2Sn2PO4SEM picture of-LDH.
FIG. 2 shows Zn7.5Al2Sn2PO4Of LDHAnd (4) an infrared spectrum.
Fig. 3 is a picture of carbon residue after combustion of a coating of an epoxy acrylate flame retardant material to which a phosphate-intercalated layered hydroxide containing zinc, aluminum and tin is applied, wherein the left picture is sample 56, and the right picture is a comparison graph of samples 55, 56 and 57 in sequence from left to right.
FIG. 4 is an infrared spectrum of a sample 56 of an epoxy acrylate flame retardant material employing a phosphate-intercalated layered hydroxide containing zinc aluminum tin before and after UV curing, where a-before curing; b-after curing.
Fig. 5 is an infrared spectrum of sample 56 of an epoxy acrylate flame retardant material employing a phosphate-intercalated layered hydroxide containing zinc aluminum tin at different UV cure times.
Fig. 6 is a relation between the double bond conversion rate and the curing time of the epoxy acrylate flame retardant material applying the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin.
Fig. 7 is a coating light transmittance of an epoxy acrylate flame retardant material employing a phosphate-intercalated layered hydroxide containing zinc aluminum tin.
Fig. 8 is a TG curve of a coating of an epoxy acrylate flame retardant material to which a phosphate-insertion layered hydroxide containing zinc aluminum tin is applied.
Fig. 9 is a heat release rate curve for a coating of an epoxy acrylate flame retardant material that employs a phosphate-insertion layered hydroxide containing zinc aluminum tin.
FIG. 10 is a thermal degradation infrared spectrum of sample No. 56 of an epoxy acrylate flame retardant material applying a phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin at 25-600 ℃.
Detailed Description
The present invention will be described in detail with reference to the following examples:
the reagents and instrumentation used in the following examples are as follows:
sodium AR metaaluminate (NaAlO)2) Tianjin chemical reagent wholesale company; AR phosphoric acid, chemical reagent wholesale company of Tianjin; AR Acrylic Acid (AA), shin & re fine chemical research institute of tianjin; AR sodium dihydrogen phosphate (NaH)2PO4) Chemical reagent batch of TianjinA company; AR stannous chloride (SnCl)2) Tianjin, Maotai chemical reagent; AR Zinc chloride (ZnCl)2) Zhongshantou Hao Fine Chemicals, Shantou city; AR Acrylamide (AM), chemical reagent wholesale company, tianjin; AR sodium hydroxide (NaOH), chemical reagent wholesale company, tianjin; AR Darocur 1173, national pharmaceutical group chemical agents ltd; AR Epoxy Acrylate (EA), Shanghai reagent III. UV2250 UV/visible spectrophotometer, shimadzu corporation; a UV-1KW portable UV curing light source; baodingda electronics limited; JCZ-1 cone calorimeter, Jiangning district analytical Instrument factory, Nanjing; tencor 27 fourier type infrared spectrometer, BRUKER, germany; SXZ-4-10 box type resistance furnace, Shanghai Ministry electric furnace Co., Ltd; QHQ-A hardness tester, Tianjin ViidA tester; WC-5400UL-94 vertical horizontal burning test machine, Kunshan Wancheng test apparatus Co., Ltd; HC-2 oxygen index determinator, Wuhan Gerilomo detection devices, Inc.; SDT2960 thermogravimetric analyzer, usa.
Example 1: preparation of phosphate intercalation layered hydroxide containing zinc, aluminum and tin
Respectively weighing 0.025mol of sodium metaaluminate and 0.025mol of sodium hydroxide, dissolving in 7.2mL of deionized water to prepare a 10% sodium hydroxide and 20% sodium metaaluminate aqueous solution (A); weighing 0.025mol of stannic chloride and 0.9375mol of zinc chloride, and dissolving in 100mL of deionized water to prepare stannic chloride and zinc chloride aqueous solution (B); 0.0125mol of disodium hydrogen phosphate is weighed and dissolved in deionized water of l00ml to prepare a sodium salt aqueous solution (C).
Pouring the solution (C) into a 250mL three-neck round-bottom flask at room temperature, slowly dropping the solution (A) and the solution (B) into the solution (C) by using a dropping funnel under the stirring of an electric stirrer, stirring for half an hour at room temperature after the dropping is finished, adjusting the pH value of the reaction solution to 10-12 by using an aqueous solution of sodium hydroxide, aging for 12 hours in a water bath kettle at 80 ℃, filtering, washing with water until the pH value is about 7-8, leaching, soaking with a small amount of deionized water, washing the precipitate, drying at 80 ℃, and grinding to obtain the phosphate radical intercalation layered hydroxide Zn containing zinc, aluminum and tin7.5Al2Sn2PO4LDH, in which Zn, Al, Sn and PO4The molar weight ratio of the substances (1) is 7.5:2:2: 1.
Example 2: preparation of epoxy acrylate flame retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
Preparing 10g of flame-retardant coating according to a formula in a table 1, firstly weighing 20 parts of Acrylamide (AM), ultrasonically dissolving the Acrylamide (AM) in 15 parts of Acrylic Acid (AA) for 30min by using a 1000-watt ultrasonic cleaner, and then dispersing and dissolving 2.5-15 parts of ZnCl2Dissolving the zinc-aluminum-tin-containing phosphate radical intercalation layered hydroxide Zn in the solution by ultrasonic treatment for 10min, and then adding 0-10 parts of the zinc-aluminum-tin-containing phosphate radical intercalation layered hydroxide Zn prepared in the example 17.5Al2Sn2PO4And (3) dispersing the LDH in the acrylic acid solution dissolved with zinc chloride and acrylamide by using an ultrasonic cleaner for about 20min, finally adding 36-61 parts of Epoxy Acrylate (EA), then dispersing and dissolving the EA by using an ultrasonic cleaner for 30min until the system is uniform, then carrying out ultrasonic oscillation for about 20min to eliminate bubbles and disperse the EA uniformly, finally adding 4 parts of 1173 photoinitiator, and carrying out ultrasonic oscillation for 30min to eliminate bubbles and disperse the dispersed EA uniformly to obtain the epoxy acrylate flame retardant material using the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin, which is an intumescent flame retardant epoxy acrylate flame retardant system containing phosphorus, nitrogen, zinc, aluminum and tin elements.
Preparing a coating: wiping a clean and dry glass plate by absolute ethyl alcohol, and sticking a label. A100-micron wet film preparation device is used for preparing a coating with the thickness of 100 microns (the strip is prepared by pouring the coating into a mold with a certain length and width to fill the mold with the coating), an ultraviolet lamp is turned on to preheat for 1min and then is used for curing the coating, and the coating and a sample strip are cured by irradiation for later use. The curing time was about 15 seconds, with the specific curing time being determined based on the composition and shade of the sample.
TABLE 1 formulation of epoxy acrylate flame retardant materials using phosphate insertion layered hydroxides containing zinc, aluminum and tin
Example 3: morphology analysis of phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
FIG. 1 is Zn7.5Al2Sn2PO4SEM picture of-LDH. As can be seen from fig. 1: it is a nano-rod structure, with a diameter of about 20nm and a length of about 200 nm.
Example 4: infrared spectrum of phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin
An infrared spectrometer is used for measuring the wavelength of 4000-500 cm-1Internal test the infrared spectrum of the product prepared in example 1, a small sample was taken with KBr according to a 1: grinding uniformly at the ratio of 40, and tabletting for detection. To test the properties of the resultant product and to monitor the photocuring kinetics of the coating. And judging a synthesized product through the change condition of the absorption peaks under different wavelengths, and observing the change of each absorption peak to judge the change condition of each group in different active monomers and UV curing coating films. The C ═ C double bond conversion can be calculated according to the following formula:
wherein: a. the0、AtThe peak areas of the C ═ C double bond peak at t ═ 0 and t respectively; s0、StThe peak areas of the C ═ O peak at t ═ 0 and t, respectively.
FIG. 2 shows Zn7.5Al2Sn2PO4-infrared spectrum of LDH-type hydrotalcite. As can be seen from fig. 2: at 1028.84cm-1A characteristic absorption peak of phosphate radical is present nearby and is 1365cm-1The vibration characteristic absorption peak of nitrate radical exists nearby, and is 1640cm-1A vibration absorption peak of water molecules appears nearby; at 2422cm-1To generate CO2Characteristic stretching vibration peak of (1); at 3416cm-1The characteristic absorption peak of-OH exists at 531cm-1Characteristic absorption peaks of-O-M-O (M ═ Zn, Al and Sn) on the surface of the plate layer appear, and the phosphate intercalation layered hydroxide containing zinc, aluminum and tin is prepared by the analysis and experiment.
Example 5: physical properties of epoxy acrylate flame retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
The pencil hardness was measured by measuring the hardness of the coating film of the sample of example 2 using GB/T6739 as a measurement standard to determine the effect of different contents, monomers and auxiliaries on the hardness of the coating film. The test method comprises the following steps: fixing the glass sheet of the cured product on the horizontal plane of a hardness tester, grinding the pencil lead to form a tetrahedron-like pencil lead, and placing the tetrahedron-like pencil lead on the hardness tester by using a section to form an angle of 45 degrees with the paint film of the cured product at about 1 mm.s-1The speed of (2) is slowly advanced. The pencils were selected starting with the hardest, five strokes per grade of lead, until five strokes did not scratch the cured product film, the hardness of the pencils being representative of the hardness of the cured film measured. The hardness range of the pencil is 6B-6H, and 6H is the maximum hardness.
The water absorption of the coatings to be tested was determined according to the standard of GB/T1733-1993 "determination of Water resistance of paint films". Cutting the cured coating films with different contents, monomers and additives, drying and weighing to obtain M1Soaking in a beaker filled with deionized water for 24h, wiping off surface water, and weighing to obtain M2The water absorption W was calculated according to the following formula:
TABLE 2 mechanical and physical properties of epoxy acrylate flame retardant materials using phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
Samples 55 to 63 all contained Zn7.5Al2Sn2PO4Research on the EA coating with flame retardance of the synergistic intumescent flame retardant system finds that when the layered hydroxide contains Sn and Zn, the metal Sn has the function of catalyzing a polymer to form carbon, is beneficial to increasing the toughness of a carbon layer, avoids the carbon layer from cracking while generating the carbon layer, and enables gas generated by combustion to be retained in the carbon layerThe oxygen can be effectively isolated, and the transfer of a heat source is inhibited. Thereby improving the carbon residue rate.
By comparing the carbon residue ratio and the expansion factor, the following can be obtained: adding proper amount of Zn7.5Al2Sn2PO4LDH and zinc chloride, which have an optimum value for the carbon residue rate and the expansion factor. The reason is that metal ions such as zinc, aluminum, tin and the like can catalyze the polymer into carbon when burning, and the gas source generated by burning expands the carbon layer catalyzed by the gas source; meanwhile, the chlorine ions can generate chlorine free radicals at high temperature, so that hydrogen free radicals of flame can be eliminated, a gas-phase flame retardant effect is achieved, heat transfer is hindered, and the flame retardant effect of the layered hydroxide is remarkably improved. The optimal mixture ratio of the components is as follows: zn7.5Al2Sn2PO4The contents of-LDH, zinc chloride, acrylamide, acrylic acid, photoinitiator 1173 and EA are respectively: 10%, 20%, 15%, 4% and 41%, the burning carbon residue rate of the prepared EA coating can reach 57.10%, the hardness can reach 6H, the water absorption rate is 16.21%, and Zn is known7.5Al2Sn2PO4The LDH and the zinc chloride have certain synergistic flame retardant effect.
Containing Zn7.5Al2Sn2PO4EA coating hardness of LDH is greater than without Zn7.5Al2Sn2PO4Of LDH. Because the layered hydroxide is rigid particles, the layered hydroxide can play a role of physical cross-linking points and improve the hardness of the coating, and is easily dispersed in a system, the formed coating is compact, and the hardness is improved. At the same time, as the layered hydroxide content in the EA coating increases, the water absorption also increases.
Example 6: flame retardant property of epoxy acrylate flame retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
The product obtained in example 2 was subjected to a Limiting Oxygen Index (LOI) test on an HC-2 type oxygen index apparatus according to GB/T2406-93: flame length: about 10 mm. Ignition time: 30 s; criterion is as follows: combustion length: 40mm, namely 30s of ignition, the spline can not burn, or the combustion length is less than 40mm although the spline can burn, the oxygen concentration is low, and the spline needs to be adjusted to a high position; if the sample is ignited within 30s and the burning length of the sample exceeds 40mm, the oxygen concentration is high and the temperature needs to be lowered. The test was conducted until a critical oxygen concentration was found, which was taken as the limiting oxygen index of the sample.
The vertical burning (UL-94) test was carried out on a WC-5400 type horizontal vertical burning tester according to the standard of GB 2408-80. The dimensions of the sample strips are 100X 12.7X 3mm3。
FIG. 3 is a photograph of carbon residue after combustion of a portion of the coating prepared. From the comparison of samples 55, 56, 57, it can be seen that when zinc chloride and Zn are used7.5Al2Sn2PO4The carbon residue expansion effect is best when the content of the-LDH is 10%. At the moment, Zn and Sn jointly catalyze the polymer into carbon, and simultaneously, the metal Sn is beneficial to increasing the toughness of the carbon layer, so that the carbon layer is prevented from cracking, gas generated by combustion is kept in the carbon layer, oxygen is effectively isolated, the transfer of a heat source is inhibited, and the carbon residue rate is improved; meanwhile, the chloride ions can generate chlorine free radicals at high temperature, and can eliminate hydrogen and hydroxyl free radicals of flame, thereby playing a role in gas-phase flame retardance and obviously improving the flame retardant effect of the coating.
TABLE 3 limiting oxygen index and vertical burn of epoxy acrylate flame retardant materials employing phosphate-intercalated layered hydroxides containing zinc aluminum tin
As can be seen from Table 3, the limiting oxygen index of sample 56 was the greatest and the vertical burn rating reached V-0. This is consistent with the above-mentioned char formation rate and expansion factor, and also indicates Zn7.5Al2Sn2PO4the-LDH and the zinc chloride have good synergistic flame retardant effect and can obviously improve the flame retardant property of the coating.
Example 7: curing rate of epoxy acrylate flame-retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
FIG. 4 shows sample No. 56 containing 10% Zn7.5Al2Sn2PO4-EA coating of LDH infrared spectrum, as can be seen, at 1641cm with increasing curing time of the coating-1The characteristic absorption peak of C ═ C double bond is gradually reduced; at a wavelength of 3380cm-1Evaporating part of water on the surface or inside of the crystal; wavelength of 1274cm-1The cleavage of P ═ O and C ═ C crosslink. The light transmittance of the coating tends to be flat when the curing time is 15s, namely the characteristic absorption peak of C ═ C double bonds is not obvious, namely the coating is basically cured, and the C ═ C double bonds are basically disappeared. The coating cure tends to be complete.
FIG. 5 is an infrared spectrum of sample 56, as can be seen, at 1640.5cm as the cure time of the coating increases-1The characteristic absorption peak of C ═ C double bond is gradually reduced; the light transmission flattens out when the curing time of the coating is 15s, i.e. the characteristic absorption peak for the C ═ C double bonds is not already apparent, i.e. the coating has substantially finished curing and its C ═ C double bonds have substantially disappeared. The coating cure tends to be complete.
FIG. 6 shows the double bond conversion of a UV cured coating as monitored by infrared spectroscopy, which increases with time and then levels off. Before 5s, the system is in a cross-linked network structure, so that the migration of macromolecular free radicals is inhibited, the number of free radicals in the system is increased, and further the conversion rate is increased. However, as the irradiation time of ultraviolet light increases, the conversion rate of the double bond gradually slows down, and the conversion rate tends to be stable. When the curing time is 15s, the double bond conversion rate reaches 82.65%. The curing is substantially complete.
Example 8: light transmittance of epoxy acrylate flame-retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
And measuring the UV-Vis absorption transmission spectrum of the sample coating film with different contents, monomers and additives in the range of 200-800 nm by using an ultraviolet/visible spectrophotometer.
FIG. 7 shows that in the visible light region of 400-800 nm, the transmittance of the coating is averagely over 85%, and the transmittance is better; but with Zn7.5Al2Sn2PO4The content of LDH in the coating increases and the transmission of the coating in the visible region decreases slightly.
Example 9: thermogravimetric (TG) analysis of epoxy acrylate flame retardant materials containing phosphate-intercalated layered hydroxides of zinc, aluminum and tin
The thermal stability of the cured coatings prepared was studied by thermogravimetric analysis, using a model SDT2960 thermogravimetric analyzer, of the sample coatings. Can be measured in the air, the temperature is controlled between 25 ℃ and 800 ℃, and the unit of the temperature rise speed is 10 ℃ min-1。
FIG. 8 is a TG curve of a UV cured intumescent flame retardant epoxy acrylate flame retardant coating containing phosphorus, nitrogen, zinc, aluminum and tin elements reflecting the weight percent of coating versus temperature for different formulations. As can be seen, Zn is contained7.5Al2Sn2PO4The thermal degradation process of the EA coating of the LDH can be divided into three stages, wherein the temperature of the first stage is 0-240 ℃, the weight loss of the coating is very small, and the thermal degradation process is caused by evaporation of a small part of water in the coating; the temperature of the second stage is 240-500 ℃, the degradation speed of the stage is high, and the weight percentage of the coating is reduced quickly because the polymer is decomposed into carbon dioxide, carbon monoxide and the like; the temperature of the third stage is 500-800 ℃, and the degradation of the coating tends to be slow. Because the phosphate radicals in the coating are decomposed by combustion to generate polyphosphoric acid and other strong acidic substances, the hydroxyl-containing organic substances in the coating are dehydrated and carbonized, and a porous organic carbon layer is formed under the action of an air source; meanwhile, metal ions are catalyzed to form carbon, the carbon layer is expanded by gas generated by combustion, and chlorine ions can generate chlorine free radicals at high temperature, so that the hydrogen free radicals of flame can be eliminated, the gas-phase flame-retardant effect is achieved, the heat transfer is hindered, and the coating is protected. Through the synergistic flame retardance of metal ions, phosphate radicals and chloride ions, Zn is obtained7.5Al2Sn2PO4The contents of-LDH, zinc chloride and acrylamide are respectively: 10%, 10% and 20%, the coating reached a maximum of 53.30% by weight at 800 ℃.
Example 10: analysis of heat release rate of epoxy acrylate flame retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
The test is carried out according to ISO 5660 standard in JCZ-1 cone calorimeter method, and the size of the test sample is100×100×3mm3The radiant heat flux used in the test was 35 kW.m-2。
FIG. 9 is a graph showing the variation of heat release rate of UV cured intumescent flame retardant epoxy acrylate flame retardant coatings containing phosphorus, nitrogen, zinc, aluminum and tin, as measured by a cone calorimeter, reflecting the relationship of heat release rate of the coatings with time for different formulations. As can be seen from FIG. 9, when Zn is present7.5Al2Sn2PO4EA coatings with 10%, 7%, 3% LDH content and coatings with only zinc chloride and EA with peak heat release rates down to 215kW · m-2、241kW·m-2、259kW·m-2And 285kW m-2. It can be seen that Zn is contained at the same time7.5Al2Sn2PO4-LDH and ZnCl2The peak value of the heat release rate of the flame-retardant coating is low, which shows that the metal ions, phosphate radicals and chloride ions in the coating can obviously reduce the combustion strength of the coating and improve the flame-retardant property of the coating.
Example 11: dynamic infrared analysis of epoxy acrylate flame retardant material containing phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin
The method comprises the steps of measuring samples at different calcination temperatures on a Fourier infrared spectrometer, monitoring the dynamic process of thermal degradation of the samples by using real-time infrared spectroscopy, and recording the structural change of the samples in real time, wherein the temperature rise rate of the samples is 10 ℃ min-1。
FIG. 10 shows a graph containing 10% Zn7.5Al2Sn2PO4An EA coating of the-LDH has a thermal degradation infrared spectrogram at 25-600 ℃, and a curve is relatively stable under an infrared spectrum with an absorption value of 400 ℃, namely the coating has better thermal stability at 400 ℃. The wavelength is 3380cm at 150 DEG C-1The characteristic peak of water disappears, indicating that the heat released by the coating volatilizes water molecules. At 1274cm-1Characteristic absorption peak and 1164cm of-1The characteristic absorption peak of C-O-P is obvious before 290 ℃, and the peaks at two positions at 310 ℃ disappear gradually, because phosphate radicals are combusted and decomposed to generate strong acidic substances such as polyphosphoric acid and the like. At a wavelength of 2812cm-1Having a-CH function at 310 DEG CThe front wave peak is larger, the wave peak becomes smaller along with the combustion, and the wave peak still exists at 600 ℃. Because the metal ions and phosphate radicals in the coating catalyze the coating to form carbon during combustion, and simultaneously, the gas source generated by combustion expands the coating, so that the-CH functional group in the coating is protected. The coating has good flame retardant effect at high temperature.
And (4) conclusion: the invention synthesizes phosphate radical intercalation layered hydroxide Zn containing zinc, aluminum and tin by a coprecipitation method7.5Al2Sn2PO4LDH, and use of the Zn7.5Al2Sn2PO4The epoxy acrylate flame-retardant material is prepared by LDH, and the light transmittance, the oxygen index, the thermal degradation behavior, the heat release rate, the mechanical property and the like of the coating of the epoxy acrylate flame-retardant material are represented by an ultraviolet-visible spectrophotometry and oxygen index tester, a thermogravimetric analyzer, an infrared and cone calorimeter, a mechanical tester and the like, so that the optimal formula of the flame-retardant coating is determined, and the flame-retardant mechanism of the flame-retardant coating is proved. The results show that: when Zn7.5Al2Sn2PO4The contents of-LDH, zinc chloride, acrylamide, acrylic acid, photoinitiator 1173 and EA are respectively: 10%, 20%, 15%, 4% and 41%, the burning carbon residue rate of the prepared EA coating is up to 57.10%, the hardness is up to 6H, the water absorption rate is 16.21%, the LOI is up to 46, the vertical burning level is V-0 level, the peak heat release rate is the lowest, and is 215 kW.m-2And the carbon layer has the best expansion effect, and the expansion multiple is 300 times. Zinc chloride and Zn7.5Al2Sn2PO4The LDH has a synergistic flame retardant effect on the EA coating. The intumescent flame-retardant coating prepared under the optimal process conditions has excellent flame-retardant and mechanical properties, and the Zn7.5Al2Sn2PO4The formula of the-LDH and the flame-retardant EA material thereof is simple, the preparation cost is low, and the flame-retardant effect is obvious. Zinc chloride Zn7.5Al2Sn2PO4The LDH has good synergistic flame retardant effect on the EA coating.
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 and their equivalents.
Claims (4)
1. The epoxy acrylate flame-retardant material containing phosphate intercalation layered hydroxide containing zinc, aluminum and tin is characterized by comprising the following components in parts by mass: 9-11 parts of phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin, 9-11 parts of zinc chloride, 19-21 parts of acrylamide, 14-16 parts of acrylic acid and 40-42 parts of epoxy acrylate, wherein in the phosphate radical intercalation layered hydroxide containing zinc, aluminum, Sn and PO4The molar ratio of the substances is 7-8: 1.5-2.5: 0.8-1.2, the preparation method of the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin comprises the steps of simultaneously dropwise adding a mixed aqueous solution of sodium hydroxide and sodium metaaluminate and a mixed aqueous solution of tin chloride and zinc chloride into a disodium hydrogen phosphate aqueous solution, stirring for 20-40 min at normal temperature after dropwise adding, adjusting the pH value to 10-12, aging for 10-14 h at 75-85 ℃, carrying out solid-liquid separation, washing a solid part until the pH value of a washing solution is 7-8, and drying to obtain the phosphate radical intercalation layered hydroxide containing zinc, aluminum and tin.
2. The epoxy acrylate flame retardant material containing phosphate-intercalated layered hydroxide of zinc aluminum tin according to claim 1, characterized in that: further comprising: 3-5 parts of an initiator.
3. The epoxy acrylate flame retardant material containing phosphate-intercalated layered hydroxide of zinc aluminum tin according to claim 2, characterized in that: the initiator is a photoinitiator 1173.
4. A preparation method of the epoxy acrylate flame retardant material containing the zinc-aluminum-tin phosphate insertion layer layered hydroxide, which is described in any one of claims 1 to 3, is characterized by comprising the following steps: and dispersing and dissolving the acrylamide in the acrylic acid, and then uniformly dispersing the zinc chloride, the phosphate insertion layer type layered hydroxide containing zinc, aluminum and tin and the epoxy acrylate in sequence.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5994447A (en) * | 1996-12-10 | 1999-11-30 | Daihan Paint & Ink Co., Ltd. | Organic-inorganic complex composition for coating metal surface |
| CN1215130C (en) * | 2000-01-17 | 2005-08-17 | Dsmip财产有限公司 | Curable compsn. contg. reactive melamine derivative, cured product, and laminate |
| EP1778413A1 (en) * | 2004-08-03 | 2007-05-02 | Chemetall GmbH | Process for coating metallic surfaces with an anti-corrosive coating |
| CN101035630A (en) * | 2004-08-03 | 2007-09-12 | 坎梅陶尔股份有限公司 | Process for coating metallic surfaces with an anti-corrosive coating |
| CN105008466A (en) * | 2013-03-08 | 2015-10-28 | 比克化学有限公司 | Process for providing metallic substrates with corrosion resistance |
| CN105038521A (en) * | 2015-07-23 | 2015-11-11 | 莆田学院 | Metal-silica sol expanding flame-retardant coating and preparing method thereof |
| CN105131688A (en) * | 2015-09-17 | 2015-12-09 | 莆田学院 | Tin ion contained liquid flame retardant and photo-curing intumescent flame retarding coating applying flame retardant |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100813953B1 (en) * | 2002-04-22 | 2008-03-14 | 삼성전자주식회사 | Ultraviolet-curing composition having antistatic property |
| US20110213065A1 (en) * | 2008-11-23 | 2011-09-01 | Albemarle Corporation | Synthetic inorganic flame retardants, methods for their preparation, and their use as flame retardants |
| CN101503581B (en) * | 2009-03-09 | 2011-06-29 | 中国科学技术大学 | Radiation curable expansion type flame-retardant transparent nano composite coating and preparation thereof |
| CN101775100B (en) * | 2010-02-12 | 2012-05-23 | 长兴化学材料(珠海)有限公司 | Acrylic ester/laminated double hydroxide nanometer composite material and preparation method thereof |
| CN103159238B (en) * | 2013-03-20 | 2015-03-04 | 北京化工大学 | Nano-size layered composite hydroxide and step-by-step precipitation preparation method thereof |
| CN104130638B (en) * | 2014-07-18 | 2016-08-24 | 安徽千和新材料科技发展有限公司 | A kind of aqueous fire-proof corrosion resistant paint for steel structure and preparation method thereof |
-
2019
- 2019-04-23 CN CN201910329122.8A patent/CN110218508B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5994447A (en) * | 1996-12-10 | 1999-11-30 | Daihan Paint & Ink Co., Ltd. | Organic-inorganic complex composition for coating metal surface |
| CN1215130C (en) * | 2000-01-17 | 2005-08-17 | Dsmip财产有限公司 | Curable compsn. contg. reactive melamine derivative, cured product, and laminate |
| EP1778413A1 (en) * | 2004-08-03 | 2007-05-02 | Chemetall GmbH | Process for coating metallic surfaces with an anti-corrosive coating |
| CN101035630A (en) * | 2004-08-03 | 2007-09-12 | 坎梅陶尔股份有限公司 | Process for coating metallic surfaces with an anti-corrosive coating |
| CN105008466A (en) * | 2013-03-08 | 2015-10-28 | 比克化学有限公司 | Process for providing metallic substrates with corrosion resistance |
| CN105038521A (en) * | 2015-07-23 | 2015-11-11 | 莆田学院 | Metal-silica sol expanding flame-retardant coating and preparing method thereof |
| CN105131688A (en) * | 2015-09-17 | 2015-12-09 | 莆田学院 | Tin ion contained liquid flame retardant and photo-curing intumescent flame retarding coating applying flame retardant |
| CN105131688B (en) * | 2015-09-17 | 2017-08-29 | 莆田学院 | A kind of photocuring expandable flame retardant coating of stanniferous ionic liquid fire retardant and the application fire retardant |
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