CN115558375B - Metal doped intumescent flame retardant coating liquid, flame retardant, preparation and application thereof - Google Patents
Metal doped intumescent flame retardant coating liquid, flame retardant, preparation and application 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention relates to the technical field of flame retardants, in particular to a metal doped intumescent flame retardant coating liquid, a flame retardant, and preparation and application thereof. The invention provides a metal doped intumescent flame retardant coating liquid or a solid metal doped intumescent flame retardant, which comprises the following raw materials: amino macromolecular compounds, organic phosphonic acid compounds and metal compounds; the metal mass in the metal compound accounts for 0.1-10% of the total mass of the raw materials. The expansion carbon layer of the flame retardant has high strength, can bear more than 2000 times of the weight of the flame retardant, and can obtain excellent smoke and heat reducing effects under low metal content; and the preparation method is simple and environment-friendly.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a metal doped intumescent flame retardant coating liquid, a flame retardant, and preparation and application thereof.
Background
As one of three major materials, the organic polymer material has the characteristics of low density, easy molding and processing and the like compared with metal materials and inorganic nonmetallic materials, and is widely used in various fields of national economy and people life, and becomes a major material with the largest volume yield. However, unlike metal and non-metal materials, most of the polymer materials are flammable and combustible materials, and have the advantages of high heat release rate, high heat value, high flame propagation speed and difficulty in extinguishing during combustion, and usually release of a large amount of smoke and toxic gas, so that serious and oversized fire accidents are continuously caused, and huge economic losses and casualties are caused. Therefore, it is necessary to flame-retardant the polymer material.
Intumescent Flame Retardants (IFRs) can impart both excellent flame retardancy and inhibition properties to polymeric materials due to their excellent condensed phase flame retardant mechanism. However, the IFRs have the problems of low flame-retardant efficiency and the like, and the metal particles and the metal compounds have catalytic oxidation and catalytic carbonization effects, so that the quality of the expanded carbon layer can be obviously improved, and the flame-retardant and smoke-suppressing efficiency of the IFRs is improved. However, inorganic metal ions have problems such as poor compatibility with the substrate, and the like, thereby affecting other properties. The method for constructing the metal doped intumescent flame retardant by a chemical bond has the problems of complex preparation method, need of using an organic solvent and the like. Therefore, how to prepare a metal doped intumescent flame retardant with high flame retarding and smoke suppressing efficiency by a simple and environment-friendly method remains a challenge.
Disclosure of Invention
Aiming at the defects, the invention provides the metal doped expansion coating liquid and the metal doped expansion flame retardant, wherein the expansion carbon layer of the flame retardant has high strength which can bear more than 2000 times of the weight of the flame retardant, and can obtain excellent smoke and heat reducing effects under the condition of low metal content; and the preparation method is simple and environment-friendly.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a metal doped intumescent flame retardant coating liquid or a solid metal doped intumescent flame retardant, which comprises the following raw materials: amino macromolecular compounds, organic phosphonic acid compounds and metal compounds; the metal mass in the metal compound accounts for 0.1-10% of the total mass of the raw materials. Total mass of each raw material = mass of amino macromolecular compound + mass of organic phosphonic acid compound + mass of metal in metal compound.
Further, the amino macromolecular compound is selected from the group consisting of: at least one of Chitosan (CH), carboxymethylated chitosan (O-CH, N-CH), gelatin (Gelatin), pectin (pectin), polyethylenimine (PEI) or branched polyethylenimine (bPEI).
Further, the organophosphonic acid compound is selected from the group consisting of: phosphoric acid (H) 3 PO 4 ) Phenyl Phosphonic Acid (PPA), diphenyl hypophosphorous acid, dicarboxyethylphenyl hypophosphorous acid, phytic Acid (PA), hydroxyethylidene diphosphonic acid (HEDP), amino groupsAt least one of trimethylene phosphonic Acid (ATMP), ethylene diamine tetramethylene phosphonic acid (EDTMP), or diethylene triamine pentamethylene phosphonic acid (DTPMP).
Further, the mass ratio of the amino macromolecular compound to the organic phosphonic acid compound is: 1: 5-5: 1.
further, the metal compound is selected from: metal oxides, metal peroxides, metal hydroxides or metal carbonates of alkali metals of the first main group (Na, K, ru, cs), alkaline earth metals of the second main group (Mg, ca, sr, ba) or of the first transition series elements of the d region (Sc, ti, V, cr, mn, fe, co, ni, cu, zn).
Further, the solid content of the metal doped intumescent flame retardant coating liquid (M-IFR) is as follows: 1 to 20 percent.
Further, the strength of the expanded carbon layer formed by the metal doped expanded flame retardant coating liquid or the solid metal doped expanded flame retardant can bear more than 2000 times of the weight of the expanded carbon layer.
The second technical problem to be solved by the invention is to provide a preparation method of a metal doped intumescent flame retardant coating liquid, which comprises the following steps: stirring and mixing the amino macromolecular compound, the organic phosphonic acid compound and water uniformly to form a blending solution (the pH value of the solution is acidic at the moment); then adding a metal compound, and after the metal compound is completely reacted under mechanical stirring, separating and purifying to obtain the metal doped intumescent flame retardant coating liquid (M-IFR).
Further, the purification method includes a suction filtration separation method or a centrifugal separation method.
The third technical problem to be solved by the invention is to provide a preparation method of a solid metal doped intumescent flame retardant, which comprises the following steps: stirring and mixing the amino macromolecular compound, the organic phosphonic acid compound and water uniformly to form a blending solution (the pH value of the solution is acidic at the moment); then adding a metal compound, and separating to obtain a metal doped intumescent flame retardant coating solution (M-IFR) after the metal compound fully reacts under mechanical stirring; finally, the obtained flame-retardant coating liquid is subjected to drying treatment (vacuum freeze drying) to obtain the solid metal doped intumescent flame retardant.
The fourth technical problem to be solved by the invention is to provide the application of the metal-doped intumescent flame retardant coating liquid or the solid metal-doped intumescent flame retardant in epoxy resin, polyurethane foam or polyester-Vilon-cotton ternary blended cloth.
Further, the solid flame retardant or the coating liquid is added in an amount of 10 to 25wt% of the matrix resin.
The fifth technical problem to be solved by the invention is to provide a flame-retardant epoxy resin, wherein the raw materials of the flame-retardant epoxy resin comprise epoxy resin, flame retardant or curing agent, and the flame retardant is the prepared metal-doped intumescent flame retardant coating liquid or solid metal-doped intumescent flame retardant.
Further, the strength of the expanded carbon layer formed by the flame-retardant epoxy resin can bear more than 60 times of the weight of the expanded carbon layer.
Further, the addition amount of the metal doped intumescent flame retardant coating liquid or the solid metal doped intumescent flame retardant is 10-25 wt% of the epoxy resin.
Further, the curing agent is selected from: polyamide curing agents (PA 650 or PA 610) or aromatic amine curing agents (4' 4-diaminodiphenylmethane, or 4, 4-diaminophenylsulfone).
Further, the addition amount of the curing agent is 20-80 wt% of the epoxy resin.
The sixth technical problem to be solved by the invention is to provide a preparation method of flame-retardant epoxy resin, which comprises the following steps: mechanically stirring and uniformly mixing the metal-doped intumescent flame retardant coating liquid or the solid metal-doped intumescent flame retardant with epoxy resin; and then adding a preheated curing agent for curing to obtain the flame-retardant epoxy resin.
Further, the curing temperature is 80 ℃ to 200 ℃.
The invention has the beneficial effects that:
the invention provides a metal doped expansion coating liquid and a solid metal doped expansion flame retardant, wherein the strength of an expansion carbon layer of the flame retardant is high, namely the flame retardant can bear more than 2000 times of the weight of the flame retardant, and meanwhile, the excellent smoke and heat reducing effect can be obtained under the condition of low metal content; and the preparation method is simple and environment-friendly. The invention also solves the problem that the existing metal doped intumescent flame retardant has poor compatibility between metal particles and a base material; solves the problems of complex preparation process of the metal doped intumescent flame retardant coating liquid and the intumescent flame retardant and the use of organic solvents. In addition, when the flame retardant is used for flame-retardant epoxy resin, the obtained flame-retardant epoxy resin has high carbon residue strength and can bear more than 60 times of the weight of the flame-retardant epoxy resin; and the obtained flame retardant obviously improves the ablation resistance of the epoxy resin.
Drawings
FIG. 1 is an SEM image of the inner surface (a) and outer surface (b) of the IFR carbon residue obtained in example 1.
FIG. 2 shows the results of the IFR carbon residue strength test obtained in example 1: a weight of 200g was placed on top of the carbon residue for 30s.
FIG. 3 shows the Pure EP, EP/IFR obtained in example 1 18％ Cone calorimetric test results (a) heat release rate, (b) total smoke release.
FIG. 4 is an SEM image of the inner surface (a) and the outer surface (b) of the Cu-IFR carbon residue obtained in example 2.
FIG. 5 shows the results of the Cu-IFR carbon residue strength test obtained in example 2.
FIG. 6 is a Pure EP, EP/Cu-IFR obtained in example 2 18％ Cone calorimetric test results (a) heat release rate, (b) total smoke release results.
FIG. 7 shows the results of the strength test of the Fe-IFR carbon residue obtained in example 4.
FIG. 8 is a Pure EP, EP/Fe-IFR obtained in example 4 18％ Cone calorimetric test results (a) heat release rate, (b) total smoke release results.
FIG. 9 is a schematic diagram of the mechanism of the present preparation of flame retardant.
FIG. 10 shows the results of the carbon residue strength test of the flame retardant epoxy resin obtained in example 1 of the present invention.
FIG. 11 is a graph showing the results of the strength test of the carbon residue of the flame retardant epoxy resin obtained in example 2 of the present invention.
FIG. 12 shows the results of high temperature spray gun test for the flame retardant epoxy resins obtained in examples (a-c), examples (d-f) and examples 2 (g-i) of the present invention.
Detailed Description
The invention takes amino macromolecular compound, organic phosphonic acid compound and metal compound as raw materials to prepare a metal doped intumescent flame retardant; wherein, the amino macromolecular compound provides a gas source and a carbon source, the organic phosphonic acid provides an acid source, the two are combined together in an ionic bond mode through an acid-base neutralization reaction, and the metal ions are combined in an ionic bond and coordination bond mode. The ratio of amino macromolecular compound to organic phosphonic acid must be such that: 1: 5-5: 1, a step of; therefore, the mixed solution formed by the two is ensured to be acidic, the metal compound and the mixed solution of the system can be reacted, and meanwhile, the metal ions are introduced without introducing other impurity ions. In addition, the proportion of ions in the amino macromolecular compound, the organic phosphonic acid and the metal ions is also required to be in a specific range, so that the crosslinking speed and the foaming rate of the carbon layer can be matched in the formation process of the expanded carbon layer, and an ideal carbon layer with compact outer surface, a three-dimensional closed cell structure of the inner surface and high strength can be obtained, and the excellent flame retardant property can be endowed to the substrate in the later use process.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Example 1:
after 4g of chitosan is weighed and evenly dispersed in 90g of deionized water, 6g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan water solution, and the solution is mechanically stirred for 0.5h at room temperature to gradually form pale yellow transparent liquid, and the Intumescent Flame Retardant (IFR) is obtained through freeze drying. 0.1g of flame retardant is weighed and pressed into a disc with the thickness of 1mm and the diameter of 1cm, the temperature is raised to 700 ℃ at 10 ℃/min in a nitrogen atmosphere environment in a tube furnace, the obtained expanded carbon layer has discontinuous microscopic morphology and is not crushed and compact (the SEM result diagram is shown in figure 1), a weight with the mass of 200g is placed on the top of carbon residue, and the carbon layer is crushed and collapses and cannot bear more than 2000 times of the weight of the carbon residue (shown in figure 2).
The obtained flame retardant is used for flame retarding polyamide curing epoxy resin, and the specific method is as follows: the flame retardant IFR and the epoxy resin are mechanically stirred and mixed for 0.5h at the temperature of 80 ℃, and the addition amount of the flame retardant is 18 weight percent of the total mass of the cured epoxy resin; adding preheated polyamide curing agent PA650 (the addition amount of the curing agent is 8 of the mass of the epoxy resin)0 percent) is poured into a preheated mould after being rapidly and evenly stirred, and is respectively cured for 2 hours at the temperature of 80 ℃ and the temperature of 120 ℃ to obtain the flame-retardant polyamide cured epoxy resin (EP/IFR) 18％ ). Testing the flame retardant property: UL-94NR, LOI:27%. The cone calorimetric test results of 35kW of heat radiation show that: the peak heat release (pHRR) was reduced by 65% and the total smoke release (TSP) was reduced by 35% (results are shown in FIG. 3).
0.6g of flame-retardant epoxy resin is taken, and the size is as follows: 10mm 3mm in a nitrogen atmosphere in a tube furnace at 10 ℃/min to 500 ℃, a weight of 10g mass was placed on top of the carbon residue, and the results showed EP/IFR 18％ Is weak, is easy to break, and cannot bear more than 60 times of the weight of the carbon residue (as shown in figure 10). The principle ratios and the performance results of each example and comparative example are shown in table 1.
Example 2:
after 3.8g of chitosan is weighed and evenly dispersed in 90g of deionized water, 5.7g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan water solution, mechanical stirring is carried out for 0.5h at room temperature, pale yellow transparent liquid is gradually formed, 0.625g of copper oxide (the mass of copper ions accounts for 5% of the mass of solids, the mass of solids=the total mass of chitosan+amino trimethylene phosphonic acid+copper) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. Weighing 0.1g of flame retardant, pressing into a disc with the thickness of 1mm and the diameter of 1cm, heating to 700 ℃ at 10 ℃/min in a nitrogen atmosphere environment in a tube furnace, and obtaining an expanded carbon layer with a microscopic morphology which shows a three-dimensional closed cell structure (SEM result diagram is shown in figure 4); a weight of 200g was placed on top of the carbon residue for 30s without collapsing and crushing, and was able to withstand more than 2000 times its weight (as shown in fig. 5).
The flame retardant obtained was used for flame retarding polyamide cured epoxy resin (EP/Cu-IFR 18％ The preparation process is the same as in example 1), and when the addition amount is 18wt%, the flame retardant property is that: UL-94V-0, LOI:31%. The cone calorimetric test results are shown in FIG. 6, and as can be seen from FIG. 6: the peak heat release (pHRR) was reduced by 70% and the total smoke release (TSP) was reduced by 53%. 0.6g of flame-retardant epoxy resin is taken, and the size is as follows: 10 mm. Times.10 mm. Times.3 mm, under a nitrogen atmosphere in a tube furnace at 10 ℃ C./mn is heated to 500 ℃, and a weight with the mass of 10g is placed on the top of the carbon residue for 30 seconds without collapsing and crushing, and the result shows that the weight of the carbon residue can bear more than 60 times of the weight of the carbon residue (shown in figure 11), which indicates that metal ions can enhance the strength of the carbon layer.
The invention also carries out high-temperature spray gun test on the pure epoxy resin used in the examples and the flame-retardant epoxy resin obtained in the examples 1 and 2, and the specific test method is as follows: the sample is vertically downward, butane flame (-1400 ℃) is adopted to continuously burn the surface of the epoxy resin, the length of the flame is 10cm, and the distance between the flame and the sample is 5cm; the test results are shown in fig. 12; the result shows that the flame retardant prepared by the invention obviously improves the high-temperature ablation resistance of the epoxy resin.
Example 3:
3.88g of pectin is weighed and evenly dispersed in 90g of deionized water, 5.82g of ethylenediamine tetramethylene phosphonic acid (EDTMP) is weighed and gradually added into the aqueous solution of the pectin, the mixture is mechanically stirred for 0.5h at room temperature to gradually form pale yellow transparent liquid, 0.43g of ferric oxide (the mass of Fe is 3% of the mass of the solid) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Fe-IFR) is obtained through freeze drying. The flame-retardant polyamide epoxy resin is used for flame-retardant polyamide cured epoxy resin (the curing agent is PA650, the addition amount of the curing agent is 80% of the mass of the epoxy resin), and when the addition amount is 18% by weight, the flame-retardant performance is as follows: UL-94V-0, LOI:29%.
Example 4:
3.84g of gelatin is weighed and evenly dispersed in 90g of deionized water, 5.76g of ethylenediamine tetramethylene phosphonic acid (EDTMP) is weighed and gradually added into an aqueous solution of gelatin, the mixture is mechanically stirred for 0.5h at room temperature to gradually form pale yellow transparent liquid, 0.57g of ferric oxide (the mass of Fe is 4% of the mass of solid) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Fe-IFR) is obtained through freeze drying.
0.1g of flame retardant is weighed, pressed into a disc with the thickness of 1mm and the diameter of 1cm, heated to 700 ℃ at 10 ℃/min in a nitrogen atmosphere environment in a tube furnace, and a weight with the mass of 200g is placed on the top of carbon residue for 30s, so that the weight of the flame retardant can bear more than 2000 times of the weight of the flame retardant (as shown in figure 7). The flame retardant is used for flame retarding polyamide cured epoxy resin (curing agent)The addition amount of the PA650 curing agent is 80% of the mass of the epoxy resin, and when the addition amount is 18% by weight, the flame-retardant polyamide cured epoxy resin (EP/Fe-IFR) is obtained 18％ ) The method comprises the steps of carrying out a first treatment on the surface of the The flame retardant property of the flame retardant is as follows: UL-94V-0, LOI:29%. The cone calorimetric test results show that: the peak heat release (pHRR) was reduced by 71% and the total smoke release (TSP) was reduced by 52% (results are shown in FIG. 8).
Example 5:
3.80g of chitosan is weighed and evenly dispersed in 90g of deionized water, then 5.70g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan water solution, mechanical stirring is carried out for 0.5h at room temperature, pale yellow transparent liquid is gradually formed, then 0.86g of basic copper carbonate (the copper mass accounts for 5% of the solid mass) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. The obtained flame retardant is used for flame retarding polyamide cured epoxy resin (the addition amount of the curing agent PA650 is 80% of the mass of the epoxy resin), and when the addition amount is 16wt%, the flame retarding performance is that: UL-94V-0, LOI:29%.
Example 6:
3.80g of chitosan is weighed and evenly dispersed in 90g of deionized water, then 5.7g of diethylenetriamine penta methylene phosphonic acid (DTPMP) is weighed and gradually added into chitosan water solution, mechanical stirring is carried out for 0.5h at room temperature, pale yellow transparent liquid is gradually formed, then 0.93g of calcium hydroxide (the proportion of calcium mass to solid mass is 5%) is added, and after the metal compound is completely reacted, the intumescent flame retardant (Ca-IFR) is obtained through freeze drying. When the flame retardant polyamide is used for curing the epoxy resin (the curing agent is PA650, the addition amount of the curing agent is 80% of the mass of the epoxy resin), and the addition amount of the flame retardant is 16wt%, the flame retardant performance is that: UL-94V-1, LOI:28%.
Example 7:
after 4g of polyethyleneimine is weighed and evenly dispersed in 90g of deionized water, 6g of ethylenediamine tetramethylene phosphonic acid (EDTMP) is weighed and gradually added into the polyethyleneimine water solution, and the mixture is mechanically stirred for 0.5h at room temperature to gradually form white precipitate, and the white precipitate is filtered, washed and dried. When the flame retardant polyamide is used for curing the epoxy resin (the curing agent is PA650, the addition amount of the curing agent is 80% of the mass of the epoxy resin), and the addition amount of the flame retardant is 20wt%, the flame retardant performance is that: UL-94V-2, LOI:26%.
Example 8:
3.84g of polyethyleneimine is weighed and uniformly dispersed in 90g of deionized water, 5.76g of ethylenediamine tetramethylene phosphonic acid (EDTMP) is weighed and gradually added into an aqueous polyethyleneimine solution, the solution is mechanically stirred for 0.5h at room temperature, 0.57g of potassium hydroxide (the mass of potassium accounts for 4% of the mass of the solid) is added, and after the metal compound is completely reacted, the solution is filtered, washed and dried. When the flame retardant polyamide is used for curing the epoxy resin (the curing agent is PA650, the addition amount of the curing agent is 80% of the mass of the epoxy resin), and the addition amount of the flame retardant is 20wt%, the flame retardant performance is that: UL-94V-1, LOI:29%.
Example 9:
after 5g of chitosan is weighed and uniformly dispersed in 90g of deionized water, 5g of amino trimethylene phosphonic acid is weighed and slowly added into the chitosan water solution, and the solution is mechanically stirred for 0.5h at room temperature, so that the transparent liquid intumescent flame retardant coating liquid is obtained. The flame-retardant polyester-vinylon-cotton ternary blended fabric is cured and dried in a buffer solution with pH of 5 by adopting a knife coating mode. When the weight gain is 21%, the vertical burning test is carried out from fire to self-extinguish, and the original length is as follows: 30cm, break length: 13cm; limiting Oxygen Index (LOI): 28%. The cone calorimetric test results show that: the peak heat release (pHRR) was reduced by 32% and the total smoke release (TSP) was reduced by 39%.
Example 10:
after 4.9g of chitosan is weighed and uniformly dispersed in 90g of deionized water, 4.9g of amino trimethylene phosphonic acid is weighed and slowly added into chitosan water solution, the solution is mechanically stirred for 0.5h at room temperature, then 0.3g of copper hydroxide (copper mass accounts for 2% of the solid mass) is added, and after the metal compound is completely reacted, the transparent liquid intumescent flame retardant coating liquid is obtained. The flame-retardant polyester-vinylon-cotton ternary blended fabric is cured and dried in a buffer solution with pH of 5 by adopting a knife coating mode. When the weight gain is 21%, the vertical burning test is carried out from fire to self-extinguish, and the original length is as follows: 30cm, break length: 8cm; limiting Oxygen Index (LOI): 30%. The cone calorimetric test results show that: the peak heat release (pHRR) was reduced by 51% and the total smoke release (TSP) was reduced by 47%.
Example 11:
after 8.33g of chitosan is weighed and evenly dispersed in 83g of deionized water, 8.33g of amino trimethylene phosphonic acid is weighed and slowly added into chitosan water solution, the solution is mechanically stirred for 0.5h at room temperature, then 0.52g of copper hydroxide (copper mass accounts for 2% of the solid mass) is added, and after the metal compound is completely reacted, the transparent liquid intumescent flame retardant coating liquid is obtained. The flame-retardant polyester-vinylon-cotton ternary blended fabric is cured and dried in a buffer solution with pH of 5 by adopting a knife coating mode. When the weight gain is 21%, the vertical burning test is carried out from fire to self-extinguish, and the original length is as follows: 30cm, break length: 7cm; limiting Oxygen Index (LOI): 31%.
Example 12:
after 3.80g of carboxymethylated chitosan is weighed and uniformly dispersed in 90g of deionized water, 5.7g of aminotrimethylene phosphonic acid is weighed and gradually added into a carboxymethylated chitosan water solution, the solution is mechanically stirred for 0.5h at room temperature to gradually form pale yellow transparent liquid, then 0.86g of basic copper carbonate (the copper mass accounts for 5% of the solid mass) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. The method is used for soft polyurethane foam, and comprises the following specific steps: adding polyether polyol for polyurethane, water, a physical foaming agent, a surfactant and a catalyst into the same container, stirring and mixing uniformly at a high speed, then blending with isocyanate, rapidly pouring into a mould, and curing to obtain flame-retardant polyurethane foam, wherein when the addition amount is 20wt%, LOI:24%. The cone calorimetric test results show that: the peak heat release (pHRR) was reduced by 61% and the total smoke release (TSP) was reduced by 48%.
Example 13:
1.96g of carboxymethylated chitosan is weighed and uniformly dispersed in 90g of deionized water, 7.84g of aminotrimethylene phosphonic acid is weighed and gradually added into the carboxymethylated chitosan water solution, the solution is mechanically stirred for 0.5h at room temperature to gradually form yellow transparent liquid, 0.30g of copper hydroxide (copper mass accounts for 2% of the solid mass) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. The epoxy resin is used for curing the flame-retardant aromatic amine, and the specific modes are as follows: mechanically stirring and mixing the flame retardant and the epoxy resin for 0.5h at 90 ℃, adding the preheated aromatic amine curing agent 4' 4-diaminodiphenylmethane (the adding amount of the curing agent is 20% of the mass of the epoxy resin), pouring the mixture into a preheated mold after rapid stirring uniformly, and curing the mixture for 2h at 100 ℃ and 150 ℃ respectively to obtain the flame-retardant aromatic amine cured epoxy resin, wherein when the adding amount is 25wt%, the flame-retardant performance is as follows: UL-94V-0, LOI:34%. The cone calorimetric test results show that: peak heat release (pHRR) was reduced by 69% and total smoke release (TSP) was reduced by 52%.
Example 14:
3.68g of chitosan is weighed and uniformly dispersed in 90g of deionized water, then 5.52g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan water solution, mechanical stirring is carried out for 0.5h at room temperature, yellow transparent liquid is gradually formed, then 1.38g of basic copper carbonate (the copper mass accounts for 8% of the solid mass) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. The epoxy resin is used for flame-retardant polyamide curing, and the concrete mode is as follows: mechanically stirring and mixing the flame retardant and the epoxy resin for 0.5h at 80 ℃, adding a preheated polyamide curing agent (the curing agent is PA650, the adding amount of the curing agent is 80% of the mass of the epoxy resin), pouring the mixture into a preheated mold after rapid stirring, and respectively curing the mixture for 2h at 80 ℃ and 120 ℃ to obtain the flame-retardant polyamide cured epoxy resin, wherein when the adding amount is 18wt%, the flame-retardant performance is as follows: UL-94V-1, LOI:28%.
Example 15:
after 6.33g of chitosan is weighed and uniformly dispersed in 90g of deionized water, 3.17g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan water solution, the solution is mechanically stirred for 0.5h at room temperature to gradually form yellow transparent liquid, then 0.86g of basic copper carbonate (the copper mass accounts for 5% of the solid mass) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying. The epoxy resin is used for flame-retardant polyamide curing, and the concrete mode is as follows: mechanically stirring and mixing the flame retardant and the epoxy resin for 0.5h at 80 ℃, adding a preheated polyamide curing agent (the curing agent is PA650, the adding amount of the curing agent is 80% of the mass of the epoxy resin), pouring the mixture into a preheated mold after rapid stirring, and respectively curing the mixture for 2h at 80 ℃ and 120 ℃ to obtain the flame-retardant polyamide cured epoxy resin, wherein when the adding amount is 18wt%, the flame-retardant performance is as follows: UL-94V-1, LOI:27%.
Example 16:
3.20g of pectin is weighed and evenly dispersed in 90g of deionized water, 6.40g of hydroxyethylidene diphosphonic acid (HEDP) is weighed and gradually added into the aqueous solution of the pectin, the mixture is mechanically stirred for 0.5h at room temperature to gradually form pale yellow liquid, 0.60g of zinc hydroxide (the mass of zinc accounts for 4% of the mass of solid) is added, and after the metal compound is completely reacted, the metal doped intumescent flame retardant (Zn-IFR) is obtained through freeze drying. Weighing 0.1g of flame retardant, pressing into a disc with the thickness of 1mm and the diameter of 1cm, heating to 700 ℃ at 10 ℃/min in a nitrogen atmosphere environment in a tube furnace, and placing a weight with the mass of 200g on the top of carbon residue for 30s, wherein the weight can bear more than 2000 times of the weight of the carbon residue. The epoxy resin is used for flame-retardant polyamide curing, and the concrete mode is as follows: mechanically stirring and mixing the flame retardant and the epoxy resin for 0.5h at 80 ℃, adding a preheated polyamide curing agent (the curing agent is PA650, the adding amount of the curing agent is 80% of the mass of the epoxy resin), pouring the mixture into a preheated mold after rapid stirring, and respectively curing the mixture for 2h at 80 ℃ and 120 ℃ to obtain the flame-retardant polyamide cured epoxy resin, wherein when the adding amount is 20wt%, the flame-retardant performance is as follows: UL-94V-0, LOI:30%. The cone calorimetric test results show that: the peak heat release (pHRR) was reduced by 65% and the total smoke release (TSP) was reduced by 54%.
Comparative example 1
After 3.4g of chitosan is weighed and evenly dispersed in 90g of deionized water, 5.1g of amino trimethylene phosphonic acid is weighed and gradually added into chitosan aqueous solution, mechanical stirring is carried out for 0.5h at room temperature, pale yellow transparent liquid is gradually formed, 1.875g of copper oxide (copper ion mass accounts for 15% of solid mass, total mass of chitosan + amino trimethylene phosphonic acid + copper) is added, after metal compound is completely reacted, metal doped intumescent flame retardant (Cu-IFR) is obtained through freeze drying, the obtained flame retardant is used for flame retardant polyamide cured epoxy resin (the preparation method is the same as in example 2), and when the addition amount is 18wt%, the flame retardant performance is obtained: UL-94NR, LOI:28%.
TABLE 1 raw material ratios and Properties of the examples of the invention
In table 1, x=chitosan, y=carboxymethylated chitosan, z=pectin, m=gelatin, n=polyethylenimine; a=aminotrimethylene phosphonic acid, b=ethylenediamine tetramethylene phosphonic acid, c=diethylenetriamine pentamethylene phosphonic acid, d=hydroxyethylene diphosphonic acid.
Claims (14)
1. The metal doped intumescent flame retardant coating liquid is characterized by comprising the following raw materials: amino macromolecular compounds, organic phosphonic acid compounds and metal compounds; the mass ratio of the metal in the metal compound to the total mass of the raw materials is 0.1-10%, and the mass ratio of the amino macromolecular compound to the organic phosphonic acid compound is as follows: 1: 5-5: 1, a step of; wherein the amino macromolecular compound is selected from the group consisting of: at least one of chitosan, carboxymethylated chitosan, gelatin, pectin, polyethylenimine or branched polyethylenimine; the organic phosphonic acid compound is selected from: at least one of phosphoric acid, phenylphosphonic acid, diphenylphosphinic acid, dicarboxyethylphenylphosphinic acid, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, or diethylenetriamine pentamethylene phosphonic acid; the metal compound is selected from: a first main group alkali metal, a second main group alkaline earth metal, or a metal oxide, a metal peroxide, a metal hydroxide, or a metal carbonate of a d-block first transition system element;
and the flame-retardant coating liquid is prepared by the following preparation method: stirring and uniformly mixing an amino macromolecular compound, an organic phosphonic acid compound and water to form a blending solution; then adding a metal compound, and separating and purifying after the metal compound completely reacts under mechanical stirring to obtain the metal doped intumescent flame retardant coating liquid.
2. The method for preparing the metal-doped intumescent flame retardant coating liquid of claim 1, which is characterized in that the preparation method comprises the following steps: stirring and uniformly mixing an amino macromolecular compound, an organic phosphonic acid compound and water to form a blending solution; then adding a metal compound, and separating and purifying after the metal compound completely reacts under mechanical stirring to obtain the metal doped intumescent flame retardant coating liquid.
3. Use of the metal-doped intumescent flame retardant coating solution of claim 1 in epoxy resin, polyurethane foam, or polyester-velen-cotton ternary blend cloth.
4. The solid metal doped intumescent flame retardant is characterized by comprising the following raw materials: amino macromolecular compounds, organic phosphonic acid compounds and metal compounds; the mass ratio of the metal in the metal compound to the total mass of the raw materials is 0.1-10%, and the mass ratio of the amino macromolecular compound to the organic phosphonic acid compound is as follows: 1: 5-5: 1, a step of; wherein the amino macromolecular compound is selected from the group consisting of: at least one of chitosan, carboxymethylated chitosan, gelatin, pectin, polyethylenimine or branched polyethylenimine; the organic phosphonic acid compound is selected from: at least one of phosphoric acid, phenylphosphonic acid, diphenylphosphinic acid, dicarboxyethylphenylphosphinic acid, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, or diethylenetriamine pentamethylene phosphonic acid; the metal compound is selected from: a first main group alkali metal, a second main group alkaline earth metal, or a metal oxide, a metal peroxide, a metal hydroxide, or a metal carbonate of a d-block first transition system element;
and the solid metal doped intumescent flame retardant is prepared by the following preparation method: stirring and uniformly mixing an amino macromolecular compound, an organic phosphonic acid compound and water to form a blending solution; then adding a metal compound, and separating to obtain a metal doped intumescent flame retardant coating liquid after the metal compound fully reacts under mechanical stirring; finally, the obtained flame-retardant coating liquid is dried to obtain the solid metal doped intumescent flame retardant.
5. The solid metal doped intumescent flame retardant of claim 4, wherein the solid metal doped intumescent flame retardant forms an intumescent carbon layer having a strength capable of withstanding more than 2000 times its weight.
6. The method for preparing the solid metal doped intumescent flame retardant as claimed in claim 4 or 5, characterized in that the preparation method comprises the following steps: stirring and uniformly mixing an amino macromolecular compound, an organic phosphonic acid compound and water to form a blending solution; then adding a metal compound, and separating to obtain a metal doped intumescent flame retardant coating liquid after the metal compound fully reacts under mechanical stirring; finally, the obtained flame-retardant coating liquid is dried to obtain the solid metal doped intumescent flame retardant.
7. Use of the solid metal-doped intumescent flame retardant of claim 4 or 5 in epoxy resins, polyurethane foams, or polyester-velen-cotton ternary blends.
8. A flame-retardant epoxy resin, the raw materials for preparing the flame-retardant epoxy resin comprise epoxy resin, a flame retardant and a curing agent, and the flame retardant is the solid metal doped intumescent flame retardant of claim 4 or 5.
9. The flame retardant epoxy resin of claim 8, wherein the expanded carbon layer formed from the flame retardant epoxy resin has a strength capable of withstanding more than 60 times its weight.
10. The flame-retardant epoxy resin according to claim 8, wherein the solid metal-doped intumescent flame retardant is added in an amount of 10-25 wt% of the epoxy resin.
11. The flame retardant epoxy resin of claim 8, wherein the curing agent is selected from the group consisting of: polyamide curing agents or aromatic amine curing agents.
12. The flame retardant epoxy resin of claim 8, wherein the curing agent is added in an amount of 20 to 80wt% of the epoxy resin.
13. A method of preparing a flame retardant epoxy resin according to any one of claims 8 to 12, characterized in that the method of preparation is: mechanically stirring and uniformly mixing the solid metal doped intumescent flame retardant with epoxy resin; and then adding a preheated curing agent for curing to obtain the flame-retardant epoxy resin.
14. The method of preparing a flame retardant epoxy resin of claim 13, wherein the curing temperature is 80 ℃ to 200 ℃.
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| JP4941804B2 (en) * | 2005-03-02 | 2012-05-30 | Ｄｉｃ株式会社 | Epoxy resin composition, cured product thereof, semiconductor sealing material, novel phenol resin, and novel epoxy resin |
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| CN1823138A (en) * | 2003-05-26 | 2006-08-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| CN106380788A (en) * | 2016-10-24 | 2017-02-08 | 西华大学 | halogen-free flame retardant, halogen-free flame retardant epoxy resin and preparation method thereof |
| CN107523024A (en) * | 2017-09-12 | 2017-12-29 | 太原理工大学 | CNT base Chitosan Phosphate composite flame-retardant agent and its preparation method and application |
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