CN112480474A - Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof - Google Patents

Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof Download PDF

Info

Publication number
CN112480474A
CN112480474A CN202011336335.2A CN202011336335A CN112480474A CN 112480474 A CN112480474 A CN 112480474A CN 202011336335 A CN202011336335 A CN 202011336335A CN 112480474 A CN112480474 A CN 112480474A
Authority
CN
China
Prior art keywords
flame retardant
deionized water
ldhs
hydrotalcite
intumescent flame
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011336335.2A
Other languages
Chinese (zh)
Inventor
吴唯
沈辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN202011336335.2A priority Critical patent/CN112480474A/en
Publication of CN112480474A publication Critical patent/CN112480474A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses a smoke-suppressing intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and a preparation method thereof. The intumescent flame retardant consists of 70-99 wt% of intumescent flame retardant and 30-1 wt% of Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation. The present invention utilizes Ca2+、Mg2+、Al3+Performing cation replacement modification on hydrotalcite by using equal cations, and performing cation replacement modification on hydrotalcite by using carbonate, borate and dodecaborateThe hydrotalcite is subjected to interlayer intercalation modification by anions such as alkyl sulfate radicals and the like to enlarge interlayer spacing and improve the flame retardant property of the hydrotalcite flame retardant, and the hydrotalcite flame retardant and the intumescent flame retardant are compounded 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 a high polymer material added with the flame retardant is cooperatively ensured.

Description

Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof
Technical Field
The invention relates to hydrotalcite synthesis modification applicable to high polymer materials, and a synergistic flame retardant system formed by compounding modified hydrotalcite and intumescent flame retardant, belonging to the technical field of organic synthesis and flame retardant materials. In particular discloses an intumescent flame retardant containing different inorganic and organic anion intercalation Ca-based ternary hydrotalcite smoke-suppressing additives and a preparation method thereof.
Background
At present, in the application process of the high polymer material in the flame retardant industry, an additive method is mainly adopted, and a reaction method is rarely adopted, so that the additive is more widely used in the flame retardant material, and even the performance of the flame retardant material is determined. So far, the focus of the research on flame-retardant polymer materials is still on the research on additives, and good additives like enzymes for chemical reactions can accelerate the rate of chemical reactions. As the high molecular material is ignited by an open fire, violent oxidation reaction can occur, a great deal of hydroxyl can be released in the combustion process, and as the hydroxyl is very active and is easy to combine with other substances, the product after combination is water and other organic matters. And other organic matters and oxygen are further combined to generate further decomposition reaction and form new organic matters, and in the cyclic reaction, the combustion can be continuously carried out, which is the flame-retardant process of the high-molecular flame retardant.
With the continuous expansion of the application field of materials, the research on the flame retardant technology of the materials will get more and more attention. The intumescent flame retardant has excellent flame retardant performance and can not generate secondary pollution during combustion, so that the intumescent flame retardant can be more and more widely applied to the field of plastic flame retardance in the future. In future, the source of the intumescent flame retardant raw material is expanded by polymer molecule design and combining the technologies of surface modification, superfine treatment, microencapsulation and the like, so that the flame retardant property of the intumescent flame retardant and plastic composite material is further improved. In addition, the synergistic flame retardant or compound flame retardant property of the intumescent flame retardant and other additives is actively researched and developed to reduce the production cost and expand the application field.
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 a gas 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 a very wide application field. One of the disadvantages of the halogen-free intumescent flame retardant is that the addition amount is relatively large, and the addition amount of the traditional IFR system is more than 30%. In the case of a polymer material, a high addition amount means a loss of mechanical properties, and a series of properties such as flowability and gloss of the material are also affected. The addition of the IFR synergist improves the flame retardant efficiency of IFR and reduces the addition amount of the IFR synergist, and is a very effective measure for solving the problems.
In order to reduce the influence of the addition amount of the intumescent flame retardant on the polymer, a synergist with a special structure (such as a porous structure and a laminated structure) is selected and added, and then the synergist is compounded with the intumescent flame retardant, so that the flame retardant efficiency is further improved. Hydrotalcite (LDHs, also called layered double hydroxides) is one of inorganic flame retardants, has a structure and a composition similar to those of aluminum hydroxide and magnesium hydroxide, and has characteristics of a special layered structure, interchangeability of interlayer ions, memory effect, thermal stability, and the like. The LDHs serving as a flame retardant is added into a high polymer material, and can be decomposed to release a large amount of water and carbon dioxide after being heated, and absorb a large amount of heat, so that the thermal decomposition and combustion rate of the material are reduced, and the flame retardance, thermal stability and smoke suppression performance of the material can be effectively improved. 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, thereby playing a role in absorbing acid gas generated by combustionHas smoke inhibiting effect.
As an inorganic additive flame retardant, LDHs has the problems of large addition amount, poor compatibility with materials, poor flame retardant efficiency and the like; meanwhile, magnesium in the LDHs is active in chemical property and is very easy to oxidize and burn, which seriously hinders the large-scale application of the LDHs.
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. Ion exchange is an important method for synthesizing LDHs intercalation structure, and a commonly used precursor is MgAl-Cl-LDHs and MgAl-NO3 --LDHs. Therefore, before being used as a flame retardant, LDHs are inevitably subjected to surface modification or compounded with other flame retardant systems.
The layered double hydroxide has the characteristic similar to that of molecular sieve in the layer space, and may be used directly as the rigid support of the fire retarding expansion layer to raise the fire retarding performance of the material.
The invention adopts Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation to improve the compatibility with high polymer materials; 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. Therefore, the polypropylene composite material prepared by compounding the layered hydroxide and the intumescent flame retardant has good flame retardant effect, low smoke generation and good mechanical property.
Disclosure of Invention
The invention aims to provide an intumescent flame retardant containing different inorganic and organic anion intercalation Ca-based ternary hydrotalcite smoke suppression additives and a preparation method thereof.
As the surface of the LDH has stronger polar groups-OH, stronger hydrogen bond action is generated among hydrotalcite particles, on one hand, the LDH is easy to agglomerate, on the other hand, the compatibility of the LDH and the hydrotalcite particles is poor due to polarity difference, so that the LDH is polymerizedPoor dispersion in the polymer matrix reduces the stability of the flame retardant polymer material. The invention prepares the modified hydrotalcite by a coprecipitation method. Using Ca2+、Mg2+、Al3+And (3) carrying out cation replacement modification on the hydrotalcite by using cations such as carbonate, borate, dodecyl sulfate and the like, and carrying out interlayer intercalation modification on the hydrotalcite to enlarge the interlayer spacing so as to finally obtain the Ca-based hydrotalcite with excellent flame retardance and mechanical property.
The Ca-based ternary hydrotalcite containing different inorganic and organic anions intercalation is used for improving the compatibility of IFR and materials, and the flame-retardant system is halogen-free, efficient, green and environment-friendly, and can remarkably improve the flame-retardant performance of the materials. The synthesized LDHs layers contain crystal water, a large number of hydroxyl groups are arranged on the laminates, and when the Ca-based hydrotalcite flame retardant added into the high polymer material is heated and decomposed, the released water, carbon dioxide and the like can dilute the concentration of combustible gas and isolate the further invasion of oxygen, so that the fire behavior is weakened, and the purpose of flame retardance is achieved. The metal oxide generated by decomposition can form a heat insulation layer; 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 technical scheme of the invention is as follows:
a smoke suppression intumescent flame retardant containing multiple anion intercalation Ca-based ternary hydrotalcite consists of 70-99 wt% of intumescent flame retardant and 30-1 wt% of Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation;
the intumescent flame retardant consists of 60-80 wt% of ammonium polyphosphate and 40-20 wt% of pentaerythritol;
further, the preparation method of Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation layers comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) Dissolving 0.5-3 mol of NaOH in deionized water, and marking as solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value between 9 and 12, continuing stirring for 1 to 6 hours after dripping is finished, and crystallizing for 10 to 24 hours at the temperature of between 60 and 90 ℃.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60-90 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m), and marking as NO3 --LDHs。
(5) Taking 15gNO3 -And (3) dissolving LDHs, 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate in deionized water, and stirring for 10-24 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60-90 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the molar ratio of the divalent metal ions to the trivalent metal ions is 1-4, and the total concentration of the metal ions is 0.1-1 mol/L.
The invention has the following beneficial effects:
(1) with Ca2+The intercalation material of the metal laminate has good flame retardant effect theoretically, because the metal layer of the laminate can be decomposed into substances with flame retardant effect such as metal oxide and the like after the intercalation material meets high temperature, and carbonate and borate inserted between layers can also play the role of a flame retardant, thereby blocking the contact of a combustion body and oxygen.
(2) The LDHs is halogen-free and non-toxic, and the organic intercalation of the LDHs prepared by introducing long-chain anion pairs is modified, so that the LDHs is hydrophobized, the interlayer spacing is improved, and the compatibility of the LDHs and macromolecules is also improved.
(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 sodium carbonate, the boric acid and the lauryl sodium sulfate have the advantages of wide sources, low price and the like, the hydrotalcite can be modified by the sodium carbonate, the boric acid and the lauryl sodium sulfate to play the synergistic flame-retardant function of the hydrotalcite, so that the addition amount of the hydrotalcite flame retardant is reduced, and the preparation cost is reduced.
(5) A small amount of synergist is added into IFR, so that the using amount of the flame retardant can be reduced, and the flame retardant property of the polymer can be obviously improved.
(6) The intumescent flame retardant is a halogen-free environment-friendly 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 is a scanning electron microscope image of a ternary water-slide containing multiple anion intercalation Ca radicals.
Detailed Description
The present invention will be further described with reference to the following 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 Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 0.5mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-1, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 2
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 0.5mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuing stirring for 1h after dripping is finished, and crystallizing for 10h at 60 ℃.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -Dissolving LDHs, 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate in deionized water, and stirring at normal temperatureStirring for 10 h.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-1, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 3
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 0.5mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 11, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-1, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 4
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 0.5mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 12, stirring for 1 hr, and crystallizing at 60 deg.C for 10 hr.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-1, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 5
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtering and removingWashing the seeds to be neutral, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and marking as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 6
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 7
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuing stirring for 1h after dripping is finished, and crystallizing for 10h at 60 ℃.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 8
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 11, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-3, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 9
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 70 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-4, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 10
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 11 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-4, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 11
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 12, stirring for 1 hr, and crystallizing at 60 deg.C for 10 hr.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 70 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-3, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 12
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuing stirring for 2h after dripping is finished, and crystallizing for 10h at 60 ℃.
(4) Filtering, washing with deionized water to neutrality,drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 13
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 3h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 1 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 14
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 12, stirring for 1h after dripping, and crystallizing at 75 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-3, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 15
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) And respectively dripping the solution A, B into a flask, stirring at normal temperature, keeping the pH value at 10, continuing stirring for 1h after dripping is finished, and crystallizing for 10h at 60 ℃.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 65 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and marking as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 90 wt% of IFR and 10 wt% of LDHs to form the composite intumescent flame retardant.
Example 16
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 80 wt% of IFR and 20 wt% of LDHs to form the composite intumescent flame retardant.
Example 17
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 82 wt% of IFR and 18 wt% of LDHs to form the composite intumescent flame retardant.
Example 18
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 84 wt% of IFR and 16 wt% of LDHs to form the composite intumescent flame retardant.
Example 19
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Filtering, washing to neutrality with deionized water, drying at 60 deg.C,grinding, sieving with 60-80 mesh sieve (177-250 μm) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
weighing 88 wt% of IFR and 12 wt% of LDHs to form the composite intumescent flame retardant.
Example 20
The preparation method of the Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalation comprises the following steps:
(1) taking Ca (NO)3)2·4H2O, divalent metal nitrate and trivalent metal nitrate dissolved in the deionized water, labeled solution A.
(2) 1mol of NaOH was dissolved in deionized water and labeled as solution B.
(3) Dripping the solution A, B into a flask, stirring at normal temperature, keeping pH at 9, stirring for 1h after dripping, and crystallizing at 60 deg.C for 10 h.
(4) Suction filtration, washing to neutrality by using deionized water, drying at 60 ℃, grinding, sieving with a 60-80 mesh sieve (177-250 mu m) and recording as NO3 --LDHs。
(5) Taking 15gNO3 -LDHs and 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate are dissolved in deionized water and stirred for 10 hours at normal temperature.
(6) And (4) carrying out suction filtration, washing the mixture to be neutral by using deionized water, drying the mixture at 60 ℃, grinding the mixture, and sieving the ground mixture by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
Wherein the mole ratio of the divalent metal ions to the trivalent metal ions is n-2, and the total concentration of the metal ions is 0.5 mol/L.
The preparation method of the composite intumescent flame retardant comprises the following steps:
89 wt% of IFR and 11 wt% of LDHs are weighed to form the composite intumescent flame retardant.
The application effect is as follows:
the composite intumescent flame retardant prepared from the above 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, example 17, example 18, example 19 and example 20 and the polypropylene (PP) are put into an oven and dried at 90 ℃ for 13h to remove the excess moisture and volatiles in the raw materials. Taking 70 parts by mass of PP and 30 parts by mass of composite intumescent flame retardant, weighing raw materials, and carrying out melt blending on the mixed materials for about 15min at 185 ℃ by adopting a double-roll open mill to obtain the PP composite material before and after modification. The composite material is hot pressed by a flat vulcanizing machine at 185 ℃, cold-pressed and molded, and placed for 20 hours at room temperature to be processed into a standard sample strip for testing. The performance test was performed according to the following criteria: the horizontal vertical burning test GB/T2408-2008 is carried out, the limit oxygen index test is carried out according to GB/T2406.2-2009, and the cone calorimetry test is carried out according to ISO 5660. The results of the UL-94, LOI and total cone calorimetry (TSP) measurements obtained for the standard samples are shown in Table 1.
TABLE 1 flame retardancy test results of the standard test specimens of the examples
Figure BDA0002797255070000151
The performance tests were carried out on the flame-retardant polypropylene materials prepared in the above examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 according to the following criteria: tensile tests were carried out according to GB/T1040.3-2006 and bending tests were carried out according to GB/T9341-2008. The results of the mechanical property tests of the obtained standard samples are shown in table 2.
TABLE 2 mechanical property test results of the standard samples of the examples
Figure BDA0002797255070000161
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 (4)

1. A smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite is characterized by consisting of 70-99 wt% of intumescent flame retardant and 30-1 wt% of Ca-based ternary hydrotalcite containing different inorganic and organic anion intercalated layers;
the intumescent flame retardant consists of 60-80 wt% of ammonium polyphosphate and 40-20 wt% of pentaerythritol;
the different inorganic and organic anions are carbonate or borate or dodecyl sulfate.
2. The smoke suppressing and expanding type flame retardant of Ca-based ternary hydrotalcite containing multiple anion intercalation according to claim 1, wherein in the Ca-based ternary hydrotalcite, divalent metal ion M2+Is Mg2+、Co2+、Cu2+、Fe2+One of (1); trivalent metal ion M3+Is Al3+、Mn3+、Fe3+One kind of (1).
3. The preparation method of the smoke suppression intumescent flame retardant containing the multiple anion intercalated Ca-based ternary hydrotalcite of claim 1 is characterized by comprising the following preparation steps:
(1) taking Ca (NO) by coprecipitation method3)2x4H2Dissolving O, divalent metal nitrate and trivalent metal nitrate in deionized water, marking as solution A, dissolving 0.5-3 mol of NaOH in deionized water, marking as solution B, respectively dropwise adding the solution A, B into a flask, stirring at normal temperature, keeping the pH value between 9-12, continuously stirring for 1-6 h after dropwise adding is finished, crystallizing for 10-24 h at 60-90 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 60-90 ℃, grinding, sieving by a 60-80-mesh sieve (177-250 mu m), marking as NO3 --LDHs；
(2) By ion exchange method, 15gNO is taken3 -And (3) dissolving LDHs, 5g of sodium carbonate, 5g of boric acid and 5g of sodium dodecyl sulfate in deionized water, stirring for 1-6 h at normal temperature, carrying out suction filtration, washing to be neutral by using the deionized water, drying at 60-90 ℃, grinding, and sieving by using a 60-80-mesh sieve (177-250 mu m) to obtain LDHs.
4. The method for preparing the smoke suppression intumescent flame retardant containing the multiple anion intercalated Ca-based ternary hydrotalcite of claim 3, wherein the molar ratio of divalent metal ions to trivalent metal ions is 1-4, and the total concentration of the metal ions is 0.1-1 mol/L.
CN202011336335.2A 2020-11-25 2020-11-25 Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof Pending CN112480474A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011336335.2A CN112480474A (en) 2020-11-25 2020-11-25 Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011336335.2A CN112480474A (en) 2020-11-25 2020-11-25 Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112480474A true CN112480474A (en) 2021-03-12

Family

ID=74934112

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011336335.2A Pending CN112480474A (en) 2020-11-25 2020-11-25 Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112480474A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478061A (en) * 2022-04-01 2022-05-13 舒城诚鑫建材有限公司 Modified fireproof uniform board and production process thereof
CN114806071A (en) * 2022-05-27 2022-07-29 史凤华 Environment-friendly flame-retardant anti-aging ABS composite material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1468913A (en) * 2003-03-14 2004-01-21 北京化工大学 Borate radical intercalated hydrotalcite and its prepn process and application as fire retardant
CN101456929A (en) * 2008-12-31 2009-06-17 浙江工业大学 Styrene-acrylic/hydrotalcite-like nano composite emulsion and preparation method thereof
US20100256269A1 (en) * 2007-07-05 2010-10-07 Braterman Paul S Nickel incorporation into ldh chlorobenzenesulfonate
CN103756371A (en) * 2013-12-31 2014-04-30 福建师范大学 Preparation method of different acid radical ion mixed and intercalated hydrotalcite flame retardant
CN106674598A (en) * 2017-01-05 2017-05-17 广州光通电子科技有限公司 Preparation method for efficient modified layered double-hydroxide flame retardant additive
CN110627079A (en) * 2019-09-27 2019-12-31 广西大学 Ternary borate hydrotalcite flame retardant and preparation method and application thereof
CN110862575A (en) * 2019-11-15 2020-03-06 南京理工大学 Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1468913A (en) * 2003-03-14 2004-01-21 北京化工大学 Borate radical intercalated hydrotalcite and its prepn process and application as fire retardant
US20100256269A1 (en) * 2007-07-05 2010-10-07 Braterman Paul S Nickel incorporation into ldh chlorobenzenesulfonate
CN101456929A (en) * 2008-12-31 2009-06-17 浙江工业大学 Styrene-acrylic/hydrotalcite-like nano composite emulsion and preparation method thereof
CN103756371A (en) * 2013-12-31 2014-04-30 福建师范大学 Preparation method of different acid radical ion mixed and intercalated hydrotalcite flame retardant
CN106674598A (en) * 2017-01-05 2017-05-17 广州光通电子科技有限公司 Preparation method for efficient modified layered double-hydroxide flame retardant additive
CN110627079A (en) * 2019-09-27 2019-12-31 广西大学 Ternary borate hydrotalcite flame retardant and preparation method and application thereof
CN110862575A (en) * 2019-11-15 2020-03-06 南京理工大学 Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478061A (en) * 2022-04-01 2022-05-13 舒城诚鑫建材有限公司 Modified fireproof uniform board and production process thereof
CN114478061B (en) * 2022-04-01 2022-12-13 舒城诚鑫建材有限公司 Modified fireproof uniform board and production process thereof
CN114806071A (en) * 2022-05-27 2022-07-29 史凤华 Environment-friendly flame-retardant anti-aging ABS composite material and preparation method thereof

Similar Documents

Publication Publication Date Title
Shang et al. Facile preparation of layered melamine-phytate flame retardant via supramolecular self-assembly technology
Du et al. Flammability characteristics and synergistic effect of hydrotalcite with microencapsulated red phosphorus in halogen-free flame retardant EVA composite
CN112280100A (en) Composite intumescent flame retardant and preparation method thereof
Qu et al. A novel intumescent flame retardant and smoke suppression system for flexible PVC
CN103113623B (en) Preparation method of LDHs (Layered Double Hydroxides) composite flame retardant
CN112480474A (en) Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof
Xu et al. The effect of ammonium polyphosphate on the mechanism of phosphorous-containing hydrotalcite synergism of flame retardation of polypropylene
CN105061761A (en) Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof
CN1468913A (en) Borate radical intercalated hydrotalcite and its prepn process and application as fire retardant
CN103382676A (en) Flame retardant paper containing rare earth-containing hydrotalcite, and preparation method and application thereof
CN113817287A (en) Bio-based nano synergistic flame retardant and preparation method and application thereof
JP2017078014A (en) Layered double hydroxide in which hydrogen phosphate ion is intercalated, flame retardant containing layered double hydroxide, flame-retardant synthetic resin composition, and method for producing layered double hydroxide
Jiao et al. Synthesis of a magnesium/aluminum/iron layered double hydroxide and its flammability characteristics in halogen‐free, flame‐retardant ethylene/vinyl acetate copolymer composites
Shen et al. Effect of modified layered double hydroxide on the flammability of intumescent flame retardant PP nanocomposites
Liu et al. Interaction between magnesium hydroxide and microencapsulated red phosphorus in flame‐retarded high‐impact polystyrene composite
CN110564058B (en) Green intumescent flame-retardant polypropylene and preparation method thereof
CN112210629B (en) Biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and preparation method thereof
CN113999534B (en) Graphene ultraviolet-resistant flame-retardant synergist and preparation method thereof
CN109082017B (en) Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof
CN110627079B (en) Ternary borate hydrotalcite flame retardant and preparation method and application thereof
CN110005464B (en) Coal spontaneous combustion inhibitor based on rare-earth hydrotalcite and preparation method thereof
CN117050519A (en) Preparation method of flame-retardant nylon 66 composite material
CN106904627B (en) 2MgO·B2O3·1.5H2O/Mg(OH)2Nanometer flame retardent materials and its in-situ preparation method
CN114395167A (en) Carbon microsphere @ hydrotalcite @ polyphosphazene hybrid flame retardant and preparation method thereof
CN115558164A (en) Nano flame retardant with core-shell structure and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210312

WD01 Invention patent application deemed withdrawn after publication