CN112063019B - Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof - Google Patents
Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biomass composite ammonium polyphosphate intumescent flame retardant, a preparation method and application thereof, wherein the biomass composite ammonium polyphosphate intumescent flame retardant comprises the following raw materials in parts by weight: 65-85 parts of ammonium polyphosphate, 10.5-28 parts of starch derivatives and 4-7 parts of biomass, wherein the starch derivatives comprise one or a mixture of two of starch phosphate and starch polyphosphate, and the biomass comprises one or a mixture of more of sodium alginate, hyaluronic acid, chitosan derivatives and cellulose derivatives. In the biomass composite ammonium polyphosphate intumescent flame retardant disclosed by the invention, the starch derivative and the biomass are used as carbon sources, the biomass is subjected to high-temperature dry-heat reaction and composite crosslinking with the starch derivative, and a compact coating layer is formed on the surface of the ammonium polyphosphate.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a biomass composite ammonium polyphosphate intumescent flame retardant, and a preparation method and application thereof.
Background
The Intumescent Flame Retardant (IFR) is a novel flame retardant mainly comprising an acid source, a gas source and a carbon source, when a high polymer material is combusted, phosphoric acid generated by thermal decomposition of the acid source is used as a dehydrating agent to dehydrate and carbonize the carbon source; meanwhile, the molten system is expanded and foamed by water vapor generated by the heating reaction and non-combustible gas generated by the gas source to form an expanded carbon layer to prevent external heat and oxygen from entering a combustion area, so that the flame-retardant effect is achieved. IFR has advantages such as low smoke, low toxicity, non-corrosive gas production, becomes the focus of current fire-retardant technology development, in recent years wide application in the fire-retardant of macromolecular material.
However, for the traditional IFR, the commonly used carbon source is a polyhydroxy low molecular compound such as pentaerythritol and the like, mainly comes from petrochemical products, has the problems of poor water resistance, easy migration and the like, and has low char forming rate and flame retardant efficiency; in the prior art, the flame retardance of the high polymer material is generally improved by increasing the dosage of IFR, but the physical and mechanical properties of the high polymer material are negatively affected, and the excessive exploitation of petroleum causes the exhaustion of resources and brings about a series of environmental problems.
The biomass such as starch, cellulose, Cyclodextrin (CD), chitosan and the like is used as a green renewable resource, is a natural carbon source, has wide attention on application research, and domestic reports show that the biomass replaces the intumescent flame retardant of pentaerythritol, for example, the intumescent flame retardant prepared by using the starch or cyclodextrin and the like as the carbon source has a certain flame retardant effect, and the cost of the intumescent flame retardant can be reduced. However, most of the methods currently studied are to mix biomass as a carbon source directly with ammonium polyphosphate to prepare the flame retardant for the high polymer material, and the synergistic flame retardant effect is low. How to utilize biomass resources with abundant reserves to replace petrochemicals and combine with a flame retardant technology, and developing an environment-friendly and efficient biomass intumescent flame retardant is one of the development directions of the flame retardant technology.
Disclosure of Invention
In order to solve the defects of poor water resistance and insufficient flame retardant efficiency of the existing intumescent flame retardant, the invention provides the biomass composite ammonium polyphosphate intumescent flame retardant which is environment-friendly, small in hygroscopicity and high in flame retardant efficiency, and the technical scheme is as follows:
a biomass composite ammonium polyphosphate intumescent flame retardant comprises the following raw materials in parts by weight:
65-85 parts of ammonium polyphosphate,
10.5 to 28 parts of starch derivative,
4-7 parts of biomass, namely,
wherein the starch derivative comprises one or a mixture of two of starch phosphate and starch polyphosphate.
Preferably, the biomass comprises a mixture of one or more of sodium alginate, hyaluronic acid, chitosan derivatives, cellulose derivatives.
Preferably, the chitosan derivative comprises one or a mixture of two of carboxymethyl chitosan and carboxylated chitosan; the cellulose derivative is carboxymethyl cellulose.
A preparation method of the biomass composite ammonium polyphosphate intumescent flame retardant specifically comprises the following steps:
step 1, weighing 65-85 parts of ammonium polyphosphate, 10.5-28 parts of starch derivative and 4-7 parts of biomass;
step 2, adding the starch derivatives weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch derivatives to obtain a starch dispersion, heating the starch dispersion, stirring at constant temperature until starch is gelatinized, and cooling to obtain a starch paste liquid;
step 3, adding the biomass weighed in the step 1 into deionized water, stirring and dissolving at room temperature to obtain a biomass solution;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature until the starch paste and the biomass solution are uniformly mixed, and adjusting the pH value to obtain a composite solution;
step 5, drying the composite solution obtained in the step 4 to obtain a biomass composite ammonium polyphosphate compound containing moisture, and grinding, crushing and sieving the obtained biomass composite ammonium polyphosphate compound to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Preferably, the mass percentage concentration of the starch dispersoid in the step 2 is 3-12wt%, the starch gelatinization temperature is 70-130 ℃, the gelatinization time is 0.5-3h, and the temperature of the starch paste liquid is 30-60 ℃.
Preferably, the mass percentage concentration of the biomass solution in the step 3 is 2-7 wt%.
Preferably, the pH value of the composite solution in the step 4 is 7-11.
Preferably, the water content of the biomass composite ammonium polyphosphate blend in the step 5 is more than 0wt% and less than or equal to 10 wt%.
Preferably, the dry heat reaction temperature of the biomass composite ammonium polyphosphate blend in the step 6 is 100-180 ℃, and the dry heat reaction time is 2-8 h.
The application of the biomass composite ammonium polyphosphate intumescent flame retardant in flame retardance of polar high polymer materials comprises polyurethane, urea resin and epoxy resin.
The invention has the following beneficial effects:
(1) according to the biomass composite ammonium polyphosphate intumescent flame retardant, a starch derivative and biomass are used for synergistically modifying ammonium polyphosphate, the starch derivative and the biomass are coated on the surface of the ammonium polyphosphate, and the biomass is bonded and crosslinked with the starch derivative through dry-heat reaction to form a compact coating layer, so that the water resistance and the heat resistance of the ammonium polyphosphate are improved;
(2) the starch derivative and the biomass are rich in carbon and hydroxyl, have excellent char forming property, and serve as a char source in the biomass composite ammonium polyphosphate intumescent flame retardant, so that a biomass cross-linked starch derivative composite layer rich in carbon and phosphorus is formed on the surface of ammonium polyphosphate, and the prepared 'three-in-one' composite intumescent flame retardant has high char forming rate and flame retardant efficiency;
(3) according to the method, the starch derivative and the biomass are optimized, the using amounts of the starch derivative, the biomass and the ammonium polyphosphate are optimized, and the technological conditions such as the gelatinization temperature and time of the starch derivative, the temperature and time of high-temperature dry heat reaction, the water content and the pH value of a system are optimized, so that the biomass composite ammonium polyphosphate intumescent flame retardant has low hygroscopicity and excellent carbon residue rate, expansion rate, oxygen index and flame retardant property when being used as a polar high polymer material flame retardant, and the composite intumescent flame retardant with high flame retardant efficiency is obtained;
(4) the starch derivatives and biomass raw materials have rich sources and low cost;
(5) the starch derivative and the biomass modify ammonium polyphosphate through dry heat reaction, the production process is simple, the working procedures of post-treatment and the like are avoided, and the method is pollution-free and environment-friendly.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The present invention is more particularly described in the following paragraphs by way of example. Advantages and features of the present invention will become apparent from the following description and from the claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The biomass composite ammonium polyphosphate intumescent flame retardant comprises 65-85 parts of ammonium polyphosphate, 10.5-28 parts of starch derivatives and 4-7 parts of biomass, wherein the starch derivatives and the biomass form a compact coating layer on the surface of the ammonium polyphosphate through dry-heat reaction. On one hand, the starch derivative and the biomass improve the water resistance and the heat resistance of the ammonium polyphosphate, on the other hand, the starch derivative and the biomass are rich in carbon and hydroxyl and have excellent char forming property, and serve as a carbon source in the biomass composite ammonium polyphosphate intumescent flame retardant, so that a biomass crosslinked starch derivative composite layer rich in carbon and phosphorus is formed on the surface of the ammonium polyphosphate, and the prepared 'three-in-one' composite intumescent flame retardant has high char forming rate and flame retardant efficiency.
The preparation method of the biomass composite ammonium polyphosphate intumescent flame retardant specifically comprises the following steps:
step 1, weighing 65-85 parts of ammonium polyphosphate, 10.5-28 parts of starch derivative and 4-7 parts of biomass;
step 2, adding the starch derivatives weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch derivatives to obtain a starch dispersion with the mass percentage concentration of 3-12wt%, heating the starch dispersion to 70-130 ℃, stirring at constant temperature for 0.5-3h until starch is gelatinized, and cooling to 30-60 ℃ to obtain a starch paste liquid;
step 3, adding the biomass weighed in the step 1 into deionized water, stirring at room temperature to dissolve the biomass, and obtaining a biomass solution with the mass percentage concentration of 2-7 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 10-40 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 30-60 ℃ for 15-90min until the starch paste and the biomass solution are uniformly mixed, and adding 0.1-2mol/L HCl or NaOH solution to adjust the pH value to 7-11 to obtain a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 30-60 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of more than 0wt% and less than or equal to 10 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a sieve of 150 meshes and 300 meshes to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at the temperature of 100-180 ℃ for 2-8h to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Based on the preparation method of the biomass composite ammonium polyphosphate intumescent flame retardant, the following examples and comparative examples are provided, wherein the starch derivative used in the examples comprises one or a mixture of two of starch phosphate and starch polyphosphate; the biomass comprises one or more of sodium alginate, hyaluronic acid, chitosan derivative and cellulose derivative, wherein the chitosan derivative is one or two of carboxymethyl chitosan and carboxylated chitosan, and the cellulose derivative is carboxymethyl cellulose; and the polymerization degree of the ammonium polyphosphate in the embodiment of the application is more than 1000.
Based on the above preparation method, the examples and comparative examples of the present application are set forth below:
example 1
Step 1, weighing 70 parts of ammonium polyphosphate, 17 parts of starch phosphate and 6.5 parts of hyaluronic acid;
step 2, adding the starch phosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch phosphate to obtain a starch dispersion with the mass percentage concentration of 5 wt%, heating the starch dispersion to 80 ℃, stirring at constant temperature for 2.5 hours until starch is gelatinized, and cooling to 40 ℃ to obtain a starch paste;
step 3, adding the hyaluronic acid weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the hyaluronic acid to obtain a biomass solution with the mass percentage concentration of 4 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 40 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 40 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution, and adjusting the pH value to 8 to obtain a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 40 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 1 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 110 ℃ for 3h to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 2
Step 1, weighing 80 parts of ammonium polyphosphate, 15 parts of starch phosphate and 5 parts of sodium alginate;
step 2, adding the starch phosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch phosphate to obtain a starch dispersion with the mass percentage concentration of 8 wt%, heating the starch dispersion to 130 ℃, stirring at constant temperature for 1h to gelatinize starch, and cooling to 50 ℃ to obtain a starch paste liquid;
step 3, adding the sodium alginate weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the sodium alginate to obtain a biomass solution with the mass percentage concentration of 6 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 40 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 50 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution, and adjusting the pH value to 9.5 to obtain a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 50 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 2wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 120 ℃ for 5 hours to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 3
Step 1, weighing 75 parts of ammonium polyphosphate, 19 parts of starch phosphate and 6 parts of carboxylated chitosan;
step 2, adding the starch phosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch phosphate to obtain a starch dispersion with the mass percentage concentration of 6 wt%, heating the starch dispersion to 110 ℃, stirring at constant temperature for 1.5 hours until starch is gelatinized, and cooling to 45 ℃ to obtain a starch paste;
step 3, adding the carboxylated chitosan weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the carboxylated chitosan to obtain a biomass solution with the mass percentage concentration of 5 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 30 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 45 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution, and adjusting the pH value to 8.5 to obtain a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 45 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 5 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 130 ℃ for 4h to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 4
Step 1, weighing 85 parts of ammonium polyphosphate, 25.5 parts of starch phosphate and 7 parts of carboxymethyl chitosan;
step 2, adding the starch phosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch phosphate to obtain a starch dispersion with the mass percentage concentration of 7wt%, heating the starch dispersion to 100 ℃, stirring at constant temperature for 0.5h to gelatinize starch, and cooling to 55 ℃ to obtain a starch paste liquid;
step 3, adding the carboxymethyl chitosan weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the carboxymethyl chitosan to obtain a biomass solution with the mass percentage concentration of 4 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 30 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at the constant temperature of 55 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution to adjust the pH value to 7, and obtaining a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at 55 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 4 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 150 ℃ for 7h to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 5
Step 1, weighing 65 parts of ammonium polyphosphate, 28 parts of starch polyphosphate, 1 part of carboxylated chitosan, 1 part of carboxymethyl cellulose and 2.5 parts of hyaluronic acid;
step 2, adding the starch polyphosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch polyphosphate to obtain a starch dispersion with the mass percentage concentration of 12wt%, heating the starch dispersion to 120 ℃, stirring at constant temperature for 2 hours until starch is gelatinized, and cooling to 60 ℃ to obtain a starch paste;
step 3, adding the carboxylated chitosan, the carboxymethyl cellulose and the hyaluronic acid weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the carboxylated chitosan, the carboxymethyl cellulose and the hyaluronic acid to obtain a biomass solution with the mass percentage concentration of 2 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 20 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 60 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution to adjust the pH value to 9, and obtaining a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 30 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 6 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 100 ℃ for 8 hours to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 6
Step 1, weighing 70 parts of ammonium polyphosphate, 22 parts of starch polyphosphate, 2 parts of carboxymethyl cellulose, 1 part of hyaluronic acid and 1 part of sodium alginate;
step 2, adding the starch polyphosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch polyphosphate to obtain a starch dispersion with the mass percentage concentration of 3 wt%, heating the starch dispersion to 70 ℃, stirring at constant temperature for 3 hours until starch is gelatinized, and cooling to 30 ℃ to obtain a starch paste;
step 3, adding the carboxymethyl cellulose, hyaluronic acid and sodium alginate weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the carboxymethyl cellulose, hyaluronic acid and sodium alginate to obtain a biomass solution with the mass percentage concentration of 7 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 10 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature of 30 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution to adjust the pH value to 11, and obtaining a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 40 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 10 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 160 ℃ for 2h to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Example 7
Step 1, weighing 80 parts of ammonium polyphosphate, 10.5 parts of starch polyphosphate, 1.5 parts of carboxylated chitosan, 1 part of carboxymethyl chitosan, 1 part of hyaluronic acid and 1 part of sodium alginate;
step 2, adding the starch polyphosphate weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch polyphosphate to obtain a starch dispersion with the mass percentage concentration of 10 wt%, heating the starch dispersion to 90 ℃, stirring at constant temperature for 2 hours until starch is gelatinized, and cooling to 55 ℃ to obtain a starch paste;
step 3, adding the carboxylated chitosan, the carboxymethyl chitosan, the hyaluronic acid and the sodium alginate weighed in the step 1 into deionized water, and stirring at room temperature to dissolve the materials to obtain a biomass solution with the mass percentage concentration of 3 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion with the mass percentage concentration of 10 wt%, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at the constant temperature of 55 ℃ for 60min until the starch paste and the biomass solution are uniformly mixed, adding 1mol/L HCl or NaOH solution to adjust the pH value to 10, and obtaining a composite solution;
step 5, drying the composite solution obtained in the step 4 in an oven at the temperature of 60 ℃ to obtain a biomass composite ammonium polyphosphate compound with the water content of 8 wt%, grinding and crushing the obtained biomass composite ammonium polyphosphate compound, and sieving the ground biomass composite ammonium polyphosphate compound with a 200-mesh sieve to obtain a biomass composite ammonium polyphosphate blend;
and 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 at 180 ℃ for 6 hours to obtain the biomass composite ammonium polyphosphate intumescent flame retardant.
Comparative example 1
In the difference from example 3, in the step 1, 75 parts of ammonium polyphosphate, 9 parts of starch phosphate and 6 parts of carboxylated chitosan are weighed.
Comparative example 2
Different from the embodiment 3, in the step 1, 75 parts of ammonium polyphosphate, 30 parts of starch phosphate and 6 parts of carboxylated chitosan are weighed.
Comparative example 3
In the difference from example 3, in the step 1, 75 parts of ammonium polyphosphate, 19 parts of starch phosphate and 3 parts of carboxylated chitosan are weighed.
Comparative example 4
In the difference from example 3, in the step 1, 75 parts of ammonium polyphosphate, 19 parts of starch phosphate and 8 parts of carboxylated chitosan are weighed.
Comparative example 5
In contrast to example 3, the starch dispersion in step 2 has a concentration of 2 wt.%.
Comparative example 6
In contrast to example 3, the starch dispersion in step 2 has a concentration of 13 wt.%.
Comparative example 7
Unlike example 3, the temperature of starch gelatinization in step 2 was 60 ℃.
Comparative example 8
Unlike example 3, the temperature of starch gelatinization in step 2 was 150 ℃.
Comparative example 9
Unlike example 3, the biomass solution obtained in step 3 had a concentration of 1 wt%.
Comparative example 10
Unlike example 3, the biomass solution obtained in step 3 had a concentration of 8 wt%.
Comparative example 11
Unlike example 3, the pH of the composite solution obtained in step 4 was 6.
Comparative example 12
Unlike example 3, the pH of the composite solution obtained in the step 4 was 12.0.
Comparative example 13
Unlike example 3, in the step 5, the water content of the biomass composite ammonium polyphosphate compound was 11 wt%.
Comparative example 14
Unlike example 3, in the step 5, the water content of the biomass composite ammonium polyphosphate compound was 0 wt%.
Comparative example 15
In the step 6, the biomass composite ammonium polyphosphate blend obtained in the step 5 is subjected to high-temperature dry heat reaction at 90 ℃ for 4 hours, which is different from the example 3.
Comparative example 16
In the step 6, the biomass composite ammonium polyphosphate blend obtained in the step 5 is subjected to high-temperature dry heat reaction at 200 ℃ for 4 hours, which is different from the example 3.
Comparative example 17
In the step 6, the biomass composite ammonium polyphosphate blend obtained in the step 5 is subjected to high-temperature dry heat reaction at 130 ℃ for 1h, which is different from example 3.
Comparative example 18
In the step 6, the biomass composite ammonium polyphosphate blend obtained in the step 5 is subjected to high-temperature dry heat reaction at 130 ℃ for 9 hours, which is different from the example 3.
Comparative example 19
Unlike example 3, comparative example 19 employs ammonium polyphosphate as a flame retardant.
Comparative example 20
Different from example 3, 75 parts of ammonium polyphosphate, 19 parts of starch and 6 parts of carboxylated chitosan are weighed in the step 1, and starch is adopted to prepare starch paste in the step 2.
The flame retardants prepared in examples 1 to 3 and comparative examples 1 to 20 were used as flame retardants for thermoplastic polyurethane elastomers (TPU), and the specific method for preparing the thermoplastic polyurethane elastomer composite flame retardant material was as follows: weighing a certain amount of the flame retardant prepared in the examples 1-3 and the comparative examples 1-20 and the thermoplastic polyurethane elastomer (TPU) according to the dosage ratio of the following tables 1 and 2, uniformly mixing, adding into a double-screw extruder, melting and uniformly mixing at the temperature of 170-230 ℃ to obtain a flame-retardant polyurethane mixture, and preparing a test sample strip from the obtained flame-retardant polyurethane mixture at the temperature of 190-230 ℃ by using an injection machine;
the specific method for preparing the urea-formaldehyde resin composite flame-retardant material by using the flame retardant prepared in the embodiment 4-5 as the flame retardant of the urea-formaldehyde resin is as follows: weighing a certain amount of the flame retardant prepared in the embodiment 4 and the embodiment 5 according to the dosage ratio in the table 1, adding the flame retardant into urea resin, stirring and mixing the mixture evenly at room temperature, adding the mixture into a mold, curing the mixture for 2 hours at 160 ℃, and preparing a test sample strip;
the flame retardant prepared in the embodiment 6-7 is used as the flame retardant of the epoxy resin, and the specific method for preparing the urea resin composite flame-retardant material comprises the following steps: weighing a certain amount of the flame retardants prepared in examples 6 and 7 according to the dosage ratio shown in Table 1, adding the flame retardants into epoxy resin, stirring and mixing the flame retardants at room temperature uniformly, then adding a polyamide curing agent according to the epoxy value of the epoxy resin, stirring and mixing the flame retardants at room temperature uniformly, adding the mixture into a mold, and curing the mixture for 4 hours at 65 ℃ to prepare test sample strips.
The flame retardants prepared in examples 1 to 7 and comparative examples 1 to 20 were respectively subjected to performance tests as follows:
swelling and solubility test: the flame retardants obtained in examples 1 to 7 and comparative examples 1 to 20 were dispersed in water, and their dispersion crumbliness and swellability in water were observed; calculating the solubility of the ammonium polyphosphate according to the amount of the ammonium polyphosphate dissolved in the aqueous solution;
vertical burning test: testing according to GB/T2408 + 2008 standard;
limiting oxygen index test: testing according to GB/T2406.2-2009 standard;
carbon residue and expansion ratio tests were conducted by placing the test specimens obtained in examples 1 to 7 and comparative examples 1 to 20 in a muffle furnace, heating the specimens to 600 ℃ for carbonization, and observing the volume ratio before and after expansion and the amount of carbon residue, the test results of examples 1 to 7 are shown in Table 1, and the test results of comparative examples 1 to 20 are shown in Table 2.
TABLE 1 test results for examples 1-7
TABLE 2 test results for comparative examples 1-20
From the test results of tables 1 and 2, the following conclusions were drawn:
(1) the flame retardants obtained in examples 1 to 7 did not swell in water and had high water resistance, and the flame retardants obtained in examples 1 to 3, when used as polyurethane flame retardants, the flame retardants obtained in examples 4 to 5, and the flame retardants obtained in examples 6 to 7, when used as urea resin flame retardants, both had high char formation rates and flame retardant efficiencies;
(2) according to the comparison of the test results of comparative examples 1 to 18 and example 3, the flame retardants prepared in comparative examples 1 to 18 have swelling phenomenon in water, even the starch coating layer is broken; when the flame retardant is used as a polyurethane flame retardant, the flame retardant efficiency is poorer than that of the flame retardant prepared in the embodiment 3;
(3) according to the test results of comparative example 19, it is known that polyphosphate as a flame retardant has poor flame retardant efficiency.
(4) According to the test result of the comparative example 20, the flame retardant efficiency is poor when the starch and biomass composite ammonium polyphosphate is used as the intumescent flame retardant.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those of ordinary skill in the art can readily practice the present invention as described herein; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (2)
1. The biomass composite ammonium polyphosphate intumescent flame retardant is characterized by comprising the following raw materials in parts by weight:
65-85 parts of ammonium polyphosphate,
10.5 to 28 parts of starch derivative,
4-7 parts of biomass, namely,
wherein the starch derivative is one or a mixture of two of starch phosphate and starch polyphosphate; the biomass comprises one or more of sodium alginate, hyaluronic acid, chitosan derivatives and cellulose derivatives; the chitosan derivative comprises one or a mixture of two of carboxymethyl chitosan and carboxylated chitosan; the cellulose derivative is carboxymethyl cellulose;
the biomass composite ammonium polyphosphate intumescent flame retardant is prepared by the following method, and specifically comprises the following steps:
step 1, weighing 65-85 parts of ammonium polyphosphate, 10.5-28 parts of starch derivative and 4-7 parts of biomass;
step 2, adding the starch derivatives weighed in the step 1 into deionized water, stirring at room temperature to uniformly disperse the starch derivatives to obtain a starch dispersion, heating the starch dispersion, stirring at constant temperature until starch is gelatinized, and cooling to obtain a starch paste liquid;
step 3, adding the biomass weighed in the step 1 into deionized water, stirring and dissolving at room temperature to obtain a biomass solution; the mass percentage concentration of the biomass solution is 2-7 wt%;
step 4, dispersing the ammonium polyphosphate weighed in the step 1 in deionized water to obtain an ammonium polyphosphate dispersion, adding the starch paste obtained in the step 2 and the biomass solution obtained in the step 3 into the ammonium polyphosphate dispersion, stirring at a constant temperature until the starch paste and the biomass solution are uniformly mixed, and adjusting the pH value to obtain a composite solution; the pH value of the composite solution is 7-11;
step 5, drying the composite solution obtained in the step 4 to obtain a biomass composite ammonium polyphosphate compound containing moisture, and grinding, crushing and sieving the obtained biomass composite ammonium polyphosphate compound to obtain a biomass composite ammonium polyphosphate blend; the water content of the biomass composite ammonium polyphosphate blend is more than 0wt% and less than or equal to 10 wt%;
step 6, carrying out high-temperature dry-heat reaction on the biomass composite ammonium polyphosphate blend obtained in the step 5 to obtain a biomass composite ammonium polyphosphate intumescent flame retardant;
wherein, the mass percentage concentration of the starch dispersoid in the step 2 is 3-12wt%, the gelatinization temperature of the starch is 70-130 ℃, the gelatinization time is 0.5-3h, and the temperature of the starch paste liquid is 30-60 ℃; in the step 6, the dry heat reaction temperature of the biomass composite ammonium polyphosphate blend is 100-180 ℃, and the dry heat reaction time is 2-8 h.
2. The application of the biomass composite ammonium polyphosphate intumescent flame retardant of claim 1 in flame retardance of polar high polymer materials, wherein the polar high polymer materials comprise polyurethane, urea-formaldehyde resin and epoxy resin.
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| CN114672068A (en) * | 2022-04-08 | 2022-06-28 | 四川大学 | Intumescent flame retardant for polyurethane, flame-retardant polyurethane and preparation of flame-retardant polyurethane |
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