CN115353669B - Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof - Google Patents
Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof Download PDFInfo
- Publication number
- CN115353669B CN115353669B CN202210925287.3A CN202210925287A CN115353669B CN 115353669 B CN115353669 B CN 115353669B CN 202210925287 A CN202210925287 A CN 202210925287A CN 115353669 B CN115353669 B CN 115353669B
- Authority
- CN
- China
- Prior art keywords
- containing monomer
- sulfur
- nitrogen
- phosphorus
- mgal
- 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.)
- Active
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
- 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
- C08K3/28—Nitrogen-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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a hydrotalcite-based flame retardant containing sulfur, nitrogen, phosphorus and transition metal and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and a preparation method thereof.
Background
Hydrotalcite (LDHs) is an anionic layered compound, has no fixed chemical composition, and the metal element types and the composition proportion of the laminate, the types and the quantity of interlayer anions and the two-dimensional pore structure can be regulated and controlled within a certain range according to the needs, so that the material with special structure and function is obtained. Divalent metal cations on the laminate can be isomorphously substituted with trivalent metal cations of similar ionic radius within a certain proportion range, so that the main laminate has partial positive charges, and the surface of the main laminate can be modified by utilizing electrostatic force. The composition of LDHs and the regulation and control of anions between layers enable the LDHs to have multiple functions, and the LDHs becomes a novel functional material with great research potential and application prospect. In addition, the non-toxic low-cost and easy-to-prepare LDHs can absorb a large amount of heat when being heated, and reduce the temperature of a combustion system, so that the LDHs becomes a hot spot for domestic and foreign flame retardant research.
While LDHs have excellent flame-retardant smoke-suppressing effect, do not contain halogen, do not generate toxic gas and corrosive gas during combustion, have the advantages of no toxicity, low price and easy preparation, hydrotalcite is easy to agglomerate. In order to achieve excellent flame retardant effect in flame retardant applications, a large amount of LDHs needs to be added into the polymer, and the physical and mechanical properties and processability of the polymer are seriously affected by the addition amount and agglomeration phenomenon.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and the preparation method thereof, wherein the nitrogen-containing monomer (CS) and the phosphorus-containing monomer (PA) are assembled layer by layer on the surface of hydrotalcite modified by the sulfur-containing monomer (LS), and transition metal elements are introduced, so that the thermal stability of the hydrotalcite is enhanced, the agglomeration of the hydrotalcite is reduced, the dispersibility of the hydrotalcite in a polymer matrix is improved, and the char formation performance of the hydrotalcite is enhanced, thereby greatly enhancing the flame retardant performance of the hydrotalcite-based flame retardant.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal, comprising the following steps:
(1) The mixed salt solution of magnesium salt and aluminum salt and the mixed alkali solution of sodium hydroxide, sodium carbonate and sulfur-containing monomer are used as raw materials, and MgAl-LDH modified by the sulfur-containing monomer is prepared by coprecipitation;
(2) Dispersing MgAl-LDH modified by sulfur-containing monomers in deionized water to obtain a suspension A; dispersing a nitrogen-containing monomer into deionized water to obtain a dispersion liquid B; dripping the dispersion liquid B into the suspension liquid A, fully and uniformly mixing to enable the nitrogen-containing monomer to be adsorbed on MgAl-LDH modified by the sulfur-containing monomer, and drying after solid-liquid separation to obtain the MgAl-LDH modified by the sulfur-containing nitrogen monomer;
(3) Dispersing MgAl-LDH modified by sulfur-nitrogen-containing monomer in deionized water to obtain suspension C; dispersing a phosphorus-containing monomer into a NaOH aqueous solution to obtain phosphorus-containing monomer alkali liquor D; dropping the phosphorus-containing monomer alkali liquor D into the suspension C, fully and uniformly mixing to enable the phosphorus-containing monomer to be adsorbed on MgAl-LDH modified by the sulfur-containing nitrogen monomer, then adding the transition metal salt solution, fully and uniformly mixing, and drying after solid-liquid separation to obtain the hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal.
It is known to those skilled in the art that hydrotalcite can be produced not only by releasing H 2 O and CO 2 Can dilute the combustible gas, and can also play a role of a physical barrier for isolating flame and absorbing smoke dust particles, thereby effectively improving the flame retardance and smoke suppression of the polymer matrix. However, hydrotalcite is highly susceptible to agglomeration in the matrix due to poor compatibility with the polymer matrix, and the presence of strong van der Waals and electrostatic forces between the layers, resulting in unsatisfactory flame retardant properties. According to the invention, the charged base material is alternately immersed into positively and negatively charged substances through electrostatic interaction to realize layer-by-layer assembly, the MgAl-LDH modified by the sulfur-containing monomer is prepared, and then the nitrogen-containing monomer is assembled on the surface of the MgAl-LDH modified by the sulfur-containing monomer by utilizing electrostatic force between the nitrogen-containing monomer and the charge opposite to that of the sulfur-containing monomer. Similarly, the electrostatic force existing between the phosphorus-containing monomer and the nitrogen-containing monomer is utilized to assemble the phosphorus-containing monomer on the MgAl-LDH surface modified by the sulfur-containing nitrogen monomer, and meanwhile, transition metal ions are chelated on the outermost layer because of the negative charge carried by the phosphorus-containing monomer. The hydrotalcite assembled and modified layer by layer improves the problem of self-agglomeration of the hydrotalcite, improves the dispersion performance of the hydrotalcite, improves the compatibility of the hydrotalcite and a polymer matrix, contains rich flame retardant elements such as sulfur, nitrogen, phosphorus and transition metal, plays a flame retardant role in gas phase and condensed phase simultaneously, dilutes oxygen required for maintaining combustion, interrupts the chain reaction of combustion due to the free radical capturing effect of the phosphorus, and improves the defect of insufficient carbon forming effect of the hydrotalcite by adding the phosphorus element and the transition metal element, thereby forming a continuous compact carbon layer and further protecting the lower matrix from being burnt.
The hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal constructs a flame-retardant multilayer film between a base material and the flame retardant, directly interferes the combustion process, weakens the adverse effect on mechanical properties when the flame retardant is added into the base material, reduces the deterioration of the mechanical properties of a polymer matrix due to the addition of the flame retardant as much as possible, obviously improves the flame retardant property of a polyolefin matrix material through multiple synergistic effect, simultaneously reduces the damage of the flame retardant to the mechanical properties of the matrix material, and obtains the flame-retardant high polymer composite material with excellent comprehensive properties.
The inventor finds that in the layer-by-layer assembly process of hydrotalcite, when hydrotalcite, monomers containing sulfur, nitrogen, phosphorus, transition metal elements and the like are simultaneously put into the same container for reaction, the assembly cannot be controlled, various products can be obtained, and the hydrotalcite is not single layer-by-layer assembled and modified. The hydrotalcite with uniformly assembled medium on the surface can be prepared only by adopting the step-by-step layer-by-layer assembly of the charged medium, so that the problem of dispersibility of the hydrotalcite is solved, the compatibility of the hydrotalcite and a polyolefin matrix is improved, the synergistic effect is improved, the flame retardant property of a polymer matrix material is obviously improved, and meanwhile, the damage of the flame retardant to the mechanical property of the matrix material is reduced as much as possible.
It should be noted that, the coprecipitation method for preparing the magnesium aluminum hydrotalcite is an existing conventional preparation process, and is not described herein.
Preferably, in the step (1), the sulfur-containing monomer is selected from one of lignosulfonate, cysteine and sulfosalicylic acid; the mass ratio of the magnesium salt to the sulfur-containing monomer is 2-3:1.
preferably, in the step (2), the nitrogen-containing monomer is selected from one of 2-aminodiphenyl ether, melamine, p-nitron, N-dimethylaniline and chitosan, and the mass ratio of MgAl-LDH modified by the sulfur-containing monomer to the nitrogen-containing monomer is 2-5:1.
preferably, in the step (2), the mass-volume ratio of MgAl-LDH modified by sulfur-containing monomers to deionized water in the suspension A is 0.5-1.5 g/100 ml; the mass volume ratio of the nitrogen-containing monomer and the deionized water in the dispersion liquid B is 0.2-0.8 g/100 ml.
Preferably, in the step (3), the phosphorus-containing monomer is selected from one of monoester triphosphate, hexachlorocyclotriphosphazene and phytic acid, and the mass-volume ratio of MgAl-LDH modified by the sulfur-nitrogen-containing monomer to the phosphorus-containing monomer is 2.5-4.0g:1.5-2.5ml.
Preferably, in the step (3), the mass-volume ratio of MgAl-LDH modified by sulfur-nitrogen-containing monomer and deionized water in the suspension C is 2.5-4.0g:100ml; the mass concentration of the phosphorus-containing monomer lye D is 20-25%; the pH value of the phosphorus-containing monomer lye D is 6-7.
Preferably, in the step (3), the transition metal salt is a soluble metal salt of one of manganese, nickel and cobalt, and the mass ratio of the MgAl-LDH modified by the sulfur-nitrogen-containing monomer to the soluble transition metal salt is 5-8:1, a step of; the mass concentration of the soluble transition metal salt is 0.01-0.02 g.mL -1 。
The invention also provides the hydrotalcite-based flame retardant containing sulfur, nitrogen, phosphorus and transition metal, which is prepared by the preparation method.
The invention has the advantages that:
according to the invention, the sulfur-containing monomer, the nitrogen-containing monomer, the phosphorus-containing monomer and the transition metal modified hydrotalcite are subjected to a layer-by-layer assembly method, so that uniform distribution of various flame retardant elements is realized, the compatibility of the hydrotalcite and a polymer matrix is improved to a great extent, and the damage of filling of the hydrotalcite to mechanical properties is relieved. Meanwhile, the sulfur, nitrogen, phosphorus, manganese and other elements contained in the flame retardant composite material play a role in flame retardance in a gas phase and a condensed phase, the concentrations of oxygen and combustible gas are diluted in the gas phase, a free radical capturing effect is exerted, a flame retardant chain reaction is interrupted, the roles of catalytic carbonization and physical barrier are exerted in the condensed phase, the defect of poor carbonization effect of hydrotalcite is overcome, a compact carbon layer is formed, and a lower substrate is protected from being combusted.
In a word, the hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal constructs a flame-retardant multilayer film between the matrix and hydrotalcite, improves the problem of incompatibility of hydrotalcite and a polymer matrix, and reduces the adverse effect on mechanical properties when the flame retardant is added into the matrix. The flame retardant property of the polyolefin matrix material is obviously improved through the synergistic effect of hydrotalcite, sulfur-containing monomer, nitrogen-containing monomer, phosphorus-containing monomer and transition metal, and meanwhile, the damage of the flame retardant to the mechanical property of the matrix material is reduced, so that the flame retardant-grade polymer composite material with excellent comprehensive properties is obtained.
Drawings
FIG. 1 is a schematic representation of the synthesis of LDH-LS@CS@PAMn of example 1.
FIG. 2 is an XRD comparison of the LDH, LDH-LS, LDH-LS@CS prepared in comparative examples 1-3 and LDH-LS@CS@PAMn prepared in example 1;
as shown in fig. 2, the XRD diffraction peaks of all samples showed that they still remained the layered structure of LDH, and the (003) diffraction peak, the (006) diffraction peak, and the (009) diffraction peak were not shifted from the original LDH, indicating that the modification occurred only at the surface and did not enter the interlayer, while the weakening of the intensity of the diffraction peak and the progressive instability of the baseline further demonstrated that the LDH surface was successfully assembled with LS, CS and PA.
FIG. 3 is a FT-IR comparison of the LDH, LDH-LS, LDH-LS@CS prepared in comparative examples 1-3 and LDH-LS@CS@PAMn prepared in example 1;
as shown in FIG. 3, the characteristic peaks newly appeared in FTIR of LDH-LS@CS@PAMn indicate that LDH was successfully modified by LS, CS and PA and that the surface was successfully chelated with Mn 2+ 。
FIG. 4 is a SEM comparison of the LDH (A), LDH-LS (B), LDH-LS@CS (C) prepared in comparative examples 1-3 and LDH-LS@CS@PAMn (D) prepared in example 1;
as shown in fig. 4, the LDH has a morphology in which a plurality of nano-sheets are stacked together to form a nano-flower structure, and the surface of LDH-ls@cs@pamn is covered with a layer of floc.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1
(1) According to Mg 2+ :Al 3+ Is 3:1 molar ratio of 7.69203g Mg (NO 3 ) 2 ·6H 2 O and 2.1299gAl (NO 3) 3 ·9H 2 O, dissolving the two into 200ml of deionized water together to form mixed salt solution; then accurately weighing 3g of sodium Lignin Sulfonate (LS) and 5g of sodium hydroxideAnd 6.29g of sodium carbonate are dissolved in 200ml of deionized water to form mixed alkali solution, and the mixed alkali solution is respectively dissolved for 10 minutes by ultrasonic with the ultrasonic power of 200W; after the ultrasonic treatment is finished, the mixed salt solution and the mixed alkali solution are dripped into a three-necked flask at the dripping speed of 1.5ml/min under the action of a stirrer, the pH value of the system is kept at 9-11 in the dripping process, after the solution is completely dripped, the solution is dynamically crystallized at the constant temperature of 90 ℃ for 8 hours, after the solution is finished, the obtained mixed solution is filtered and washed, the obtained filter cake is dried in vacuum at 60 ℃ for 12 hours, and the obtained product is magnesium aluminum hydrotalcite (LDH-LS) modified by sulfur-containing monomers.
(2) 1g of magnesium aluminum hydrotalcite (LDH-LS) modified by sulfur-containing monomer and 0.25g of Chitosan (CS) are accurately weighed, LDH-LS is dispersed in 100ml of deionized water, the ultrasonic power is 200W for 10min, then CS is placed in 50ml of deionized water, acetic acid is added to enable CS to be completely dissolved, colloidal solution is obtained, then the colloidal solution is slowly dripped into a beaker filled with LDH-LS, and magnetic stirring is carried out for 30min at normal temperature after the dripping is completed, and the stirring speed is 1500rpm. And after the completion, filtering and washing the obtained mixed solution, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain the product which is the magnesium aluminum hydrotalcite (LDH-LS@CS) modified by the sulfur-nitrogen-containing monomer.
(3) 3g of magnesium aluminum hydrotalcite modified by sulfur-nitrogen containing monomer (LDH-LS@CS) and 2ml of Phytic Acid (PA) are taken, LDH-LS@CS is dispersed in 100ml of deionized water, and the ultrasonic power is 200W after ultrasonic treatment for 10 min. Then, PA is dissolved in 50ml of deionized water, sodium hydroxide solution is added to adjust the pH value to 6-7, PA solution is slowly dripped into LDH-LS@CS, then 0.5g of manganese acetate is weighed and dissolved in 30ml of deionized water, and the mixture is dripped into the mixed slurry. After the completion of the dropping, magnetic stirring was performed at room temperature for 30 minutes at a stirring speed of 1500rpm. And after the process is finished, filtering and washing the obtained mixed solution, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain a product which is magnesium aluminum hydrotalcite (LDH-LS@CS@PAMn) containing sulfur/nitrogen/phosphorus/transition metal.
Comparative example 1
(1) According to Mg 2+ :Al 3+ Is 3:1 molar ratio of 7.69203g Mg (NO 3 ) 2 ·6H 2 O and 2.1299gAl (NO 3) 3 ·9H 2 O, dissolving both in 200ml deionized water to form mixed salt solutionA liquid; then accurately weighing 5g of sodium hydroxide and 6.29g of sodium carbonate, dissolving in 200ml of deionized water to form mixed alkali solution, respectively carrying out ultrasonic dissolution for 10min, wherein the ultrasonic power is 200W; after the ultrasonic treatment is finished, the mixed salt solution and the mixed alkali solution are dripped into a three-necked flask at the dripping speed of 1.5ml/min under the action of a stirrer, the pH value of the system is kept at 9-11 in the dripping process, after the solution is completely dripped, the solution is dynamically crystallized at the constant temperature of 90 ℃ for 8 hours, after the solution is finished, the obtained mixed solution is filtered and washed, the obtained filter cake is dried in vacuum for 12 hours at the temperature of 60 ℃, and the obtained product is magnesium aluminum hydrotalcite (LDH).
Comparative example 2
(1) According to Mg 2+ :Al 3+ Is 3:1 molar ratio of 7.69203g Mg (NO 3 ) 2 ·6H 2 O and 2.1299gAl (NO 3) 3 ·9H 2 O, dissolving the two into 200ml of deionized water together to form mixed salt solution; then accurately weighing 3g of sodium Lignin Sulfonate (LS), 5g of sodium hydroxide and 6.29g of sodium carbonate, dissolving in 200ml of deionized water to form mixed alkali solution, respectively carrying out ultrasonic dissolution for 10min, wherein the ultrasonic power is 200W; and after the ultrasonic treatment is finished, simultaneously dripping a salt solution and an alkali solution into a three-necked flask at a dripping rate of 1.5ml/min under the action of a stirrer, keeping the pH value of the system at 9-11 in the dripping process, and dynamically crystallizing at a constant temperature of 90 ℃ for 8 hours after the solution is completely dripped.
Comparative example 3
(1) According to Mg 2+ :Al 3+ Is 3:1 molar ratio of 7.69203g Mg (NO 3 ) 2 ·6H 2 O and 2.1299gAl (NO 3) 3 ·9H 2 O, dissolving the two into 200ml of deionized water together to form mixed salt solution; then accurately weighing 3g of sodium Lignin Sulfonate (LS), 5g of sodium hydroxide and 6.29g of sodium carbonate, dissolving in 200ml of deionized water to form mixed alkali solution, respectively carrying out ultrasonic dissolution for 10min, wherein the ultrasonic power is 200W; after the ultrasonic treatment, the salt solution and the alkali solution are simultaneously dripped into a three-necked flask at the dripping rate of 1.5ml/min under the action of a stirrer, and the pH value of the system is kept during the dripping processAnd (3) after 9-11, dynamically crystallizing at a constant temperature of 90 ℃ for 8 hours after the solution is completely dripped, filtering and washing the obtained mixed solution after the solution is ended, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain the product which is the magnesium aluminum hydrotalcite (LDH-LS) modified by sulfur-containing monomers.
(2) 1g of magnesium aluminum hydrotalcite (LDH-LS) modified by sulfur-containing monomer and 0.25g of Chitosan (CS) are accurately weighed, LDH-LS is dispersed in 100ml of deionized water, the ultrasonic power is 200W for 10min, then CS is placed in 50ml of deionized water, acetic acid is added to enable CS to be completely dissolved, colloidal solution is obtained, then the colloidal solution is slowly dripped into a beaker filled with LDH-LS, and magnetic stirring is carried out for 30min at normal temperature after the dripping is completed, and the stirring speed is 1500rpm. And after the completion, filtering and washing the obtained mixed solution, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain the product which is the magnesium aluminum hydrotalcite (LDH-LS@CS) modified by the sulfur-nitrogen-containing monomer.
Comparative example 4
(1) According to Mg 2+ :Al 3+ Is 3:1 molar ratio of 7.69203g Mg (NO 3 ) 2 ·6H 2 O and 2.1299gAl (NO 3) 3 ·9H 2 O, dissolving the two into 200ml of deionized water together to form mixed salt solution; then accurately weighing 3g of sodium Lignin Sulfonate (LS), 5g of sodium hydroxide and 6.29g of sodium carbonate, dissolving in 200ml of deionized water to form mixed alkali solution, respectively carrying out ultrasonic dissolution for 10min, wherein the ultrasonic power is 200W; and after the ultrasonic treatment is finished, simultaneously dripping a salt solution and an alkali solution into a three-necked flask at a dripping rate of 1.5ml/min under the action of a stirrer, keeping the pH value of the system at 9-11 in the dripping process, and dynamically crystallizing at a constant temperature of 90 ℃ for 8 hours after the solution is completely dripped.
(2) 1g of magnesium aluminum hydrotalcite (LDH-LS) modified by sulfur-containing monomer and 0.25g of Chitosan (CS) are accurately weighed, LDH-LS is dispersed in 100ml of deionized water, the ultrasonic power is 200W for 10min, then CS is placed in 50ml of deionized water, acetic acid is added to enable CS to be completely dissolved, colloidal solution is obtained, then the colloidal solution is slowly dripped into a beaker filled with LDH-LS, and magnetic stirring is carried out for 30min at normal temperature after the dripping is completed, and the stirring speed is 1500rpm. And after the completion, filtering and washing the obtained mixed solution, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain the product which is the magnesium aluminum hydrotalcite (LDH-LS@CS) modified by the sulfur-nitrogen-containing monomer.
(3) 3g of magnesium aluminum hydrotalcite modified by sulfur-nitrogen containing monomer (LDH-LS@CS) and 2ml of Phytic Acid (PA) are taken, LDH-LS@CS is dispersed in 100ml of deionized water, and the ultrasonic power is 200W after ultrasonic treatment for 10 min. Then, the PA is dissolved in 50ml of deionized water, the pH value is adjusted to 6-7 by adding sodium hydroxide solution, and the PA solution is slowly dripped into LDH-LS@CS. After the completion of the dropping, magnetic stirring was performed at room temperature for 30 minutes at a stirring speed of 1500rpm. And after the completion, filtering and washing the obtained mixed solution, and vacuum drying the obtained filter cake at 60 ℃ for 12 hours to obtain the product which is the magnesium aluminum hydrotalcite (LDH-LS@CS@PA) modified by the sulfur-containing nitrogen-phosphorus monomer.
Performance test:
the flame retardants obtained in example 1 (S1) and comparative examples 1 to 4 (D1 to 4) were melt-blended with polypropylene by a melt blending method to obtain PP composite materials having a mass fraction of 20wt% of the flame retardant, and flame retardance and mechanical properties were tested, and the results are shown in table 1.
TABLE 1 flame retardant Properties and mechanical Property test results of different PP composite materials
Claims (5)
1. A method for preparing a hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal, which is characterized by comprising the following steps:
(1) The mixed salt solution of magnesium salt and aluminum salt and the mixed alkali solution of sodium hydroxide, sodium carbonate and sulfur-containing monomer are used as raw materials, and MgAl-LDH modified by the sulfur-containing monomer is prepared by coprecipitation;
the sulfur-containing monomer is lignosulfonate, and the mass ratio of the magnesium salt to the sulfur-containing monomer is 2-3:1, a step of;
(2) Dispersing MgAl-LDH modified by sulfur-containing monomers in deionized water to obtain a suspension A; dispersing a nitrogen-containing monomer into deionized water to obtain a dispersion liquid B; dripping the dispersion liquid B into the suspension liquid A, fully and uniformly mixing to enable the nitrogen-containing monomer to be adsorbed on MgAl-LDH modified by the sulfur-containing monomer, and drying after solid-liquid separation to obtain the MgAl-LDH modified by the sulfur-containing nitrogen monomer;
the nitrogen-containing monomer is chitosan, and the mass ratio of MgAl-LDH modified by the sulfur-containing monomer to the nitrogen-containing monomer is 2-5:1, a step of;
(3) Dispersing MgAl-LDH modified by sulfur-nitrogen-containing monomer in deionized water to obtain suspension C; dispersing a phosphorus-containing monomer into a NaOH aqueous solution to obtain phosphorus-containing monomer alkali liquor D; dropping phosphorus-containing monomer alkali liquor D into suspension C, fully and uniformly mixing to enable phosphorus-containing monomers to be adsorbed on MgAl-LDH modified by sulfur-containing nitrogen monomers, then adding transition metal salt solution, fully and uniformly mixing, and drying after solid-liquid separation to obtain the hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal;
the phosphorus-containing monomer is phytic acid, and the mass volume ratio of MgAl-LDH modified by the sulfur-containing nitrogen monomer to the phosphorus-containing monomer is 2.5-4.0g:1.5-2.5ml;
the mass concentration of the phosphorus-containing monomer lye D is 20-25%;
the transition metal salt is soluble metal salt of manganese, and the mass ratio of MgAl-LDH modified by sulfur-nitrogen-containing monomer to the soluble transition metal salt is 5-8:1.
2. the preparation method according to claim 1, wherein in the step (2), the mass-to-volume ratio of MgAl-LDH modified by sulfur-containing monomer to deionized water in the suspension a is 0.5-1.5 g/100 ml; the mass volume ratio of the nitrogen-containing monomer and the deionized water in the dispersion liquid B is 0.2-0.8 g/100 ml.
3. The method of claim 1, wherein in step (3), the mass to volume ratio of MgAl-LDH modified with sulfur-nitrogen containing monomer to deionized water in suspension C is 2.5-4.0g:100ml; the pH value of the phosphorus-containing monomer lye D is 6-7.
4. The method according to claim 1, wherein in the step (3), the mass concentration of the soluble transition metal salt solution is 0.01 to 0.02g ∙ mL −1 。
5. A sulfur/nitrogen/phosphorus/transition metal containing hydrotalcite-based flame retardant prepared by the process of any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925287.3A CN115353669B (en) | 2022-08-03 | 2022-08-03 | Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925287.3A CN115353669B (en) | 2022-08-03 | 2022-08-03 | Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115353669A CN115353669A (en) | 2022-11-18 |
| CN115353669B true CN115353669B (en) | 2023-06-30 |
Family
ID=84033749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210925287.3A Active CN115353669B (en) | 2022-08-03 | 2022-08-03 | Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115353669B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084472A (en) * | 2017-12-11 | 2018-05-29 | 北京理工大学 | Hydrotalcite/phosphorus-nitrogen containing flame retardant compositional flame-retardant PET material and preparation method thereof |
| CN110305370A (en) * | 2019-06-13 | 2019-10-08 | 湘潭大学 | A kind of phosphonitrile graft modification houghite fire retardant and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009011764A2 (en) * | 2007-07-05 | 2009-01-22 | University Of North Texas | Nickel incorporation into ldh chlorobenzenesulfonate |
| WO2013147285A1 (en) * | 2012-03-26 | 2013-10-03 | 協和化学工業株式会社 | Method for manufacturing hydrotalcite particles |
| CN106893369A (en) * | 2017-01-19 | 2017-06-27 | 北京化工大学 | A kind of synthesis of phosphorous nitrogen sulfur compound and its preparation method of intercalation modifying hydrotalcite |
| CN110105298B (en) * | 2019-04-29 | 2022-08-30 | 湘潭大学 | Synthesis of nitrogen-sulfur containing synergistic flame-retardant compound and preparation method of intercalation modified hydrotalcite |
| CN110698760B (en) * | 2019-10-29 | 2022-06-10 | 烟台艾弗尔阻燃科技有限公司 | Flame retardant and application thereof in preparation of high-gloss high-black flame-retardant polypropylene material |
| CN112812371B (en) * | 2021-01-05 | 2022-07-22 | 湘潭大学 | Nitrogen-phosphorus-containing hydrotalcite-based flame retardant and preparation method thereof |
-
2022
- 2022-08-03 CN CN202210925287.3A patent/CN115353669B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084472A (en) * | 2017-12-11 | 2018-05-29 | 北京理工大学 | Hydrotalcite/phosphorus-nitrogen containing flame retardant compositional flame-retardant PET material and preparation method thereof |
| CN110305370A (en) * | 2019-06-13 | 2019-10-08 | 湘潭大学 | A kind of phosphonitrile graft modification houghite fire retardant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115353669A (en) | 2022-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112011093B (en) | Modified ammonium polyphosphate composite intumescent flame retardant and preparation method and application thereof | |
| CN112812371B (en) | Nitrogen-phosphorus-containing hydrotalcite-based flame retardant and preparation method thereof | |
| CN115353670B (en) | Hydrotalcite-based flame retardant with bio-based tannic acid crosslinked cyanuric chloride chelated iron ions and preparation method thereof | |
| CN112812372B (en) | Tannin-phosphazene network functionalized hydrotalcite-based flame retardant and preparation method thereof | |
| CN103113623A (en) | Preparation method of LDHs (Layered Double Hydroxides) composite flame retardant | |
| CN111116987B (en) | Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant | |
| CN114806601B (en) | Alkyl phosphinate composition and preparation method and application thereof | |
| CN112280100A (en) | Composite intumescent flame retardant and preparation method thereof | |
| CN115353669B (en) | Hydrotalcite-based flame retardant containing sulfur/nitrogen/phosphorus/transition metal and preparation method thereof | |
| CN103965661B (en) | Preparation method and application of secondary modified layered double hydroxide | |
| CN109251358B (en) | Polyacid intercalation surface covalent modified layered double hydroxide flame retardant and preparation method thereof | |
| Tu et al. | Waste to resource: preparation of an efficient adsorbent and its sustainable utilization in flame retardant polyurethane composites | |
| CN109082017B (en) | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof | |
| CN108395643B (en) | Modified hydrocalumite for PVC heat stabilizer and clean preparation method thereof | |
| CN112480474A (en) | Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof | |
| CN117050519A (en) | Preparation method of flame-retardant nylon 66 composite material | |
| CN114395167B (en) | Carbon microsphere @ hydrotalcite @ polyphosphazene hybrid flame retardant and preparation method thereof | |
| CN108997615B (en) | Piperazine modified lignin/aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in EVA | |
| CN112063016B (en) | Preparation method of long-acting phosphite ester antioxidant | |
| CN101139454B (en) | Non-bittern swelling flame-proof polypropylene containing porous nickel phosphate and preparation method thereof | |
| CN110436499B (en) | Method for regulating and controlling oil absorption value of superfine aluminum hydroxide | |
| CN108314844B (en) | Preparation method of modified zinc borate whisker reinforced flame-retardant waterproof breathable film | |
| CN113831597B (en) | Bio-based macromolecule modified nano zirconium phosphate flame retardant and fireproof coating prepared by using same | |
| CN115819846B (en) | Core-shell structure flame retardant and preparation method and application thereof | |
| CN118325361A (en) | Chitosan-phenylphosphoric acid self-assembled modified nickel-cobalt double-metal hydroxide flame retardant 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |