CN112280102A - Method for preparing tin-based composite flame retardant by biomimetic synthesis technology - Google Patents
Method for preparing tin-based composite flame retardant by biomimetic synthesis technology Download PDFInfo
- Publication number
- CN112280102A CN112280102A CN202011249759.5A CN202011249759A CN112280102A CN 112280102 A CN112280102 A CN 112280102A CN 202011249759 A CN202011249759 A CN 202011249759A CN 112280102 A CN112280102 A CN 112280102A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- tin
- based composite
- composite flame
- deionized water
- 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
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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
Abstract
The invention discloses a method for preparing a tin-based composite flame retardant by a biomimetic synthesis technology, which applies a biomimetic synthesis concept, adopts an even precipitation method, combines ultrasonic dispersion and azeotropic distillation, and uses different organic templates to regulate and control and synthesize the flame retardant with special morphology, thereby preliminarily improving the compatibility of the flame retardant and a matrix and simultaneously improving the flame retardant performance of the composite flame retardant; the method comprises the following steps of ultrasonically dissolving a tin source, an organic template and deionized water, adding a coating agent dispersion liquid into the solution, then adding a soluble metal zinc salt solution, reacting at 85-100 ℃, washing with deionized water and ethanol in sequence after precipitation, performing azeotropic distillation with n-butyl alcohol after washing, and drying a product to obtain the tin-based composite flame retardant. The method has the advantages of simple process flow, easy operation, low energy consumption, high yield, mild reaction conditions and green and environment-friendly product.
Description
Technical Field
The invention belongs to the field of environment-friendly composite flame retardant materials, and particularly relates to a method for preparing a tin-based composite flame retardant by utilizing a biomimetic synthesis technology.
Background
In recent years, in a plurality of serious fire safety accidents which continuously occur, the flame retardance of materials gradually attracts high attention of people, and the use of flame-retardant materials for improving the consciousness of resisting the fire risk is more and more important; in a major fire disaster, 75-80% of death reasons of dead people are caused by inhalation of toxic gas released by combustion of high polymer materials and suffocation of shielding dense smoke; the three synthetic materials (plastics, rubber and fibers) are mostly combustible or inflammable and can emit dense smoke and toxic gas during combustion, so that the flame retardant has flame retardant and smoke suppression performances, and has great advantages in application of flame-retardant high polymer materials. At present, in the domestic market, the flame retardance of high polymer materials is mainly based on a halogen and antimony composite flame retardant technology, but along with the publication of the Chinese fire-fighting law and the implementation of the international flame-retardant mandatory standard, particularly with the release of RoHS, WEEE and REACH instructions of the European Union and the emergence of 'requirements and marks on the combustion performance of flame-retardant products and components in public places', the demands for developing green, environment-friendly and efficient flame retardants and flame-retardant technologies are increasingly urgent.
The Zinc Stannate (ZS) and the Zinc Hydroxystannate (ZHS) have the dual properties of flame retardance and smoke suppression, have the properties of no toxicity and no pollution, have good flame retardance and smoke suppression in most polymers, and can be widely used for polyolefin, polyvinyl chloride, polyester, epoxy resin, nylon, chlorinated rubber and alkyd resinFlame retardancy of high molecular materials such as grease. Research shows that the tin-based flame retardant has the smoke suppression efficiency three times higher than that of an antimony smoke suppressant; meanwhile, compared with antimony flame retardants with carcinogenic risks, the tin-based flame retardant is environment-friendly and nontoxic, can meet the requirements of relevant laws and regulations on environment protection and health such as REACH, TSCA and the like, is a relatively ideal, efficient and environment-friendly flame retardant synergist, and is expected to replace Sb2O3The environment-friendly flame-retardant product.
The invention discloses a preparation method of zinc hydroxystannate, and aims to provide a preparation method of superfine zinc hydroxystannate powder which is free of pollution and simple in synthesis process. The preparation method adopts conventional equipment in the preparation process, has simple process flow, does not discharge three wastes and is easy to realize industrialization. However, the cost of the zinc hydroxystannate prepared by the method is too high, compared with other types of flame retardants, the zinc hydroxystannate prepared by the method has no advantage in price competition, and in addition, the flame retardant efficiency is not high when the zinc hydroxystannate prepared by the method is singly added into a polymer for use, and the compatibility with a substrate is poor. Therefore, in order to comprehensively improve the flame retardant performance and the cost performance of the tin-based flame retardant, improvements in these aspects are needed.
In recent years, researchers continuously try to explore and synthesize novel efficient flame retardants, and simultaneously compound flame retardants with good flame retardant effect, so that the dosage of the flame retardants is reduced, the mechanical property and the processability attenuation degree of flame retardant materials are reduced, and the flame retardant property of the composite flame retardant is improved. Biomimetic synthesis is taken as one of the leading edge and hot spot directions of the material chemistry research in recent years, plays an important role in improving the compatibility of inorganic materials and polymer matrixes, and is used for controlling the size, crystalline phase and shape of the inorganic materials
The appearance, the assembly and the like provide a new idea; by applying a bionic synthesis concept and using different organic templates to regulate and synthesize the flame retardant with special morphology, the compatibility of inorganic substances and high polymers is enhanced, and thus the application performance of the material is improved; meanwhile, the flame retardant property of the composite flame retardant can be improved by compounding the flame retardant with other types of inorganic flame retardants.
Disclosure of Invention
The invention aims to provide a method for preparing a tin-based composite flame retardant by a biomimetic synthesis technology, which solves the defects of overlarge addition amount and low flame retardant efficiency of a single flame retardant in the practical application of the existing tin-based flame retardant, and simultaneously improves the compatibility of the flame retardant and a substrate; tin is used as an important nonferrous metal, the additional value of the material is improved through deep processing, the material has obvious significance for national economic construction, but the tin price is higher, compared with the flame retardant of the same type in the market, the popularization and application difficulty of the tin-based flame retardant are higher, so that how to reduce the cost and improve the composite performance of the flame retardant becomes one of the research focuses of the tin-based flame retardant; the invention applies the bionic synthesis concept and a simple uniform precipitation method to prepare the tin-based composite flame retardant.
The preparation method of the tin-based flame retardant comprises the following steps:
(1) adding a tin source, urea and an organic template agent into a round-bottom flask, adding deionized water, and then placing the mixture into ultrasonic equipment to perform ultrasonic treatment at 75-90 ℃ until the mixture is completely dissolved;
the organic template agent is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), Cetyl Trimethyl Ammonium Bromide (CTAB), polyethylene glycol-6000 (PEG-6000), an SDBS-ethylene glycol mixture and polyvinyl alcohol (PVA), wherein the SDBS-ethylene glycol mixture is prepared by mixing sodium dodecyl benzene sulfonate and ethylene glycol according to the mass ratio of 1: 1-1: 5;
the tin source is one of sodium stannate, sodium hydroxystannate and potassium stannate;
the molar ratio of the tin source to the organic template agent is 14: 1-5: 1, and the molar ratio of the tin source to the urea is 1: 2-1: 10;
(2) dispersing a coating agent in deionized water, performing ultrasonic treatment until the coating agent is uniformly dispersed, adding a dispersion liquid into the mixed liquid obtained in the step (1), stirring to uniformly mix the dispersion liquid, and placing the mixture in a water bath for constant-temperature reaction at 85-90 ℃ for 4-8 hours;
the coating is one of magnesium hydroxide, aluminum hydroxide, calcium carbonate and magnesium carbonate; the mol ratio of the coating agent to the tin source is 6: 1-2: 1;
(3) dissolving soluble metal zinc salt in deionized water, performing ultrasonic treatment until the soluble metal zinc salt is completely dissolved, dropwise adding the solution into the mixed solution obtained in the step (2), stirring to uniformly mix the solution, and reacting for 4-8 hours at 85-100 ℃;
the soluble metal zinc salt is one of zinc chloride and zinc sulfate; the molar ratio of the soluble metal zinc salt to the tin source is 1: 1-1: 20;
(4) after the mixed solution in the step (3) is completely reacted, taking out the precipitate, and washing with deionized water and ethanol in sequence until the precipitate is washed with 0.5mol/L AgNO3Solution detection of filtrate without Cl-And then putting the filter cake into a round-bottom flask, adding n-butyl alcohol, performing ultrasonic dispersion to fully disperse the filter cake into an emulsion, performing azeotropic distillation at normal pressure and 90-95 ℃, and drying the product at 90-100 ℃ for 12-16 h to obtain the tin-based composite flame retardant.
The product prepared by the method is detected by an X-ray diffractometer (XRD), and the result shows that the product is the tin-based composite flame retardant by comparing with a standard substance; observing the appearance and the size of the product by using a Scanning Electron Microscope (SEM); and (3) detecting the product by using a synchronous thermal analyzer (TG-DSC), and observing a main functional group and a characteristic absorption peak of the product by using an infrared spectrometer, wherein the result shows the flame-retardant action temperature of the product.
Compared with the existing preparation method, the invention has the following advantages:
(1) the preparation method is simple, the reaction condition is mild, and industrialization is easy to realize;
(2) the two flame retardants are compounded, so that less tin element is added, more excellent flame retardant performance can be obtained, and the cost of the flame retardant is reduced;
(3) the appearance, crystalline phase, size and the like of the flame retardant are regulated and controlled by the organic template agent, so that the compatibility of the flame retardant and a matrix is improved;
(4) the raw materials adopted by the invention are all environment-friendly, and the prepared flame retardant meets the requirement of environmental protection.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a tin-based composite flame retardant prepared in example 1;
FIG. 2 is a thermogravimetric analysis (TG-DSC) chart of the tin-based composite flame retardant prepared in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a tin-based composite flame retardant prepared in example 3;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a tin-based composite flame retardant prepared in example 3;
FIG. 5 is a graph of the infrared spectrum (FT-IR) of the tin-based composite flame retardant prepared in example 5.
Detailed Description
The invention will be explained in more detail below with reference to examples and the accompanying drawings, without limiting the scope of the invention thereto.
Example 1:
(1) adding 0.0142mol of sodium stannate, 0.35g of Sodium Dodecyl Benzene Sulfonate (SDBS), 7g of urea and 200mL of deionized water into a round-bottom flask, performing ultrasonic treatment at 90 ℃ for 30min until the sodium stannate is completely dissolved, and preserving heat in a water bath at 90 ℃;
(2) dispersing 5g of magnesium hydroxide in 50mL of deionized water, performing ultrasonic treatment for 10min until the magnesium hydroxide is uniformly dispersed, adding the dispersion into the round-bottom flask obtained in the step (1), performing magnetic stirring to uniformly mix the magnesium hydroxide and the round-bottom flask, and placing the round-bottom flask in a water bath for reacting for 4 hours at a constant temperature of 90 ℃;
(3) dissolving 0.0015mol of zinc chloride in 100mL of deionized water, performing ultrasonic treatment for 20min until the zinc chloride is completely dissolved, dropwise adding the solution into the round-bottom flask obtained in the step (2), uniformly mixing the solution by magnetic stirring, and placing the mixed solution in a water bath at 93 ℃ for constant-temperature reaction for 4 h;
(4) after the mixed solution in the step (3) completely reacts, taking out the precipitate, and washing with deionized water and ethanol for 4 times in sequence until 0.5mol/L AgNO is used3Detecting that the filtrate has no Cl-by using the solution, then putting the filter cake into a round-bottom flask, dropwise adding 100mL of n-butyl alcohol, performing ultrasonic dispersion for 1h to fully disperse the filter cake into an emulsion, then performing azeotropic distillation at the normal pressure and the temperature of 93 ℃ to finally obtain the final product
Drying the tin-based composite flame retardant at 90 ℃ for 16h to obtain the tin-based composite flame retardant, wherein the X-ray diffraction (XRD) of the tin-based composite flame retardant prepared in the embodiment is shown in figure 1, and the product contains zinc hydroxystannate and magnesium hydroxide and the grain size is less than 100nm according to the peak width;
the flame retardant prepared in this example was used in PP (polypropylene) to prepare a flame retardant test material (added in an amount of 10% by mass of PP), resulting in an increase in the oxygen index of PP from 17.8 to 25.8.
Example 2:
(1) adding 0.03mol of sodium stannate, 0.72g of hexadecyl trimethyl ammonium bromide (CTAB), 9.5 urea and 200mL of deionized water into a round-bottom flask, performing ultrasonic treatment at 85 ℃ for 30min until the sodium stannate is completely dissolved, and preserving heat in a water bath at 85 ℃;
(2) dispersing 5g of magnesium hydroxide in 50mL of deionized water, performing ultrasonic treatment for 10min until the magnesium hydroxide is uniformly dispersed, adding the dispersion into the round-bottomed flask obtained in the step (1), performing magnetic stirring to uniformly mix the magnesium hydroxide and the round-bottomed flask, and placing the round-bottomed flask in a water bath for constant-temperature reaction at 85 ℃ for 7 hours;
(3) dissolving 0.03mol of zinc chloride in 50mL of deionized water, performing ultrasonic treatment for 20min until the zinc chloride is completely dissolved, dropwise adding the solution into the round-bottom flask obtained in the step (2), uniformly mixing the solution by magnetic stirring, and placing the mixed solution in a water bath for reacting for 6h at the constant temperature of 95 ℃;
(4) after the mixed solution in the step (3) is completely reacted, taking out the precipitate, and washing the precipitate for 5 times by using deionized water and ethanol in sequence until the precipitate is washed by 0.5mol/L AgNO3Detecting that the filtrate has no Cl-in the solution, then putting the filter cake into a round-bottom flask, dropwise adding 100mL of n-butyl alcohol, ultrasonically dispersing for 1h to fully disperse the filter cake into an emulsion, then carrying out azeotropic distillation at normal pressure and 90 ℃, and drying the product at 100 ℃ for 12h to obtain the tin-based composite flame retardant; the thermogravimetric analysis (TG-DSC) diagram of the tin-based composite flame retardant prepared in the embodiment is shown in figure 2, and figure 2 shows that zinc hydroxystannate starts to decompose when the prepared product is at 194.4 ℃, and magnesium hydroxide starts to decompose into magnesium oxide when the temperature reaches 350.2 ℃, which shows that the flame retardant component starts to react at a lower temperature to protect a substrate.
The flame retardant prepared in this example was used in PP (polypropylene) to prepare a flame retardant test material (added in an amount of 10% by mass of PP), resulting in an increase in the oxygen index of PP from 17.8 to 24.3.
Example 3:
(1) adding 3.8g of sodium hydroxystannate, 7g of urea, 0.35g of Sodium Dodecyl Benzene Sulfonate (SDBS) and 200mL of deionized water into a round-bottom flask, performing ultrasonic treatment at 80 ℃ for 40min until the sodium hydroxystannate, the urea, the SDBS and the deionized water are completely dissolved, and preserving heat in a water bath at 80 ℃;
(2) dispersing 5.6g of calcium carbonate in 50mL of deionized water, performing ultrasonic treatment for 10min until the calcium carbonate is uniformly dispersed, adding the dispersion into the round-bottomed flask obtained in the step (1), performing magnetic stirring to uniformly mix the calcium carbonate and the dispersion, and placing the mixture in a water bath for constant-temperature reaction at 85 ℃ for 6 hours;
(3) dissolving zinc sulfate (the molar ratio of the zinc sulfate to the sodium hydroxystannate is 1: 5) in 50mL of deionized water, performing ultrasonic treatment for 20min until the zinc sulfate and the sodium hydroxystannate are completely dissolved, dropwise adding the solution into the round-bottom flask obtained in the step (2), uniformly mixing the solution by magnetic stirring, and placing the round-bottom flask in a water bath for reaction for 5 hours at a constant temperature of 90 ℃;
(4) after the mixed solution in the step (3) completely reacts, taking out the precipitate, sequentially washing the precipitate for 3 times by using deionized water and ethanol, then putting the filter cake into a round-bottom flask, dropwise adding 100mL of n-butyl alcohol, and ultrasonically dispersing for 1h to fully disperse the filter cake into emulsion
Liquid, then azeotropic distillation is carried out at normal pressure and 95 ℃, and the product is dried for 14 hours at 95 ℃ to obtain the tin-based composite flame retardant;
the flame retardant prepared in this example was used in PP (polypropylene) to prepare a flame retardant test material (added in an amount of 15% by mass of PP), resulting in an increase in the oxygen index of PP from 17.8 to 28.5.
Example 4:
(1) adding 3.8g of sodium hydroxystannate, 8.5g of urea, 0.5g of Sodium Dodecyl Benzene Sulfonate (SDBS) and 200mL of deionized water into a round-bottom flask, performing ultrasonic treatment at 90 ℃ for 20min until the sodium hydroxystannate, the urea, the SDBS and the deionized water are completely dissolved, and preserving heat in a water bath at 90 ℃;
(2) dispersing 2.5g of magnesium hydroxide in 50mL of deionized water, carrying out ultrasonic treatment for 10min until the magnesium hydroxide is uniformly dispersed, adding the dispersion into the round-bottom flask obtained in the step (1), carrying out magnetic stirring to uniformly mix the magnesium hydroxide and the round-bottom flask, and placing the round-bottom flask in a water bath for carrying out constant-temperature reaction for 5 hours at 90 ℃;
(3) dissolving zinc sulfate (the molar ratio of the zinc sulfate to the sodium hydroxystannate is 1: 8) in 50mL of deionized water, performing ultrasonic treatment for 20min until the zinc sulfate and the sodium hydroxystannate are completely dissolved, dropwise adding the solution into the round-bottom flask obtained in the step (2), uniformly mixing the solution by magnetic stirring, and placing the round-bottom flask in a water bath for constant-temperature reaction at 93 ℃ for 5 h;
(4) after the mixed liquid in the step (3) completely reacts, taking out the precipitate, sequentially washing the precipitate with deionized water and ethanol for 5 times, then putting the filter cake into a round-bottom flask, dropwise adding 100mL of n-butyl alcohol, ultrasonically dispersing for 1h to fully disperse the filter cake into an emulsion, then carrying out azeotropic distillation at 93 ℃ under normal pressure, and drying the product at 100 ℃ for 15h to obtain the tin-based composite flame retardant; scanning Electron Microscopy (SEM) of the tin-based composite flame retardant prepared in this example is shown in fig. 3 and 4, and it can be seen from a microscopic picture that zinc hydroxystannate is coated on the surface of magnesium hydroxide;
the flame retardant prepared in this example was used in PP (polypropylene) to prepare a flame retardant test material (added in an amount of 10% by mass of PP), resulting in an increase in the oxygen index of PP from 17.8 to 26.2.
Example 5:
(1) adding 0.043mol of potassium stannate, an SDBS-ethylene glycol mixture (1: 1), 15g of urea and 200mL of deionized water into a round-bottom flask, performing ultrasonic treatment at 90 ℃ for 1h until the potassium stannate, the SDBS-ethylene glycol mixture and the SDBS-ethylene glycol mixture are completely dissolved, and stirring in a water bath at the constant temperature of 90 ℃ under the condition that the molar ratio of the potassium stannate to the SDBS-ethylene glycol mixture is 8: 1;
(2) dispersing aluminum hydroxide (the molar ratio of the aluminum hydroxide to the potassium stannate is 5: 1) in 50mL of deionized water, performing ultrasonic treatment for 20min until the aluminum hydroxide and the potassium stannate are uniformly dispersed, adding the dispersion into the round-bottom flask obtained in the step (1), performing magnetic stirring to uniformly mix the aluminum hydroxide and the potassium stannate, and placing the round-bottom flask in a water bath to perform constant-temperature reaction for 4 hours at 90 ℃;
(3) dissolving 0.0045mol of zinc chloride in 100mL of deionized water, performing ultrasonic treatment for 20min until the zinc chloride is completely dissolved, dropwise adding the solution into the round-bottom flask obtained in the step (2), uniformly mixing the solution by magnetic stirring, and placing the mixed solution in a water bath for constant-temperature reaction at 93 ℃ for 6 h;
(4) after the mixed solution in the step (3) completely reacts, taking out the precipitate, and washing with deionized water and ethanol for 4 times in sequence until 0.5mol/L AgNO is used3Detecting no Cl-in the filtrate by using the solution, then putting the filter cake into a round-bottom flask, dropwise adding 100mL of n-butyl alcohol, performing ultrasonic dispersion for 1h to fully disperse the filter cake into an emulsion, then performing azeotropic distillation at normal pressure and 93 ℃, and obtaining a product at 95 DEG C
Drying for 13 hours to obtain the tin-based composite flame retardant; the infrared spectrum (FT-IR) of the tin-based composite flame retardant prepared by the embodiment is shown in figure 5, and it can be seen from figure 5 that functional groups and stretching vibration peaks of the tin-based composite flame retardant prepared by the biomimetic synthesis technology in the product are changed compared with the original zinc hydroxystannate;
the flame retardant prepared in this example was used in PP (polypropylene) to prepare a flame retardant test material (added in an amount of 15% by mass of PP), resulting in an increase in the oxygen index of PP from 17.8 to 28.1.
Claims (6)
1. A method for preparing a tin-based composite flame retardant by a biomimetic synthesis technology is characterized by comprising the following specific steps:
(1) putting a tin source, an organic template and urea into deionized water, and then carrying out ultrasonic treatment on the mixture at 75-90 ℃ until the mixture is completely dissolved;
(2) dispersing a coating agent in deionized water, performing ultrasonic treatment until the coating agent is uniformly dispersed, adding a dispersion liquid into the mixed liquid obtained in the step (1), stirring to uniformly mix the dispersion liquid, and placing the mixture in a water bath for constant-temperature reaction at 85-90 ℃ for 4-8 hours;
(3) dissolving soluble metal zinc salt in deionized water, performing ultrasonic treatment until the soluble metal zinc salt is completely dissolved, dropwise adding the solution into the mixed solution obtained in the step (2), stirring to uniformly mix the solution, and reacting for 4-8 hours at 85-100 ℃;
(4) after the mixed solution in the step (3) is completely reacted, taking out the precipitate, and washing with deionized water and ethanol in sequence until the precipitate is washed with 0.5mol/L AgNO3Solution detection of filtrate without Cl-And then putting the filter cake into n-butyl alcohol, ultrasonically dispersing until the mixture becomes emulsion, carrying out azeotropic distillation on the emulsion at normal pressure and 90-95 ℃, and finally drying the product at 90-100 ℃ for 12-16 h to obtain the tin-based composite flame retardant.
2. The biomimetic synthesis technology-based preparation method of the tin-based composite flame retardant according to claim 1, characterized in that: the organic template agent is one or more of sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, polyethylene glycol-6000, an SDBS-ethylene glycol mixture and polyvinyl alcohol, wherein the SDBS-ethylene glycol mixture is prepared by mixing sodium dodecyl benzene sulfonate and ethylene glycol according to the mass ratio of 1: 1-1: 5.
3. The biomimetic synthesis technology-based preparation method of the tin-based composite flame retardant according to claim 1, characterized in that: the tin source is one of sodium stannate, sodium hydroxy stannate and potassium stannate.
4. The biomimetic synthesis technology-based preparation method of the tin-based composite flame retardant according to claim 1, characterized in that: the coating agent is one of magnesium hydroxide, aluminum hydroxide, calcium carbonate and magnesium carbonate.
5. The biomimetic synthesis technology-based preparation method of the tin-based composite flame retardant according to claim 1, characterized in that: the soluble metal zinc salt is one of zinc chloride and zinc sulfate.
6. The biomimetic synthesis technology-based preparation method of the tin-based composite flame retardant according to claim 1, characterized in that: the molar ratio of the tin source to the organic template agent is 14: 1-5: 1, the molar ratio of the tin source to the urea is 1: 2-1: 10, the molar ratio of the coating agent to the tin source is 6: 1-2: 1, and the molar ratio of the soluble metal zinc salt to the tin source is 1: 1-1: 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011249759.5A CN112280102A (en) | 2020-11-11 | 2020-11-11 | Method for preparing tin-based composite flame retardant by biomimetic synthesis technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011249759.5A CN112280102A (en) | 2020-11-11 | 2020-11-11 | Method for preparing tin-based composite flame retardant by biomimetic synthesis technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112280102A true CN112280102A (en) | 2021-01-29 |
Family
ID=74352009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011249759.5A Pending CN112280102A (en) | 2020-11-11 | 2020-11-11 | Method for preparing tin-based composite flame retardant by biomimetic synthesis technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112280102A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113136048A (en) * | 2021-04-08 | 2021-07-20 | 佛山金戈新材料股份有限公司 | Inorganic flame retardant capable of being marked by laser and preparation method thereof |
| CN115772308A (en) * | 2022-12-07 | 2023-03-10 | 江苏耀鸿电子有限公司 | Flame-retardant high-temperature-resistant hydrocarbon resin glue solution and copper-clad substrate prepared from same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012025362A1 (en) * | 2010-08-23 | 2012-03-01 | Catena Additives Gmbh & Co. Kg | Flame protection agent compositions containing triazine intercalated metal phosphates |
| CN108841042A (en) * | 2018-07-13 | 2018-11-20 | 广州广化塑料管道有限公司 | Inorganic nano material and high polymerization degree APP compound flame redundant and preparation method thereof |
| CN109054293A (en) * | 2018-06-26 | 2018-12-21 | 四川星奥立装饰材料有限公司 | Efficient preparation process for plastic plate |
| CN109517220A (en) * | 2018-11-13 | 2019-03-26 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of preparation method of nanometer of tinbase expanding fire retardant |
| CN110862574A (en) * | 2019-12-03 | 2020-03-06 | 苏州诺博恩新材料科技有限公司 | Efficient smoke-inhibiting magnesium hydroxide/tin compound microcapsule flame retardant and preparation method thereof |
-
2020
- 2020-11-11 CN CN202011249759.5A patent/CN112280102A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012025362A1 (en) * | 2010-08-23 | 2012-03-01 | Catena Additives Gmbh & Co. Kg | Flame protection agent compositions containing triazine intercalated metal phosphates |
| CN109054293A (en) * | 2018-06-26 | 2018-12-21 | 四川星奥立装饰材料有限公司 | Efficient preparation process for plastic plate |
| CN108841042A (en) * | 2018-07-13 | 2018-11-20 | 广州广化塑料管道有限公司 | Inorganic nano material and high polymerization degree APP compound flame redundant and preparation method thereof |
| CN109517220A (en) * | 2018-11-13 | 2019-03-26 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of preparation method of nanometer of tinbase expanding fire retardant |
| CN110862574A (en) * | 2019-12-03 | 2020-03-06 | 苏州诺博恩新材料科技有限公司 | Efficient smoke-inhibiting magnesium hydroxide/tin compound microcapsule flame retardant and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113136048A (en) * | 2021-04-08 | 2021-07-20 | 佛山金戈新材料股份有限公司 | Inorganic flame retardant capable of being marked by laser and preparation method thereof |
| CN115772308A (en) * | 2022-12-07 | 2023-03-10 | 江苏耀鸿电子有限公司 | Flame-retardant high-temperature-resistant hydrocarbon resin glue solution and copper-clad substrate prepared from same |
| CN115772308B (en) * | 2022-12-07 | 2023-08-29 | 江苏耀鸿电子有限公司 | Flame-retardant high-temperature-resistant hydrocarbon resin glue solution and copper-clad substrate prepared from same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112280102A (en) | Method for preparing tin-based composite flame retardant by biomimetic synthesis technology | |
| CN101544783B (en) | Composite heat stabilizer for hydrophobic nano-hydrotalcite PVC and preparation method thereof | |
| CN1279129C (en) | Weather-resistant and fire-proof nanometer coating for expanding ultrathin steel structure and production thereof | |
| CN109517220B (en) | Preparation method of nano tin-based intumescent flame retardant | |
| CN101058693A (en) | Fireproof paint for super-thin steel structure and preparation method thereof | |
| CN104130671A (en) | Aqueous ultrathin expansion-type fireproof coating for steel structure and preparation method thereof | |
| CN101747859A (en) | Silicone fireproof sealant for construction and preparation method thereof | |
| CN112225985A (en) | Flame-retardant PP composite material and preparation method thereof | |
| CN101735532A (en) | High weather-proof, multiple-effect, environmentally-friendly PVC composite heat stabilizer and preparation method thereof | |
| CN1113816C (en) | Process for preparing powdered zinc hydroxytannate | |
| CN110862574A (en) | Efficient smoke-inhibiting magnesium hydroxide/tin compound microcapsule flame retardant and preparation method thereof | |
| NL2030235B1 (en) | A modified melamine-phytate flame retardant, and preparation method and application thereof | |
| CN110105298A (en) | A kind of synthesis of nitrogenous sulphur synergistic flame-retardant compound and its preparation method of intercalation modifying hydrotalcite | |
| CN112321949A (en) | Synergistic flame-retardant thermoplastic polymer composite material and preparation method thereof | |
| CN105037810A (en) | Method for preparing alginate modified brucite composite flame retardant | |
| CN111004414A (en) | Two-component intercalated hydrotalcite-like additive and application thereof in polypropylene plastics | |
| CN109054099B (en) | Melamine modified lignin/magnesium aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in cable material | |
| CN105860140B (en) | The preparation method and product of a kind of aluminium hydroxide/zinc stannate microcapsule flame retardant | |
| CN110964232A (en) | Efficient environment-friendly microcapsule flame retardant with multilayer structure and preparation method thereof | |
| CN101967275A (en) | Nano magnesium carbonate modified fire protection engineering plastic and preparation method thereof | |
| CN105017793A (en) | Synthesis and preparation method for hydrophobic flame retardant material | |
| CN109054100B (en) | Melamine modified lignin/aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in EVA resin | |
| CN112593021A (en) | Preparation method of flame-retardant smoke-inhibiting fatliquor containing metal organic framework UiO-66 composite material | |
| CN110294862B (en) | Preparation method of nano-hybrid tin-based smoke suppressant | |
| CN110845779B (en) | Modified composite flame-retardant TPO resin 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210129 |
|
| RJ01 | Rejection of invention patent application after publication |