CN113831597A - Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same - Google Patents
Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same Download PDFInfo
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Abstract
The invention discloses a bio-based macromolecular modified nano zirconium phosphate flame retardant, which is prepared by firstly adsorbing piperazine on the surface of cyclodextrin by utilizing the positive and negative electric attraction of the piperazine and the cyclodextrin and then introducing nano zirconium phosphate to modify the surface of the cyclodextrin. The flame retardant can effectively solve the problem that zirconium phosphate is easy to agglomerate, can effectively improve the compatibility with resin and the thermal stability, can play a synergistic flame-retardant role with an intumescent flame-retardant system in the fireproof coating, forms a carbon-nitrogen-phosphorus-zirconium synergistic flame-retardant effect, and can obviously improve the film-forming property, the fire resistance, the durability and the like of the obtained fireproof coating. The flame retardant provided by the invention integrates flame retardance, smoke suppression and enhancement functions, and has the advantages of low halogen-free cost, good char formation, high carbon layer strength, environmental friendliness, wide applicability, simple related preparation method process, mild reaction conditions and suitability for popularization and application.
Description
Technical Field
The invention belongs to the technical field of flame-retardant smoke-suppressing additives and fireproof coatings, and particularly relates to a bio-based macromolecular modified nano zirconium phosphate flame retardant and a fireproof coating prepared by using the same.
Background
Two-dimensional layered nano material alpha-zirconium phosphate (alpha-ZrP) is of great interest due to its excellent chemical properties, thermal stability, acid and alkali resistance and potentially high catalytic performance, and is often used as a flame retardant additive for polymers. alpha-ZrP is used as an artificially synthesized layered inorganic substance with a regular structure, has the characteristics of adjustable length-diameter ratio, narrow particle size distribution and the like, and is considered to be one of excellent matrixes for preparing polymer inorganic nano composite materials. The layered zirconium phosphate not only has the commonality of layered compounds, but also has the characteristics which other layered compounds do not have, such as larger ion exchange space, easy intercalation and stripping, adjustable interlayer spacing, solid acid characteristic and the like; meanwhile, because the zirconium phosphate layer is rich in Lewis acid points, the zirconium phosphate has good catalytic carbonization effect on various polymers, so that the zirconium phosphate has unique advantages in the field of polymer flame retardance. Although zirconium phosphate has a layered barrier effect and a solid acid catalytic carbonization effect, the flame retardance of the flame retardant can be obviously improved, but the currently reported flame retardant system has the problems of poor thermal stability, low flame retardant efficiency and the like due to the fact that the carbon layer is loose and zirconium phosphate is easy to agglomerate, and the catalytic carbonization efficiency of zirconium phosphate is limited.
In order to solve the problems that the flame retardant efficiency is limited because zirconium phosphate can not efficiently catalyze the polymer to form carbon; in patent CN108203519A, methylamine is used to intercalate zirconium phosphate and strip into sheets, nano-sheet zirconium phosphate is added in the MCA synthesis process, and zirconium phosphate is used as a synergist to be applied in PA6 composite materials. However, the problem that zirconium phosphate nano-sheets are easy to agglomerate is not solved in the patent, so that the catalytic carbonization of zirconium phosphate cannot be effectively released, and meanwhile, the problem of compatibility with resin is not considered, so that the flame retardant efficiency is still not ideal. Therefore, the further optimization of the modification means and the performance of the zirconium phosphate compound has important research and application significance.
Disclosure of Invention
The invention mainly aims to solve the problems of poor char quality, low loose strength of a char layer, low flame retardant efficiency and the like of the existing flame retardant, and provides a bio-based macromolecular modified nano-zirconium phosphate flame retardant, wherein piperazine is adsorbed on the surface of cyclodextrin by utilizing the positive and negative electric attraction effect of the piperazine and the cyclodextrin, and then nano-zirconium phosphate is introduced to modify the surface of the cyclodextrin, so that the bio-based macromolecular modified nano-zirconium phosphate flame retardant is prepared; the intumescent fire-retardant coating is applied to preparation of intumescent fire-retardant coatings, can show the advantages of excellent char forming property, good film forming property, long fire-resistant time, good water resistance and durability, short drying time, environmental friendliness and the like, and the related preparation process is simple, the reaction condition is mild, and the intumescent fire-retardant coating is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
a bio-based macromolecule modified nano zirconium phosphate flame retardant is prepared by the following steps:
1) dissolving piperazine in an alcohol-water solution, adding cyclodextrin, stirring for reaction, filtering, and collecting a solid product;
2) dispersing the solid product obtained in the step 1) in 1, 4-dioxane, adding nano zirconium phosphate, mechanically stirring at a certain temperature, centrifugally washing, and drying to obtain the bio-based macromolecular modified nano zirconium phosphate flame retardant.
In the scheme, the volume ratio of the alcohol solvent to water adopted in the alcohol-water solvent is 1: 5-10: 1.
In the scheme, the alcohol solvent can be one or more of absolute ethyl alcohol, absolute methyl alcohol, isopropanol and the like.
In the scheme, the dissolving step adopts ultrasonic dissolving conditions, and the temperature is 20-50 ℃.
In the scheme, the stirring reaction time in the step 1) is 6-18h, and the reaction temperature is 40-90 ℃.
In the scheme, the molar ratio of the piperazine to the cyclodextrin is 1: 3-10: 1.
In the above scheme, the nano zirconium phosphate is alpha-zirconium phosphate (alpha-ZrP); the particle size is 50-900 nm.
In the scheme, the mechanical stirring temperature in the step 2) is 30-95 ℃, and the time is 12-24 h.
In the scheme, the molar ratio of the nano zirconium phosphate introduced in the step 2) to the piperazine introduced in the step 1) is 5: 1-1: 10.
In the scheme, in the step 2), the washing step comprises washing with acetone for 2-3 times, washing with ethanol for 2-3 times and washing with water for 2-3 times in sequence.
The environment-friendly flame retardant obtained by the scheme is applied to preparation of the intumescent fire-retardant coating, and comprises the following components in percentage by mass: 20-30% of high polymer emulsion, 30-36% of ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octanol, 1-10% of flame retardant of bio-based macromolecule modified nano zirconium phosphate, and the balance of water.
Preferably, the mass percentage of the flame retardant of the bio-based macromolecule modified nano zirconium phosphate is 3.5-5.5%, and under the condition of a lower mixing amount of the flame retardant, excellent flame retardant performance can be realized, and better comprehensive performance is also considered.
In the scheme, the high polymer emulsion is one or more of pure acrylic emulsion, methacrylate modified core-shell emulsion, water-based epoxy resin emulsion and derivative new emulsion obtained by modifying the three emulsions.
The intumescent fire-retardant coating prepared according to the scheme has the advantages of excellent fire-resistant and smoke-suppression performance, good durable waterproof performance, low halogen-free cost, good char forming property, high carbon layer strength, environmental friendliness and wide applicability.
The principle of the invention is as follows:
the method comprises the steps of firstly, adsorbing piperazine on the surface of bio-based macromolecular cyclodextrin by utilizing the positive and negative electric attraction effect of the piperazine and the cyclodextrin, and then coating the surface of the bio-based macromolecular cyclodextrin by utilizing nano zirconium phosphate, so that the thermal decomposition temperature of the cyclodextrin is increased, and meanwhile, the piperazine with excellent char formation and the cyclodextrin containing a large number of hydroxyl groups are catalyzed and carbonized by the solid acid effect of the nano zirconium phosphate at high temperature, so that a compact and high-strength carbon layer can be formed, and the effects of heat insulation and oxygen isolation are achieved;
the flame retardant is applied to preparing a fireproof coating, when a fire disaster happens, pentaerythritol in the fireproof coating reacts with ammonium polyphosphate at high temperature, dehydration and carbonization are carried out, melamine is heated and decomposed to release non-combustible gas, a honeycomb-shaped carbon layer is formed, and the flame retardant effect is played; the bio-based flame retardant disclosed by the invention can quickly form carbon on the surface of a base material while playing a flame retardant role, fills gaps among loose carbon layers of a coating, forms a plurality of dense micro-nano carbon cages, blocks oxygen in air, seals a large amount of degradation products, simultaneously introduces piperazine to act in the micro carbon cages, and has a cross-linked space network structure with high thermal stability due to the synergistic flame retardant reaction of zirconium phosphate, piperazine and cyclodextrin, so that the graphitization degree of the carbon layers is further improved, the P-N-Zr synergistic effect can be realized, the carbon layer strength of the carbon cages can be effectively improved, the flame retardant role is further played on the level of the micro structure, and the flame retardant role and an expansion flame retardant system in the fireproof coating play a synergistic flame retardant role and improve the durability of the carbon cages.
Compared with the prior art, the invention has the beneficial effects that:
1) the problem of agglomeration of zirconium phosphate is fully solved by modifying the zirconium phosphate with the bio-based macromolecular cyclodextrin, and the high-efficiency flame retardance and excellent char formation of piperazine and an expansion system consisting of ammonium polyphosphate, pentaerythritol and melamine in the fireproof coating exert a synergistic flame retardant effect, so that the fireproof coating forms a combustion carbon layer with high graphitization degree, high strength and compactness, and has high-efficiency flame retardance.
2) Modification of the bio-based macromolecular cyclodextrin on the surface of zirconium phosphate improves the environmental friendliness of the zirconium phosphate flame retardant, the synthesis cost is lower, the preparation method is simple, convenient and quick, and the method is suitable for industrialization.
3) The surface of the zirconium phosphate sheet layer is grafted and modified by cyclodextrin and piperazine, so that the surface polarity of the zirconium phosphate can be effectively reduced, the surface uniformity of the zirconium phosphate and the zirconium phosphate can be ensured, the components of the fireproof coating can be effectively simplified, the compatibility and the dispersibility among the components of the coating are better, the film forming property and the practicability of the coating can be improved, and the fireproof performance of the fireproof coating can be further effectively improved.
4) The heterocycle in the piperazine and the polyhydroxy cyclodextrin can be used as a charring agent when a polymer matrix is burnt or degraded, play a role in delaying the thermal decomposition of the polymer and the like, can jointly play a role in phosphorus, nitrogen and zirconium, play a role in synergistic charring and flame retardance and the like, so that the obtained flame retardant has better thermal stability and durability, and can effectively improve the flame retardance of the intumescent fire-retardant coating.
5) The flame retardant provided by the invention integrates flame retardance, smoke suppression and enhancement functions, is low in halogen-free cost, excellent in char forming property, high in carbon layer strength, environment-friendly and wide in applicability, and the related preparation method is simple in process, mild in reaction conditions and suitable for popularization and application.
6) The fireproof coating prepared by the invention integrates flame retardance, smoke suppression and environment friendliness, and has the advantages of high carbon layer strength, good compactness, simple and convenient preparation method, easiness in molding, mild reaction conditions and wide application field.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the adopted zirconium phosphates are all alpha-zirconium phosphates, which specifically include the following preparation steps: 100mL of concentrated phosphoric acid with a molar concentration of 3mo1/L was prepared, and added to a 250mL three-necked flask, 10.00g of zirconium oxychloride (ZrOCl) was added2-8H20) Heating to 95 ℃, mechanically stirring for 20min to fully disperse zirconium oxychloride, stopping stirring, reacting at a reflux temperature for 24h, standing the obtained mixed solution after the reaction is finished, naturally cooling to normal temperature, pouring out the supernatant, performing centrifugal treatment (10000r/min, 10min) on the milky precipitate at the lower layer for solid-liquid separation, washing the obtained solid product with a proper amount of deionized water, performing centrifugal treatment again, and repeating the steps until the centrifugal clear liquid meets the pH requirement>5, the washed solid product was dried in an oven at 80 ℃ for 12 hours and then ground to give a white powder of zirconium phosphate having an average particle size of about 90 nm.
Example 1
A preparation method of a bio-based macromolecular modified nano zirconium phosphate flame retardant comprises the following steps:
1) ultrasonically dissolving 0.1mol of piperazine in 150ml of mixed solution formed by absolute ethyl alcohol and water (the volume ratio is 1:2) at 30 ℃, then adding 0.1mol of cyclodextrin, mechanically stirring, reacting for 12 hours at 50 ℃, filtering after the reaction is finished, and collecting a solid product;
2) mechanically stirring the solid product obtained in the step 1) and 0.1mol of nano zirconium phosphate at 60 ℃ for 16h, centrifuging, and then sequentially washing with acetone for 2-3 times, ethanol for 2-3 times and water for 2-3 times; drying for 24h at 80 ℃ to obtain the bio-based macromolecular modified nano zirconium phosphate flame retardant.
Example 2
A preparation method of a bio-based macromolecular modified nano zirconium phosphate flame retardant comprises the following steps:
1) ultrasonically dissolving 0.2mol of piperazine in 200ml of mixed solution formed by absolute ethyl alcohol and water (the volume ratio is 1:2) at 35 ℃, then adding 0.1mol of cyclodextrin, mechanically stirring, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and collecting a solid product;
2) mechanically stirring the solid product obtained in the step 1) and 0.2mol of nano zirconium phosphate at 50 ℃ for 12 hours, centrifuging, washing for 2-3 times by using acetone, washing for 2-3 times by using ethanol and washing for 2-3 times by using water; drying for 24h at 80 ℃ to obtain the bio-based macromolecular modified nano zirconium phosphate flame retardant.
Application example 1
The flame retardant obtained in the embodiment 1 is applied to the preparation of an acrylate-based intumescent fire retardant coating, and the specific steps include:
1) weighing the raw materials according to the mixture ratio, wherein the components and the mass percentage thereof comprise: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 10% of water and 5% of flame retardant of bio-based macromolecule modified nano zirconium phosphate;
2) grinding the weighed ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide and hydroxyethyl cellulose into powder, and then adding water to fully grind and uniformly mix; adding the defoaming agent and the dispersing agent, and continuously and fully grinding;
3) and finally, adding a graphitized carbon nitride composite intercalation modified zirconium phosphate flame retardant, methacrylic acid modified acrylate emulsion and n-octanol, fully grinding and uniformly mixing to obtain the fireproof coating.
Application example 2
The preparation method of the fireproof coating in application example 2 is substantially the same as that in application example 1, except that the fireproof coating comprises the following components in percentage by mass: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 12% of water and 3% of flame retardant of bio-based macromolecule modified nano zirconium phosphate.
Application example 3
The preparation method of the fireproof coating in application example 3 is substantially the same as that of application example 1, except that: the components and the mass percentage thereof are as follows: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 13% of water and 2% of flame retardant of bio-based macromolecule modified nano zirconium phosphate.
Comparative example 1
Comparative example 1 the fire retardant coating was prepared in substantially the same manner as in application example 1, except that: the components and the mass percentage thereof are as follows: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol and 15% of water.
Comparative example 2
The fire retardant coating of comparative example 2 was prepared in substantially the same manner as in application example 1, except that: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 10% of water and 5% of zirconium phosphate.
Comparative example 3
The fire retardant coating of comparative example 3 was prepared in substantially the same manner as in application example 1, except that: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 10% of water and 5% of cyclodextrin.
Comparative example 4
Comparative example 4 the fire retardant coating was prepared in substantially the same manner as in application example 1, except that: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 3% of titanium dioxide, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol, 10% of water and 5% of mixture of cyclodextrin and zirconium phosphate (3% of zirconium phosphate and 2% of cyclodextrin).
The intumescent fire-retardant coatings obtained in application examples 1-3 and comparative examples 1-4 were respectively subjected to fire resistance tests, and the results are shown in table 1.
TABLE 1 relevant Performance test of the intumescent coatings obtained in application examples 1-3 and comparative examples 1-4
The above results show that: the flame retardant obtained by the invention has the advantages of good flame retardant efficiency, high char yield of the base material, excellent comprehensive performance, good resin compatibility, good durability, environmental friendliness, no damage to other properties of the material, and wide applicability.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A preparation method of a bio-based macromolecule modified nano zirconium phosphate flame retardant is characterized by comprising the following steps:
1) dissolving piperazine in an alcohol-water solution, adding cyclodextrin, stirring for reaction, filtering, and collecting a solid product;
2) dispersing the solid product obtained in the step 1) in 1, 4-dioxane, adding nano zirconium phosphate, mechanically stirring at a certain temperature, centrifugally washing, and drying to obtain the bio-based macromolecular modified nano zirconium phosphate flame retardant.
2. The preparation method according to claim 1, wherein the volume ratio of the alcohol solvent to water in the alcohol-water solvent is 1:5 to 10: 1.
3. The preparation method according to claim 2, wherein the alcohol solvent is one or more of absolute ethyl alcohol, absolute methyl alcohol and isopropanol.
4. The preparation method according to claim 1, wherein the stirring reaction time in the step 1) is 6 to 18 hours, and the reaction temperature is 40 to 90 ℃.
5. The preparation method according to claim 1, wherein the molar ratio of the piperazine to the cyclodextrin is 1:3 to 10: 1.
6. The preparation method of claim 1, wherein the molar ratio of the nano zirconium phosphate introduced in the step 2) to the piperazine introduced in the step 1) is 5:1 to 1: 10.
7. The process according to claim 1, wherein the mechanical stirring is carried out at a temperature of 30 to 95 ℃ for 12 to 24 hours.
8. The bio-based macromolecule modified nano zirconium phosphate flame retardant prepared by the preparation method of any one of claims 1 to 7.
9. The application of the bio-based macromolecular modified nano zirconium phosphate flame retardant in intumescent fire-retardant coating as claimed in claim 8, wherein the components and the mass percentages thereof comprise: 20-30% of high polymer emulsion, 30-36% of ammonium polyphosphate, 10-20% of pentaerythritol, 10-15% of melamine, 1-5% of titanium dioxide, 0.5-1% of hydroxyethyl cellulose, 0.5-1% of dispersing agent, 0.5-1% of defoaming agent, 0.5-1% of n-octanol, 1-10% of flame retardant of bio-based macromolecule modified nano zirconium phosphate, and the balance of water.
10. The use of claim 9, wherein the flame retardant of the bio-based macromolecule modified nano zirconium phosphate is 3.5-5.5% by mass.
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