CN112280100A - Composite intumescent flame retardant and preparation method thereof - Google Patents

Composite intumescent flame retardant and preparation method thereof Download PDF

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CN112280100A
CN112280100A CN202011088532.7A CN202011088532A CN112280100A CN 112280100 A CN112280100 A CN 112280100A CN 202011088532 A CN202011088532 A CN 202011088532A CN 112280100 A CN112280100 A CN 112280100A
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flame retardant
carbon dioxide
ldhs
dissolving
intumescent flame
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吴唯
胡焕波
沈辉
刘冬梅
芮正国
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East China University of Science and Technology
Oechsler Plastic Products Taicang Co Ltd
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East China University of Science and Technology
Oechsler Plastic Products Taicang Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a composite intumescent flame retardant and a preparation method thereof. The composite intumescent flame retardant consists of 83.33-99.67 wt% of intumescent flame retardant and 16.67-0.33 wt% of sodium oleate modified lauryl sodium sulfate intercalated calcium magnesium aluminum hydrotalcite. The present invention utilizes Ca2+、Mg2+、Al3+Cation replacement modification is carried out on the hydrotalcite by the same cations, and interlayer intercalation modification is carried out on the hydrotalcite by the anions such as dodecyl sulfate radicals to enlarge interlayer spacing and improve flame retardance of the hydrotalciteThe flame retardant property of the flame retardant is compounded with the intumescent flame retardant to form a synergistic flame retardant system, so that the flame retardant property of the compounded flame retardant is effectively improved, and the mechanical property of the polymer added with the flame retardant is synergistically ensured.

Description

Composite intumescent flame retardant and preparation method thereof
Technical Field
The invention belongs to the technical field of flame retardance, discloses a composite intumescent flame retardant and a preparation method thereof, and particularly relates to hydrotalcite chemical modification and microscopic morphology modification which can be applied to polymer materials, and a synergistic flame retardant system formed by compounding modified hydrotalcite and intumescent flame retardant.
Background
With the development of science and technology, the application range of polymer materials is wider and wider, but the flammable characteristic of the polymer materials causes many safety accidents and economic losses. Therefore, improving the flame retardancy of polymer materials has become a major issue in the fields of safety science and engineering. The traditional halogen-containing flame retardant has the advantages of good flame retardant effect, small addition amount, small influence on the mechanical properties of organic matters and the like, and is widely applied to flame retardance of high polymer materials. However, most of the halogen-containing flame retardants are toxic and carcinogenic, and release a large amount of toxic gases such as smoke and hydrogen halide during combustion, which causes secondary pollution and increasingly significant adverse effects on the environment and human life, thereby forcing governments and organizations to put restrictions on the use of halogen-containing flame retardants. Therefore, the development of novel halogen-free environment-friendly flame retardant is the trend of flame retardant scientific development, is also the focus of research in the flame retardant field at present, and is also of great importance to the life and property safety of people.
The Intumescent Flame Retardant (IFR) mainly comprises three parts, namely an acid source (such as ammonium polyphosphate (APP for short) and a carbon source (such as PER) and an air source (such as melamine). Is one of the most popular flame retardant systems at present, has the advantages of no halogen, high efficiency, low toxicity and the like, and has wide application fields. However, compared with halogen flame retardants, IFR has a large smoke yield and a relatively low flame retardant efficiency, and often needs to be added in a large amount to meet the flame retardant requirement, which leads to a great reduction in the mechanical properties of the composite material.
Hydrotalcite (LDHs for short) is a kind of anionic layered clay with chemical composition formula [ M1-x 2+Mx 3+(OH)2]Ax/n n-·mH2O, wherein M2+Is a divalent metal ion, M3+Is a trivalent metal ion, An-Is an interlayer anion. M (OH)6Octahedrons are mutually prismatic to form a laminate and carry positive charges, and the interlayer anions balance the charge of the laminate to enable the whole crystal to be electrically neutral. The special structure and property of the LDHs make the LDHs have wide application prospect in the aspects of adsorption, ion exchange, catalysis, light, electricity, magnetism and the like. LDHs also have good application as a flame retardant, and the hydrotalcite material which can be used as the flame retardant at present has ZnAl-BO3-LDHs、MgAl-BO3LDHs and ZnAl-CO3-LDHs、Mg-Al-CO3LDHs, etc. The synthetic hydrotalcite has the advantages of flame retardance of magnesium hydroxide and aluminum hydroxide due to special composition. The flame retardance of the synthetic hydrotalcite is mainly realized by two modes of gas-phase flame retardance and condensed-phase flame retardance. The gas-phase flame-retardant is that when burning, the hydrotalcite releases the bound water and CO between layers at the initial stage of degradation2The oxygen diluting agent plays a role in diluting oxygen and reducing the surface temperature of the polymer; with the rise of the temperature, the synthetic hydrotalcite sheet layer metal hydroxide generates dehydration reaction, absorbs heat and releases water, and further plays a role in flame retardance. The condensed phase flame retardant is characterized in that metal hydroxide of a synthetic hydrotalcite board layer and a polymer generate a special catalytic reaction in the combustion degradation process, a compact carbon layer is formed on the surface of the composite material, external heat and oxygen are isolated from permeating into the polymer, and the mass loss rate of the polymer during thermal degradation is slowed down. After the synthetic hydrotalcite is heated and decomposed, high-dispersion solid alkali with large specific surface area is formed in the synthetic hydrotalcite, and the synthetic hydrotalcite has a good adsorption effect on acid gas generated by combustion, so that a smoke suppression effect is achieved.
The traditional hydrotalcite synthesis method has poor controllability on the morphology, the granularity and the specific surface area, and the hydrotalcite is easy to aggregate after being dried, so that the compatibility with the polymer is poor, and the flame retardance of the material is reduced; a large amount of space and ions between the laminates cannot be effectively utilized, and the flame retardant property is not fully exerted; the common magnalium binary hydrotalcite has poor thermal stability, and cannot effectively improve the flame retardant property of the material. In order to overcome the disadvantages of hydrotalcite, scholars at home and abroad conduct the ion modification research of hydrotalcite flame retardant and obtain certain effect.
At present, due to the special layered structure of magnesium-aluminum layered double hydroxide (MgAl-LDHs), the magnesium-aluminum layered double hydroxide has wide application in the aspect of polymer flame retardance, combines the flame retardance advantages of magnesium hydroxide and aluminum hydroxide, and becomes an inorganic halogen-free flame retardant with the most research value. Other divalent or trivalent metal ions are properly and properly introduced by the layer doping and interlayer intercalation technology to construct new LDHs, which has very important significance for enriching the types of polymers/layered hydroxides and expanding the flame retardant application of the polymers/layered hydroxides. However, the LDHs type flame retardant generally has the defects of large addition amount and deterioration of the mechanical property of a polymer matrix, which greatly limits the popularization and the application of the type of flame retardant. Therefore, before being used as a flame retardant, LDHs are inevitably subjected to surface modification or compounded with other flame retardant systems.
The preparation method adopts sodium dodecyl sulfate intercalation modified calcium magnesium aluminum ternary hydrotalcite, and sodium oleate is used for modifying the calcium magnesium aluminum ternary hydrotalcite so as to improve the compatibility of the calcium magnesium aluminum ternary hydrotalcite with a polymer matrix; and then the flame retardant is compounded with an intumescent flame retardant system to obtain good flame retardant synergistic effect, which is beneficial to catalytic carbonization of the system and smoke suppression, and effectively improves the flame retardant property of the material.
Disclosure of Invention
The invention aims to provide a composite intumescent flame retardant and a preparation method thereof. Using Ca2+、Mg2+、Al3+Cation replacement modification is carried out on cations, so that the flame retardance is improved, interlayer intercalation modification is carried out on the hydrotalcite flame retardant by anions such as dodecyl sulfate radicals, the interlayer spacing is enlarged, the flame retardance is improved, dodecyl sulfate radicals are creatively introduced between calcium-magnesium-aluminum hydrotalcite laminates, a better proportion is selected, and the calcium-magnesium-aluminum hydrotalcite composite material with excellent flame retardance and mechanical property is obtained. The invention utilizes sodium oleate modified dodecyl sulfuric acidThe sodium intercalation calcium magnesium aluminum hydrotalcite improves the compatibility of IFR and the material, and the flame retardant system is halogen-free, efficient, green and environment-friendly, and can obviously improve the flame retardant property of the material. The synthesized LDHs layers contain crystal water, a large number of hydroxyl groups are arranged on the laminates, and when the calcium-magnesium-aluminum hydrotalcite flame retardant added into the polymer is heated and decomposed, the discharged water can dilute the concentration of combustible gas and isolate the further invasion of oxygen, thereby weakening the fire behavior and achieving the purpose of flame retardance. And MgO and Al generated by decomposition2O3A thermal insulation layer can be formed; and simultaneously, a large amount of heat is absorbed when the material is heated and decomposed, and the temperature of a combustion system is reduced. Therefore, the LDHs has multiple functions of flame retardance, smoke abatement, filling and the like, and is a new flame retardant variety with wide development prospect. Calcium hydroxide can be used as a synergistic flame retardant, emits water after combustion, forms calcium oxide, and is often applied to the fire-proof treatment of materials. However, the calcium hydroxide is not easy to store and is easy to absorb H in the air2O and CO2But chemically changed, and thus its use is limited. Can convert Ca into2+The flame retardant is applied to hydrotalcite flame retardant in other forms for modification so as to improve the flame retardant property of hydrotalcite. Using Ca2+Modifying hydrotalcite with Ca2+Added to hydrotalcite cation layer plate as the divalent metal ion of cation layer plate.
The invention is realized by the following technical scheme: a composite intumescent flame retardant comprises 83.33-99.67 wt% of intumescent flame retardant and 16.67-0.33 wt% of sodium oleate modified sodium dodecyl sulfate intercalated calcium magnesium aluminum hydrotalcite.
Further, the intumescent flame retardant consists of ammonium polyphosphate and pentaerythritol in a mass ratio of 3: 1.
The preparation method of the sodium oleate modified lauryl sodium sulfate intercalated calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) taking Ca (NO)3)2·4H2O、Mg(NO3)2·6H2O and Al (NO)3)3·9H2O dissolved in decarbonated water and labeled solution a.
(2) Dissolving 0.5-2 mol of NaOH in the carbon dioxide-removed water, and marking as a solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value between 9 and 11, continuing stirring for 1 to 5 hours after dripping is finished, and crystallizing for 13 to 24 hours at the temperature of between 60 and 85 ℃.
(4) And (3) carrying out suction filtration, washing the mixture to be neutral by using carbon dioxide water, drying the mixture at 60-85 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain CaMgAl-LDHs.
(5) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water, and stirring for 13-24 hours at normal temperature.
(6) And (3) carrying out suction filtration, washing the mixture to be neutral by using carbon dioxide, drying the mixture at 60-85 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(7) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2-1.2 g/L of sodium oleate, and reacting for 13-24 h.
(8) Filtering, drying, and sieving with 60-80 mesh sieve (177-250 μm) to obtain sodium oleate modified dodecyl sulfate radical type calcium magnesium aluminum hydrotalcite12H25SO4 -1-LDHs。
Wherein said Ca (NO)3)2·4H2O、Mg(NO3)2·6H2O and Al (NO)3)3·9H2The molar ratio of O is 1-3: 2-3: 1-2.
The invention has the following beneficial effects:
(1) the intercalation material using calcium-magnesium-aluminum as the metal laminate also has good flame retardant effect theoretically because the metal layer of the laminate can be decomposed into CaO and Al after the intercalation material encounters high temperature2O3And the lauryl sulfate radical anion inserted between layers can also play the role of a flame retardant, thereby blocking the contact between a combustion body and oxygen.
(2) The LDHs is halogen-free and non-toxic, and the prepared LDHs is modified by introducing an anionic surfactant SDS so as to make the LDHs hydrophobic, improve the interlayer spacing and improve the compatibility of the LDHs and macromolecules.
(3) During combustion, IFR is heated and decomposed to generate PO & and HPO & free radicals, and combustible free radicals H & and HO & in the surrounding environment are easy to capture; meanwhile, LDHs are decomposed by heating to generate H2O、CO2And the concentration of the combustible gas is diluted by the non-combustible gas, phosphate, metal oxide and the like are generated to cover and isolate thermal oxygen, and the combustion is delayed, so that the flame retardant property of the material is improved.
(4) Because the calcium element has the advantages of good flame retardant property, wide source, low price and the like, the calcium element can be used for modifying the hydrotalcite to play the synergistic flame retardant function of the hydrotalcite so as to reduce the addition of the hydrotalcite flame retardant and reduce the preparation cost.
(4) The composite intumescent flame retardant is a halogen-free green flame retardant, and the combustion process and the combustion products have little harm to the environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows the composition diagram of the composite intumescent flame retardant.
Detailed Description
The invention is further illustrated by the following specific examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.06mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as solution A, dissolving 1mol NaOH in carbon dioxide-removed water, marking as solution B, respectively dripping solution A, B into flask, stirring at normal temperature, keeping pH at 9, and continuing stirring 1 after drippingAnd h, crystallizing at 60 ℃ for 13h, performing suction filtration, washing with carbon dioxide water to be neutral, drying at 60 ℃, grinding, and sieving with a 60-80-mesh sieve (177-250 mu m) to obtain CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99.67 wt% of IFR and 0.33 wt% of LDHs to form the composite intumescent flame retardant.
Example 2
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.06mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 9, continuously stirring for 1h after dropwise adding is finished, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
99.33 wt% of IFR and 0.37 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 3
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.06mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 9, continuously stirring for 1h after dropwise adding is finished, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99 wt% of IFR and 1 wt% of LDHs to form the composite intumescent flame retardant.
Example 4
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.06mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 9, continuously stirring for 1h after dropwise adding is finished, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
98.67 wt% of IFR and 1.33 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 5
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.06molMg(NO3)2·6H2O and 0.03mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as solution A, dissolving 1mol NaOH in carbon dioxide-removed water, marking as solution B, respectively dripping solution A, B into flask, stirring at normal temperature, keeping pH at 10, continuing stirring for 1h after dripping, crystallizing at 60 deg.C for 15h, vacuum filtering, washing with carbon dioxide-removed waterWashing to be neutral, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99.67 wt% of IFR and 0.33 wt% of LDHs to form the composite intumescent flame retardant.
Example 6
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.06molMg(NO3)2·6H2O and 0.03mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuously stirring for 1h after dropwise adding, crystallizing for 15h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, sieving by using a 60-80 mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
99.33 wt% of IFR and 0.67 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 7
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.06molMg(NO3)2·6H2O and 0.03mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuously stirring for 1h after dropwise adding, crystallizing for 15h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, sieving by using a 60-80 mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
99 wt% of IFR and 1 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 8
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) miningUsing coprecipitation method to obtain 0.06mol Ca (NO)3)2·4H2O、0.06molMg(NO3)2·6H2O and 0.03mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuously stirring for 1h after dropwise adding, crystallizing for 15h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, sieving by using a 60-80 mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
98.67 percent of IFR and 1.33 percent of LDHs are weighed to form the composite intumescent flame retardant.
Example 9
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.04molMg(NO3)2·6H2O and 0.02mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as solution A, dissolving 1mol NaOH in carbon dioxide-removed water, marking as solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 12, continuously stirring for 1h after dropwise adding is finished, crystallizing for 15h at 60 ℃, performing suction filtration, washing to be neutral with carbon dioxide, drying at 60 ℃, grinding, and sieving with a 60-80 mesh sieve (177℃)250 μm) and recorded as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99.67 wt% of IFR and 0.33 wt% of LDHs to form the composite intumescent flame retardant.
Example 10
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.04molMg(NO3)2·6H2O and 0.02mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding is finished, crystallizing for 17h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
99.33 wt% of IFR and 0.67 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 11
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.04molMg(NO3)2·6H2O and 0.02mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding, crystallizing at 60 ℃ for 19h, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99 wt% of IFR and 1 wt% of LDHs to form the composite intumescent flame retardant.
Example 12
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.04molMg(NO3)2·6H2O and 0.02mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding, crystallizing at 60 ℃ for 14h, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
98.67 wt% of IFR and 1.33 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 13
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.12mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99.67 wt% of IFR and 0.33 wt% of LDHs to form the composite intumescent flame retardant.
Example 14
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.12mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
99.33 wt% of IFR and 0.67 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Example 15
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.12mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuously stirring for 1h after dropwise adding, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, sieving by using a 60-80 mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 99 wt% of IFR and 1 wt% of LDHs to form the composite intumescent flame retardant.
Example 16
The preparation method of the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite comprises the following steps:
(1) by adopting a coprecipitation method, 0.06mol Ca (NO) is taken3)2·4H2O、0.12molMg(NO3)2·6H2O and 0.12mol Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 1mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 11, continuously stirring for 1h after dropwise adding, crystallizing for 13h at 60 ℃, performing suction filtration, washing to be neutral by using carbon dioxide water, drying at 60 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as CaMgAl-LDHs.
(2) Dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13 hours at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain SDS-LDHs.
(3) Dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 1.2g/L of sodium oleate, reacting for 13 hours, filtering, drying, and sieving with a 60-80 mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
The preparation method of the composite intumescent flame retardant comprises the following steps:
98.67 wt% of IFR and 1.33 wt% of LDHs are weighed to form the composite intumescent flame retardant.
Comparative example 1
Weighing IFR to form an intumescent flame retardant, putting the intumescent flame retardant and High Impact Polystyrene (HIPS) into a vacuum oven, drying for 12h at 80 ℃, and removing redundant moisture and volatile matters in the raw materials. Taking 70 parts by mass of HIPS and 30 parts by mass of intumescent flame retardant, weighing raw materials, premixing in a high-speed mixer at the rotating speed of 2000r/min for 5min, and then putting the mixed raw materials into a double-screw extruder for melt extrusion at the temperature of 190 ℃ and the rotating speed of 40 r/min. The extruded pellets were injection molded into standard bars in an injection molding machine.
Comparative example 2
Weighing high impact polystyrene, putting the high impact polystyrene into a vacuum oven, drying for 12h at 80 ℃, and removing redundant water and volatile matters in the raw materials. The raw materials are put into a double-screw extruder for melt extrusion, and the temperature of the extruder is 190 ℃ and the rotating speed of the extruder is 40 r/min. The extruded pellets were injection molded into standard bars in an injection molding machine.
Effect verification
The composite intumescent flame retardant and High Impact Polystyrene (HIPS) prepared from example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 15, example 16, comparative example 1 and comparative example 2 described above were placed in a vacuum oven and dried at 80 ℃ for 12 hours to remove excess moisture and volatiles from the raw materials. Taking 70 parts by mass of HIPS and 30 parts by mass of a composite intumescent flame retardant, weighing raw materials, premixing in a high-speed mixer at the rotating speed of 2000r/min for 5min, putting the mixed raw materials into a double-screw extruder for melt extrusion, and controlling the rotating speed of 40r/min at the temperature of 190 ℃ of the extruder. The extruded pellets were injection molded into standard bars in an injection molding machine. The performance test was performed according to the following criteria: the limit oxygen index test is carried out according to GB/T2406.2-2009, the horizontal and vertical burning test GB/T2408-2008, and the tensile test is carried out according to GB/T1040.3-2006. The obtained flame retardant property test results and mechanical property test results are shown in table 1.
TABLE 1 flame retardancy and mechanical Properties test results
Figure BDA0002721248350000221
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.

Claims (5)

1. The composite intumescent flame retardant is characterized by comprising 83.33-99.67 wt% of intumescent flame retardant and 16.67-0.33 wt% of sodium oleate modified sodium dodecyl sulfate intercalated calcium magnesium aluminum hydrotalcite.
2. A composite intumescent flame retardant as claimed in claim 1, characterized in that the intumescent flame retardant consists of ammonium polyphosphate and pentaerythritol in a mass ratio of 3: 1.
3. The composite intumescent flame retardant of claim 1, wherein said sodium oleate modified sodium dodecyl sulfate intercalated calcium magnesium aluminum hydrotalcite is prepared by the following method:
(1) taking Ca (NO) by coprecipitation method3)2·4H2O、Mg(NO3)2·6H2O and Al (NO)3)3·9H2Dissolving O in carbon dioxide-removed water, marking as a solution A, dissolving 0.5-2 mol of NaOH in the carbon dioxide-removed water, marking as a solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value between 9 and 11, continuously stirring for 1-5 h after dropwise adding is finished, crystallizing for 13-24 h at 60-85 ℃, performing suction filtration, washing with carbon dioxide to be neutral, drying at 60-85 ℃, grinding, and sieving with a 60-80-mesh sieve (177-250 mu m), marking as CaMgAl-LDHs;
(2) dissolving 15g of CaMgAl-LDHs and 16.2g of Sodium Dodecyl Sulfate (SDS) in carbon dioxide-removed water by adopting an ion exchange method, stirring for 13-24 h at normal temperature, carrying out suction filtration, washing to be neutral by using carbon dioxide, drying at 60-85 ℃, grinding, sieving by using a 60-80-mesh sieve (177-250 mu m), and marking as SDS-LDHs;
(3) dissolving 10g of SDS-LDHs in carbon dioxide-removed water, stirring at normal temperature, adding 0.2-1.2 g/L of sodium oleate, reacting for 13-24 h, performing suction filtration, drying, and sieving with a 60-80-mesh sieve (177-250 mu m) to obtain the sodium oleate modified dodecyl sulfate radical calcium magnesium aluminum hydrotalcite.
4. A composite intumescent flame retardant as claimed in claim 3, characterized in that Ca (NO)3)2·4H2O、Mg(NO3)2·6H2O and Al (NO)3)3·9H2The molar ratio of O is 1-3: 2-3: 1-2.
5. Method for using a composite intumescent flame retardant, characterized in that a composite intumescent flame retardant according to any of claims 1 to 4 is added to a polymeric material.
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