CN110804286A - Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch - Google Patents
Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch Download PDFInfo
- Publication number
- CN110804286A CN110804286A CN201911220462.3A CN201911220462A CN110804286A CN 110804286 A CN110804286 A CN 110804286A CN 201911220462 A CN201911220462 A CN 201911220462A CN 110804286 A CN110804286 A CN 110804286A
- Authority
- CN
- China
- Prior art keywords
- starch
- ammonium polyphosphate
- flame
- composite material
- preparing
- 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.)
- Granted
Links
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
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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)
Abstract
The invention relates to a process for preparing a flame-retardant composite material by using starch coated ammonium polyphosphate, which comprises the following steps: coating ammonium polyphosphate with starch: adding calcium ions and a coupling agent into the starch inclusion compound, stirring, centrifuging, washing and drying to obtain a mixture of the starch-coated ammonium polyphosphate; preparation of an intumescent flame retardant system: mixing a mixture of ammonium salt and starch-coated ammonium polyphosphate to obtain an expansion flame-retardant system; preparing a flame-retardant composite material: and melting the thermoplastic plastics, and then putting the melted thermoplastic plastics into an expansion flame-retardant system for molding to obtain the flame-retardant composite material. According to the invention, no harmful reagent is added in the preparation process, and the prepared flame retardant has excellent performance and is environment-friendly. The method has the advantages of wide raw material source, low cost and low production cost, and is suitable for wide application.
Description
Technical Field
The invention relates to the field of flame-retardant composite materials, in particular to a method for preparing a flame-retardant composite material by coating ammonium polyphosphate particles with a calcium ion-induced starch/sodium oleate clathrate compound and performing coupling treatment with a coupling agent.
Background
With the rapid development of polymer materials, electronics, electrical appliances, machinery, automobiles, ships, aerospace and chemical industries, plastic products are increasingly widely applied to various fields in life and production of people. Especially, the application of thermoplastic plastic products brings great convenience to people. Thermoplastic plastic is a novel organic polymer synthetic material with great application potential, and has the characteristics of good toughness, large damage tolerance, good dielectric constant, unlimited storage period, no need of low-temperature storage, no need of large-scale special equipment such as autoclave and the like for molding, and particularly, the thermoplastic plastic has the characteristics of good recyclability, recoverability, reusability and no environmental pollution, thereby being suitable for the development direction of green and environment-friendly materials at present. Meanwhile, fire caused by the flammability of plastics also brings huge life and property losses to people. Therefore, flame retardant modification of plastics has been a problem of great importance.
At present, the application of novel, efficient and halogen-free flame retardant has become an important development direction of flame retardant scientific research, and the research of the halogen-free flame retardant additive mainly focuses on two aspects of metal hydrate and phosphorus compounds. The two compounds have small smoke amount during combustion and do not generate toxic and corrosive gases. For example, ammonium polyphosphate, also known as ammonium polyphosphate or condensed ammonium phosphate (abbreviated as APP), is a polyphosphate containing N and P. The ammonium polyphosphate is nontoxic and tasteless, does not generate corrosive gas during decomposition, has high thermal stability, and is a halogen-free flame retardant with excellent performance. Ammonium polyphosphate is commonly used as an acid source and a gas source in an intumescent flame retardant, and can form an intumescent flame retardant system with excellent performance with melamine and pentaerythritol, but the mechanical property of the composite material is reduced in the using process due to the polarity difference between hydrophilic and hydrophobic matrixes of the ammonium polyphosphate. Therefore, hydrophilic ammonium polyphosphate must be subjected to surface hydrophobic modification to improve the dispersibility and compatibility in a matrix.
Li jin Yu in Chinese patent application 201610765674.X discloses a preparation method of an epoxy resin coated ammonium polyphosphate flame retardant microcapsule, which comprises the steps of mixing epoxy resin, a curing agent, a reactive diluent and a catalyst, adding ammonium polyphosphate after atomization, curing, mixing, keeping warm and the like to obtain a composite material with certain flame retardant performance.
Liyanji discloses a method for coating ammonium polyphosphate with a binary composite coating agent in Chinese patent application 201410019387.5, which comprises the steps of adding ammonium polyphosphate, the binary composite coating agent and a dispersing agent into a reaction kettle for reaction, fully dissolving the ammonium polyphosphate and the binary composite coating agent, adjusting the pH value to be acidic, precipitating the coated ammonium polyphosphate, washing, drying and grinding to obtain a final product. The water solubility of the ammonium polyphosphate is reduced, the particle size distribution uniformity is improved, and the flame retardant property of the flame retardant polypropylene is improved.
In the chinese patent application 200910253739.2 of fangxiaohan, a preparation method of core-shell silica coated ammonium polyphosphate is disclosed, wherein ammonium polyphosphate and silicate ester are mixed in an ethanol aqueous solution, and the pH is adjusted for reaction; and adding a coupling agent to treat the surface, filtering, washing and drying to obtain the silicon dioxide coated ammonium polyphosphate. By utilizing the synergistic flame-retardant effect of silicon and phosphorus elements, the flame-retardant effect is enhanced, and the hydrophobicity of the ammonium polyphosphate is improved.
Said invention can obviously raise flame-retardant property of composite material by means of modification of ammonium polyphosphate flame-retardant agent and its technology. But the flame retardant performance and the hydrophobicity are improved, and simultaneously, the mechanical performance is obviously reduced. And the addition of a large amount of inorganic filler obviously reduces the degradation performance of the composite material. Therefore, how to coordinate the contradiction between the flame retardant property and the mechanical property is an important problem in the field of composite material flame retardant, so that the flame retardant property of the material is improved, and the influence on the mechanical property of the material is reduced. But the related reports are deficient at present.
Disclosure of Invention
The invention provides a process for preparing a flame-retardant composite material by coating ammonium polyphosphate with starch, which comprises the steps of coating ammonium polyphosphate with degradable starch to form a green environment-friendly ternary integrated flame-retardant system, coupling with a coupling agent to prepare the composite material with excellent flame-retardant property and mechanical property, expanding the application range of the starch and having the advantage of environmental friendliness.
In order to achieve the technical effects, the invention is realized by the following technical means:
a process for preparing a flame-retardant composite material by coating ammonium polyphosphate with starch comprises the following steps:
coating ammonium polyphosphate with starch: adding calcium ions and a coupling agent into the starch inclusion compound, stirring, centrifuging, washing and drying to obtain a mixture of the starch-coated ammonium polyphosphate;
preparation of an intumescent flame retardant system: mixing a mixture of ammonium salt and starch-coated ammonium polyphosphate to obtain an expansion flame-retardant system;
preparing a flame-retardant composite material: and melting the thermoplastic plastics, and then putting the melted thermoplastic plastics into an expansion flame-retardant system for molding to obtain the flame-retardant composite material.
As a further improvement of the present invention, before the coating of ammonium polyphosphate with starch, a preparation of a starch inclusion compound is also included, and the preparation of the starch inclusion compound specifically comprises: and adding a sodium oleate solution into the starch colloid solution, and heating to obtain the inclusion compound of the starch and the sodium oleate.
As a further improvement of the invention, in the preparation of the starch clathrate compound, the heating temperature is 53-99 ℃, and the heating time is 0.2-24 h.
As a further improvement of the invention, after the preparation of the starch inclusion compound, the cooling of the starch inclusion compound is also included, and the cooling is to cool the starch inclusion compound to 15-35 ℃.
As a further improvement of the invention, the mass fraction of the sodium oleate solution is 0.1-3%.
As a further improvement of the present invention, before the preparation of the starch clathrate, the preparation of a colloidal solution of starch is further included, and the preparation of the colloidal solution of starch specifically comprises: weighing a proper amount of starch to prepare a solution with the mass fraction of 0.1-20%, and heating in a water bath at 53-99 ℃ for 0.2-24 hours under the stirring of 50-1500 rpm to fully gelatinize the starch to obtain a starch colloid solution.
As a further improvement of the invention, in the step of coating the ammonium polyphosphate by the starch, the rotating speed of centrifugal washing is 2000-10000rpm, and the washing times are 3 times or more.
As a further improvement, in the preparation of the intumescent flame retardant system, the mass ratio of the mixture of ammonium salt and starch-coated ammonium polyphosphate is 2: 1-10: 1
As a further improvement of the invention, the thermoplastic plastic is at least one of polypropylene, polyethylene, polylactic acid, polycarbonate, polycaprolactone or polybutylene succinate.
Compared with the prior art, the invention has the following beneficial effects:
the starch is used as a carbon source, the physical distance between the coated carbon source and the acid source is smaller, and the reaction efficiency is higher during combustion, so that the flame retardant property of the intumescent flame retardant system is improved. Meanwhile, the long-chain silane coupling agent is used for modifying the coated ammonium polyphosphate particles, so that the interfacial compatibility of the flame retardant in the composite material is improved. In addition, the natural degradable high molecular starch is fully utilized, so that the flame retardant is more green and environment-friendly.
According to the invention, the starch is used for coating the ammonium polyphosphate particles, so that the problem of hydrophilicity of the ammonium polyphosphate can be effectively improved, and the surface of the ammonium polyphosphate coated by the starch is modified by using the long-chain silane coupling agent, so that the dispersibility of the ammonium polyphosphate in a polymer is improved, the interface bonding force is improved, the starch serves as a carbon source, the physical distance between the coated carbon source and an acid source is smaller, the reaction efficiency during combustion is higher, the flame retardant property of an expansion flame retardant system is improved, the composite material has excellent flame retardant property and mechanical property, the influence on the degradation property of the composite material is smaller, the cost is low, and the method is favorable for batch, continuous and large-scale industrial production.
Detailed Description
The invention is further explained in order to make the technical means, the innovative features and the completed efficacy of the invention easy to understand. The technical means for realizing the present invention should not be limited to the following examples, and can be adjusted within the scope of the above-described contents of the invention.
In the invention, the process for preparing the flame-retardant composite material by coating the ammonium polyphosphate particles with the starch comprises the following specific steps:
(1) preparing a certain amount of starch into a solution with the mass fraction of 0.1-20%, heating in a water bath at 53-99 ℃ for 0.2-24 hours under the stirring of 50-1500 rpm to ensure that the starch is fully gelatinized to form a uniformly dispersed colloidal solution.
The colloid is between the solution and the turbid solution and can exist stably under certain conditions. Colloidal particles in the colloid precipitate or settle out by binding to each other under appropriate conditions to form larger diameter particles, and colloidal solutions enable starch to be deposited more readily on the surface of ammonium polyphosphate than other solutions.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 0.1-3%, and heating the prepared solution at 53-99 ℃ for 2-24h to form an inclusion compound of the starch and the sodium oleate.
Specifically, at the moment, sodium oleate is inserted into the starch structure, the starch is a spiral macromolecular chain, the sodium oleate is a chain-shaped molecule and contains hydrophobic groups, an interpenetrating cross-linked network structure can be formed between the sodium oleate and the chain-shaped molecule, and the water solubility of the starch can be reduced; meanwhile, the formed inclusion compound is more stably deposited on the surface of the ammonium polyphosphate, and the hydrophilicity of the ammonium polyphosphate is improved.
In this case, sodium oleate is the guest molecule, which may be replaced by fatty acid.
In the step, the starch has a gelatinization temperature range, so that gelatinization cannot be realized at a temperature of less than 53 ℃ and the gelatinization temperature exceeds 99 ℃, water can boil, and coating is influenced.
And the heating time is too short to gelatinize, and the gelatinization viscosity of the starch is too high due to too long heating time, so that the coating is influenced. In this example, if the mass fraction of sodium oleate is too small, the coating is not performed, and if it is too large, the inclusion compound is bonded and becomes non-uniform.
(3) Cooling the solution to 15-35 ℃, adding 0.1-5mol/L calcium ion solution and 0.1-5% coupling agent by mass, stirring at 50-800 rpm for 5-120min, then carrying out centrifugal washing on the suspension to remove excessive calcium ions, and drying to obtain the starch-coated ammonium polyphosphate.
In the invention, calcium ions play a role in inducing coating, and the introduction of the calcium ions can enable the water solubility of the hydrophilic end of the starch to be instantly reduced, thereby reducing the water solubility of the starch in a water-containing system and realizing the deposition and coating of the starch on the surfaces of filler particles.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, taking ammonium salts as an air source, respectively placing the ammonium polyphosphate and the ammonium salts in a 60-100 ℃ blast drying oven for drying for 3-8 hours, and uniformly mixing at room temperature according to a mass ratio of 2: 1-10: 1 for later use.
Preferably, the mass ratio of starch to polyamide is 1-2: 4-5.
(5) Preparing a composite material:
firstly, placing thermoplastic plastics in a forced air drying oven at 60-100 ℃ for drying for 6-12 h for later use;
and secondly, adding thermoplastic plastics into molding equipment with the temperature of 80-230 ℃, after the thermoplastic plastics are melted, adding the intumescent flame retardant obtained in the step 2, and performing melt blending molding to obtain the composite material. The thermoplastic plastic can be completely melted at the temperature of 80-230 ℃.
In this embodiment, the starch is one or a mixture of several of corn starch, potato starch and tapioca starch.
In this embodiment, the calcium ion is one or a mixture of several of calcium chloride, calcium bromide, calcium nitrate, and calcium sulfate.
In this embodiment, the rotation speed of the centrifugal washing in the step (3) is 2000-10000rpm, and the washing times are 3 times or more; the drying method is freeze drying or spray drying.
In this embodiment, the coupling agent in step (3) is one or a mixture of several of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The coupling agents have good interface compatibility, good stability and higher efficiency.
In this embodiment, the ammonium salt used as the gas source is one or a mixture of melamine, dicyandiamide and urea. The gas sources do not generate corrosive toxic gas in the combustion process, so that the use is safer.
In this embodiment, the thermoplastic plastic is one or a mixture of polyethylene, polypropylene, polylactic acid, polycarbonate, polycaprolactone, and polybutylene succinate. The plastics have good thermal stability, good processability, excellent mechanical property and environmental friendliness.
In this embodiment, the melt processing mode is banburying/roll mixing and hot press molding or extrusion molding.
Example 1:
(1) the corn starch is prepared into a solution with the mass fraction of 3%, and the solution is heated in a water bath at 95 ℃ for 1 hour under the stirring of 250 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 2%, and heating the prepared mixed solution at 95 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 6g of starch and 15g of ammonium polyphosphate were used.
(3) Cooling the solution to 25 ℃, and adding water to dilute the solution to a solution with the mass fraction of 8%; then adding 0.2mol/L calcium chloride solution and 2% of octadecyl trimethoxy silane coupling agent by mass fraction to induce the starch/sodium oleate inclusion compound to deposit on the ammonium polyphosphate, centrifugally washing the suspension for 3 times at 4000rpm to remove excessive calcium ions, and freeze-drying to obtain the starch-coated ammonium polyphosphate.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 20% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 80% of polybutylene succinate (PBS). And (3) mixing the materials for 15mins by an open mill at the temperature of 110 ℃, and performing hot press molding to obtain the PBS/expansion flame-retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 1 is shown in table 1.
Example 2:
(1) preparing the potato starch into a solution with the mass fraction of 1%, and heating in a water bath at 85 ℃ for 12 hours under the stirring of 500 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 2%, and heating the prepared mixed solution at 95 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 3g of starch and 15g of ammonium polyphosphate were used.
(3) Cooling the solution to 25 ℃, and adding water to dilute the solution to a solution with the mass fraction of 5%; then adding 0.5mol/L calcium bromide solution and 0.7% by mass of titanate coupling agent to induce the starch/sodium oleate inclusion compound to deposit on the ammonium polyphosphate, centrifugally washing the suspension at 6000rpm for 3 times to remove excessive calcium ions, and freeze-drying to obtain the starch-coated ammonium polyphosphate.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 20% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 85% of polylactic acid (PLA). Mixing the materials for 15mins in an open mill at 180 ℃, and performing hot-press molding to obtain the PLA/intumescent flame-retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 2 is shown in table 1.
Example 3:
(1) preparing the cassava starch into a solution with the mass fraction of 5%, and heating the solution in a water bath at 75 ℃ for 10 hours under the stirring of 600 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 2%, and heating the prepared mixed solution at 75 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 6g of starch and 15g of ammonium polyphosphate were used.
(3) Cooling the solution to 25 ℃, and adding water to dilute the solution to a solution with the mass fraction of 8%; then adding 2mol/L calcium nitrate solution and 1% hexadecyl trimethoxy silane coupling agent by mass fraction to induce the starch/sodium oleate inclusion compound to deposit on the ammonium polyphosphate, centrifugally washing the suspension for 3 times at 8000rpm to remove excessive calcium ions, and freeze-drying to obtain the starch-coated ammonium polyphosphate.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 25% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 75% of Polycarbonate (PC). And (3) mixing the materials for 15mins by an open mill at 225 ℃, and performing hot press molding to obtain the PC/intumescent flame retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 3 is shown in table 1.
Example 4:
(1) corn starch and potato starch (1: 1) are prepared into a solution with the mass fraction of 8%, and the solution is heated in a water bath at 85 ℃ for 15 hours under the stirring of 300 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 2%, and heating the prepared mixed solution at 85 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 3g of starch and 15g of ammonium polyphosphate were used.
(3) And cooling the solution to 25 ℃, adding 3mol/L of calcium sulfate solution and 2.5 mass percent of dodecyl trimethoxy silane coupling agent to induce the starch/sodium oleate inclusion compound to deposit on ammonium polyphosphate, centrifugally washing the suspension at 6000rpm for 3 times to remove excessive calcium ions, and drying in vacuum at 60 ℃ for 8 hours to obtain the starch-coated ammonium polyphosphate.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 20% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 80% of poly (butylene adipate terephthalate) (PBAT). Mixing the materials for 15mins by an open mill at 130 ℃, and performing hot press molding to obtain the PBAT/intumescent flame retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 4 is shown in table 1.
Example 5:
(1) the cassava starch and the potato starch (3: 1) are prepared into a solution with the mass fraction of 6%, and the solution is heated in a water bath at 95 ℃ for 2 hours under the stirring of 1000 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 1.5%, and heating the prepared mixed solution at 95 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 3g of starch and 12g of ammonium polyphosphate were used.
(3) And cooling the solution to 25 ℃, adding 0.5mol/L calcium nitrate solution and 1.6 mass percent hexadecyl trimethoxy silane coupling agent to induce the starch/sodium oleate inclusion compound to deposit on the ammonium polyphosphate, centrifugally washing the suspension at 6000rpm for 3 times to remove excessive calcium ions, and drying in vacuum at 60 ℃ for 12 hours to obtain the starch-coated ammonium polyphosphate.
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 30% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 70% of polypropylene (PP). And (3) mixing the materials for 15mins by an open mill at the temperature of 170 ℃, and performing hot press molding to obtain the PP/intumescent flame retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 5 is shown in table 1.
Example 6:
(1) the corn starch is prepared into a solution with the mass fraction of 3%, and the solution is heated in a water bath at 85 ℃ for 4 hours under the stirring of 1000 rpm.
(2) Adding a certain amount of ammonium polyphosphate into the gelatinized starch solution, stirring, adding a sodium oleate solution with the mass fraction of 2%, and heating the prepared mixed solution at 85 ℃ for 30min to promote the starch and the sodium oleate to form an inclusion compound.
In this example, 3g of starch and 15g of ammonium polyphosphate were used.
(3) Cooling the solution to 25 ℃, adding 0.2mol/L calcium sulfate solution and 1.8 mass percent of aluminate coupling agent to induce the starch/sodium oleate inclusion compound to deposit on the ammonium polyphosphate, centrifugally washing the suspension for 3 times at 5000rpm to remove excessive calcium ions, and spray drying to obtain the starch-coated ammonium polyphosphate
(4) Preparation of an intumescent flame retardant system:
weighing a certain amount of starch-coated ammonium polyphosphate as an acid source and a carbon source, and melamine as an air source, respectively placing the ammonium polyphosphate and the melamine in a forced air drying oven at 80 ℃ for drying for 4h, and uniformly mixing at room temperature according to a mass ratio of 5:1 for later use.
(5) Preparing a composite material:
the materials are mixed according to the following mass percentage: 30% of intumescent flame retardant prepared by mixing starch modified ammonium polyphosphate and melamine and 70% of Polyethylene (PE). And (3) mixing the materials for 15mins by an open mill at the temperature of 100 ℃, and performing hot press molding to obtain the PE/intumescent flame retardant system composite material.
The performance of the flame-retardant composite material prepared by using the starch-coated ammonium polyphosphate particles in example 6 is shown in table 1.
Comparative example
(1) Preparation of an intumescent flame retardant system:
weighing a certain amount of unmodified ammonium polyphosphate as an acid source and melamine as an air source, respectively placing the ammonium polyphosphate as the acid source and the melamine as the air source in an air blast drying oven at 80 ℃ for drying for 4 hours, and uniformly mixing the ammonium polyphosphate and the melamine at room temperature according to the mass ratio of 5:1 for later use.
(2) Preparing a composite material:
the materials are mixed according to the following mass percentage: 25% of intumescent flame retardant prepared by mixing unmodified ammonium polyphosphate and melamine and 75% of polybutylene succinate (PBS). And (3) mixing the materials for 15mins by an open mill at the temperature of 110 ℃, and performing hot press molding to obtain the PBS/expansion flame-retardant system composite material.
The performance of the flame-retardant composite prepared by using the starch-coated ammonium polyphosphate particles in the comparative example is shown in table 1.
TABLE 1
| Examples of the embodiments | Base body | Tensile Strength (MPa) | Flexural modulus (Mpa) | Limiting Oxygen Index (LOI) | UL-94 |
| Comparative examples | PBS | 20.2 | 368 | 29.4% | V-0 |
| Example 1 | PBS | 23.32 | 434 | 31.12% | V-0 |
| Example 2 | PLA | 35.65 | 164 | 32.45% | V-0 |
| Example 3 | PC | 53.23 | 136 | 35.56% | V-0 |
| Example 4 | PBAT | 45.84 | 140 | 29.85% | V-1 |
| Example 5 | PP | 27.68 | 110 | 33.34% | V-0 |
| Example 6 | PE | 29.63 | 98 | 29.56% | V-1 |
It can be seen from table 1 that the unmodified ammonium polyphosphate in the comparative example achieves a certain flame retardant effect when added to the composite material, but the mechanical properties of the composite material are reduced, whereas the ammonium polyphosphate modified by the starch in the above 6 examples is added to the polymer matrix, so that the flame retardant property of the composite material is effectively improved, and the mechanical properties are also improved.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A process for preparing a flame-retardant composite material by coating ammonium polyphosphate with starch is characterized by comprising the following steps of:
coating ammonium polyphosphate with starch: adding calcium ions and a coupling agent into the starch inclusion compound, stirring, centrifuging, washing and drying to obtain a mixture of the starch-coated ammonium polyphosphate;
preparation of an intumescent flame retardant system: mixing a mixture of ammonium salt and starch-coated ammonium polyphosphate to obtain an expansion flame-retardant system;
preparing a flame-retardant composite material: and melting the thermoplastic plastics, and then putting the melted thermoplastic plastics into an expansion flame-retardant system for molding to obtain the flame-retardant composite material.
2. The process for preparing the flame-retardant composite material by using the starch-coated ammonium polyphosphate according to claim 1, wherein the preparation of the starch inclusion compound is further included before the starch-coated ammonium polyphosphate, and the preparation of the starch inclusion compound specifically comprises the following steps: and adding a sodium oleate solution into the starch colloid solution, and heating to obtain the inclusion compound of the starch and the sodium oleate.
3. The process for preparing the flame-retardant composite material by using the starch coated ammonium polyphosphate according to claim 2, wherein the heating temperature is 53-99 ℃ and the heating time is 0.2-24h in the preparation of the starch clathrate compound.
4. The process for preparing the flame-retardant composite material by using the starch-coated ammonium polyphosphate according to claim 3, wherein the preparation of the starch clathrate compound is followed by the cooling of the starch clathrate compound, and the cooling is to cool the starch clathrate compound to 15-35 ℃.
5. The process for preparing a flame-retardant composite material by using starch coated ammonium polyphosphate according to claim 2, wherein the mass fraction of the sodium oleate solution is 0.1-3%.
6. The process for preparing the flame-retardant composite material by using the starch-coated ammonium polyphosphate according to claim 4, further comprising the preparation of a colloidal solution of starch before the preparation of the starch clathrate compound, wherein the preparation of the colloidal solution of starch specifically comprises the following steps: weighing a proper amount of starch to prepare a solution with the mass fraction of 0.1-20%, and heating in a water bath at 53-99 ℃ for 0.2-24 hours under the stirring of 50-1500 rpm to fully gelatinize the starch to obtain a starch colloid solution.
7. The process for preparing flame retardant composite material by using starch coated ammonium polyphosphate according to any one of claims 1 to 6, wherein in the step of coating ammonium polyphosphate by starch, the rotation speed of centrifugal washing is 2000-10000rpm, and the washing times are 3 times or more.
8. The process for preparing the flame-retardant composite material by using the starch-coated ammonium polyphosphate according to any one of claims 1 to 6, wherein in the preparation of the expansion flame-retardant system, the mass ratio of the mixture of the ammonium salt and the starch-coated ammonium polyphosphate is 2: 1-10: 1.
9. The process for preparing flame retardant composite material according to any of claims 1-6, wherein the thermoplastic is at least one of polypropylene, polyethylene, polylactic acid, polycarbonate, polycaprolactone, or polybutylene succinate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220462.3A CN110804286B (en) | 2019-12-03 | 2019-12-03 | Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220462.3A CN110804286B (en) | 2019-12-03 | 2019-12-03 | Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110804286A true CN110804286A (en) | 2020-02-18 |
| CN110804286B CN110804286B (en) | 2021-09-28 |
Family
ID=69492231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911220462.3A Active CN110804286B (en) | 2019-12-03 | 2019-12-03 | Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110804286B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875880A (en) * | 2020-07-15 | 2020-11-03 | 江南大学 | Halogen-free flame-retardant TPV composite material and preparation method thereof |
| CN112063019A (en) * | 2020-08-06 | 2020-12-11 | 湖北工程学院 | Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof |
| CN114644781A (en) * | 2022-05-06 | 2022-06-21 | 什邡市太丰新型阻燃剂有限责任公司 | Degradable flame retardant and preparation method thereof |
| CN115678574A (en) * | 2022-10-24 | 2023-02-03 | 北京建筑材料科学研究总院有限公司 | Single-component intumescent flame retardant and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050054553A1 (en) * | 2003-06-27 | 2005-03-10 | The Procter & Gamble Company | Liquid fabric softening compositions comprising flame retardant |
| CN101143952A (en) * | 2007-09-12 | 2008-03-19 | 东北林业大学 | Flame-proof smoke-inhibiting wood-plastic composite material |
| CN101372548A (en) * | 2008-10-15 | 2009-02-25 | 珠海市远康企业有限公司 | High-impact polystyrene blend and preparation thereof |
| CN101407597A (en) * | 2007-10-12 | 2009-04-15 | 上海化工研究院 | Halogen-free flame-retardant photo-curing epoxy resin composition |
| CN104592405A (en) * | 2014-12-18 | 2015-05-06 | 新疆德美隆合成材料科技有限公司 | Amylose carbon forming agent and production method thereof |
| CN105111321A (en) * | 2015-08-31 | 2015-12-02 | 华南理工大学 | High-carbonization-rate carboxyl starch, preparation method and application thereof, and intumescent halogen-free flame retardant based on starch |
| CN107298772A (en) * | 2017-08-22 | 2017-10-27 | 南宁学院 | A kind of PLA fire retardant and preparation method thereof |
| CN107383816A (en) * | 2017-08-22 | 2017-11-24 | 南宁学院 | A kind of flame-proof polylactic acid composite and preparation method thereof |
| CN109181248A (en) * | 2018-09-05 | 2019-01-11 | 太原理工大学 | A kind of preparation method of ammonium polyphosphate cladding carbosphere fire retardant |
| CN109486348A (en) * | 2018-11-07 | 2019-03-19 | 沈阳化工大学 | A kind of fire-proof corrosive-resistant paint preparation method |
-
2019
- 2019-12-03 CN CN201911220462.3A patent/CN110804286B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050054553A1 (en) * | 2003-06-27 | 2005-03-10 | The Procter & Gamble Company | Liquid fabric softening compositions comprising flame retardant |
| CN101143952A (en) * | 2007-09-12 | 2008-03-19 | 东北林业大学 | Flame-proof smoke-inhibiting wood-plastic composite material |
| CN101407597A (en) * | 2007-10-12 | 2009-04-15 | 上海化工研究院 | Halogen-free flame-retardant photo-curing epoxy resin composition |
| CN101372548A (en) * | 2008-10-15 | 2009-02-25 | 珠海市远康企业有限公司 | High-impact polystyrene blend and preparation thereof |
| CN104592405A (en) * | 2014-12-18 | 2015-05-06 | 新疆德美隆合成材料科技有限公司 | Amylose carbon forming agent and production method thereof |
| CN105111321A (en) * | 2015-08-31 | 2015-12-02 | 华南理工大学 | High-carbonization-rate carboxyl starch, preparation method and application thereof, and intumescent halogen-free flame retardant based on starch |
| CN107298772A (en) * | 2017-08-22 | 2017-10-27 | 南宁学院 | A kind of PLA fire retardant and preparation method thereof |
| CN107383816A (en) * | 2017-08-22 | 2017-11-24 | 南宁学院 | A kind of flame-proof polylactic acid composite and preparation method thereof |
| CN109181248A (en) * | 2018-09-05 | 2019-01-11 | 太原理工大学 | A kind of preparation method of ammonium polyphosphate cladding carbosphere fire retardant |
| CN109486348A (en) * | 2018-11-07 | 2019-03-19 | 沈阳化工大学 | A kind of fire-proof corrosive-resistant paint preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875880A (en) * | 2020-07-15 | 2020-11-03 | 江南大学 | Halogen-free flame-retardant TPV composite material and preparation method thereof |
| CN112063019A (en) * | 2020-08-06 | 2020-12-11 | 湖北工程学院 | Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof |
| CN114644781A (en) * | 2022-05-06 | 2022-06-21 | 什邡市太丰新型阻燃剂有限责任公司 | Degradable flame retardant and preparation method thereof |
| CN114644781B (en) * | 2022-05-06 | 2023-09-26 | 什邡市太丰新型阻燃剂有限责任公司 | Degradable flame retardant and preparation method thereof |
| CN115678574A (en) * | 2022-10-24 | 2023-02-03 | 北京建筑材料科学研究总院有限公司 | Single-component intumescent flame retardant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110804286B (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110804286B (en) | Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch | |
| CA2826264C (en) | Flame retardant compositions | |
| CN110592709A (en) | Preparation method of flame-retardant anti-dripping polyester fiber | |
| CN105419258A (en) | Method of preparing degradable flame-retarding composite material with surface-modified magnesium salt crystal whisker | |
| CN109971037A (en) | Phosphorous nano-meter flame retardants and preparation method thereof | |
| CN116285256B (en) | Sterile barrier for sterile medical instrument | |
| CN112280260A (en) | High-barrier PLA/PBAT composite packaging film | |
| CN114752115B (en) | Flame-retardant modified cellulose and polylactic acid based composite material and preparation method thereof | |
| CN112080041B (en) | Preparation method of POSS grafted tannin modified diatomite flame-retardant modified composite material | |
| CN113214564B (en) | High-gloss flame-retardant antibacterial polypropylene composite material and preparation method thereof | |
| CN113150440B (en) | Preparation method of flame-retardant polypropylene | |
| CN113150489A (en) | ABS composite material and preparation method thereof | |
| JP3799117B2 (en) | Biodegradable chitosan-containing composition and method for producing the same | |
| CN112142996A (en) | Preparation method and application of modified polyester master batch | |
| CN114539731B (en) | Flame-retardant material and preparation method thereof | |
| CN112961406B (en) | Confined polymerization flame retardant and preparation method thereof | |
| CN116875021B (en) | PC/ABS alloy material and preparation method and application thereof | |
| CN115433395B (en) | Chitosan-based N/P/B three-element synergistic flame retardant and preparation method and application thereof | |
| CN115093694B (en) | Halogen-free flame-retardant TPU composite material and preparation method thereof | |
| CN115895209A (en) | Calcium carbonate master batch and preparation method and application thereof | |
| CN116554482B (en) | Chemically-terminated focused piperazine phosphate modified ammonium polyphosphate resistant to high temperature and precipitation as well as preparation method, device and application thereof | |
| CN117487142A (en) | High-barrier biodegradable polyester, preparation method thereof and high-barrier biodegradable film | |
| CN113621179A (en) | Surface-modified zinc alkyl phosphinate flame retardants and modified polycarbonates based thereon | |
| CN114230801A (en) | Preparation method of polyphosphazene flame retardant and application of polyphosphazene flame retardant in PET flame retardance | |
| CN116210692A (en) | Surface treatment method of inorganic antibacterial agent and application of inorganic antibacterial agent in PEI composite material |
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 |