CN112745525B - Flame-retardant filler and preparation method thereof - Google Patents
Flame-retardant filler and preparation method thereof Download PDFInfo
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- CN112745525B CN112745525B CN201911040050.1A CN201911040050A CN112745525B CN 112745525 B CN112745525 B CN 112745525B CN 201911040050 A CN201911040050 A CN 201911040050A CN 112745525 B CN112745525 B CN 112745525B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The application provides a flame-retardant filler, which is prepared from the following components in parts by mass: the mass ratio of boehmite, tri (chloroisopropyl) phosphate and titanium dioxide loaded phosphomolybdic acid flame retardant is (20-30): (40-60): (10-16). And provides a preparation method of the flame-retardant filler and a flame-retardant polymer containing the flame-retardant filler. The titanium dioxide loaded phosphomolybdic acid flame retardant and the boehmite in the flame retardant filler prepared by the application have the effect of blocking or inhibiting smoke, so that the flame retardant property of the polymer composite material can be well improved, and the flame retardant filler has great popularization value.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a flame-retardant filler and a preparation method thereof.
Background
Flame retardant property is one of important properties of automobile interior and exterior decorative parts, plastic shells and the like, flame retardant thermoplastic plastics such as flame retardant PC, flame retardant ABS, flame retardant PA, flame retardant PP and the like have the characteristics of high flame retardance, high flow and the like, are easy to injection molding, and are widely used in fields of household appliances, electronic appliances, consumer electronics, electric tools and the like. At present, flame retardant thermoplastic plastics are mainly realized by adding flame retardants, wherein the flame retardants comprise halogen flame retardants and halogen-free flame retardants, the halogen flame retardants are forbidden, the common halogen-free flame retardants mainly comprise inorganic flame retardants and phosphorus-nitrogen intumescent flame retardants, and the inorganic flame retardants have a certain flame retardant effect only when being filled in a large amount due to poor compatibility with resin, so that the mechanical property and the processing property of the resin are seriously damaged.
Disclosure of Invention
The application aims to provide a flame-retardant filler and a preparation method thereof, and the flame-retardant filler can improve the flame retardant property of a polymer composite material.
The technical scheme of the application is as follows:
the flame-retardant filler is prepared from the following components in percentage by mass: the mass ratio of boehmite, tri (chloroisopropyl) phosphate and titanium dioxide loaded phosphomolybdic acid flame retardant is (20-30): (40-60): (10-16).
The titanium dioxide loaded phosphomolybdic acid flame retardant is prepared by the following steps: firstly, mixing dioctadecyl dimethyl ammonium bromide, tetrabutyl titanate, deionized water and phosphoric acid solution for reaction, then adding phosphomolybdic acid solution for continuous reaction, and then drying the reactant and calcining in a muffle furnace.
The particle size of the boehmite is 400-480nm.
A second object of the present application is to provide a method for preparing the above flame retardant filler, comprising the steps of:
(1) Putting dioctadecyl dimethyl ammonium bromide, tetrabutyl titanate, deionized water and phosphoric acid solution into a reaction vessel for reaction for 6-8h at room temperature to obtain solution A;
(2) Adding phosphomolybdic acid solution, and reacting for 20-28h at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 300-360 ℃ for 5-7 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain the titanium dioxide-loaded phosphomolybdic acid flame retardant with the particle size of not more than 25 mu m;
(5) And (3) fully mixing boehmite, tri (chloroisopropyl) phosphate and titanium dioxide loaded phosphomolybdic acid flame retardant in a high-speed stirrer, and cooling to room temperature to obtain the flame retardant filler.
The mass ratio of dioctadecyl dimethyl ammonium bromide, tetra-n-butyl titanate, deionized water and phosphoric acid solution in the step (1) is (1-3): (20-30): (200-240): (30-40).
The mass ratio of the solution A to the phosphomolybdic acid solution in the step (2) is (80-100): (20-30).
The mass ratio of the boehmite, the tri (chloroisopropyl) phosphate and the titanium dioxide loaded phosphomolybdic acid flame retardant in the step (5) is (20-30): (40-60): (10-16), the rotating speed of the high-speed stirrer is 200-280r/min, and the stirring time is 40-60min.
A third object of the present application is to provide a flame retardant polymer comprising a matrix resin and a flame retardant filler according to claim 1 or 2, said flame retardant filler being used in an amount of 10% to 20% by weight of the total mass of the flame retardant polymer.
The matrix resin is one of Polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutylene terephthalate (PBT) and polyamide 6 (PA 6).
The preparation method of the flame-retardant polymer comprises the steps of stirring and mixing matrix resin and flame-retardant filler by a high-speed mixer, and then adding the mixture into a double-screw extruder for blending and extrusion.
The application has the beneficial effects that:
(1) The flame retardant mechanism of the titanium dioxide loaded phosphomolybdic acid flame retardant prepared by the application is as follows:
firstly, phosphomolybdic acid is heated and decomposed to generate oxo acid and phosphoric acid, a liquid film and a carbon layer protection matrix are formed on the surface of a polymer material, and the flame retardant property of the polymer material is improved;
secondly, titanium dioxide promotes the polymer matrix to be carbonized into carbon in the combustion process in the solid phase, and a barrier layer is formed on the surface of the matrix by covering the polymer matrix; in addition, the titanium dioxide can capture active free radicals in a gas phase, inhibit the chain reaction of combustion and achieve the purposes of flame retardance and smoke suppression.
(2) Boehmite in the flame-retardant filler prepared by the application can generate water and Al in the thermal decomposition process 2 O 3 The water can dilute the combustible gas, al 2 O 3 The solid is covered on the surface of the polymer matrix to block and delay the burning rate, thereby achieving the effects of flame retardance and smoke suppression.
(3) In the application, the tri (chloroisopropyl) phosphate is a common phosphorus flame retardant, and is heated to decompose and produce glass-like substances, and simultaneously promote the surface of the polymer to form a carbon layer, thereby achieving the flame retardant effect.
(4) The flame-retardant filler prepared by the application is compounded by tri (chloroisopropyl) phosphate, boehmite and titanium dioxide loaded phosphomolybdic acid, and can play a good role in synergistic flame retardance, and further improve the flame retardance of the polymer composite material.
Detailed Description
The following detailed description of the present application will provide further details in order to make the above-mentioned objects, features and advantages of the present application more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
The raw materials used in the following examples of the present application are as follows:
PBT (model 2002U), japanese Bao Ji;
PP (model Z30S), luxuriant petrochemical;
PE (model 5070), panjin ethylene;
PA6 (model IM), russian kobyshev nitrogen;
PS (model 350), taiwan arbor;
dioctadecyl dimethyl ammonium bromide, beijing Hanlong, limited development technology;
phosphoric acid, linyi Huarui chemical Co., ltd;
tetra-n-butyl titanate, green chemical auxiliary agent factory in Tianchang city;
deionized water, xiamen Australian environmental protection technologies Co., ltd;
phosphomolybdic acid, hubei Wanzhen chemical Co., ltd;
boehmite, zibo Jin Qi chemical technology Co., ltd;
tri (chloroisopropyl) phosphate, beijing torches, constant technology limited.
The flammability test of the application is detected by a UL 94V-level fireproof test vertical burning method, and the size specification of the flame retardant spline used in the flammability test of the materials prepared by each example and the comparative example is (125.0+/-5.0) mm (13.0+/-0.5) mm (1.6+/-0.2) mm.
Preparation example 1
(1) Weighing 10g of dioctadecyl dimethyl ammonium bromide, 200g of tetra-n-butyl titanate, 2.0kg of deionized water and 300g of phosphoric acid solution, and putting the solution into a reaction vessel to react for 6 hours at room temperature to obtain a solution A;
(2) Weighing 800g of solution A and 200g of phosphomolybdic acid solution, and placing the solution A and 200g of phosphomolybdic acid solution into a reaction vessel to react for 20 hours at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 300 ℃ for 5 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain a titanium dioxide-loaded phosphomolybdic acid flame retardant;
(5) 200g of boehmite with the particle size of 400nm, 400g of tri (chloroisopropyl) phosphate and 100g of titanium dioxide-loaded phosphomolybdic acid flame retardant are weighed, fully mixed for 40min in a high-speed stirrer with the rotating speed of 200r/min, and cooled to room temperature, so that the flame retardant filler P1 is obtained.
Application example 1
And adding 20 parts of flame retardant filler P1 into 80 Parts of Polypropylene (PP), stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending extrusion to obtain the PP composite material X1.
The twin-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first temperature area is 170 ℃, the temperature of the second temperature area is 220 ℃, the temperature of the third temperature area is 230 ℃, the temperature of the fourth temperature area is 240 ℃, the temperature of the fifth temperature area is 240 ℃, the temperature of the sixth temperature area is 240 ℃, the temperature of the head of the twin-screw extruder is 230 ℃, and the screw rotating speed is 220r/min.
Comparative example 1
80 Parts of Polypropylene (PP) is taken and stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain the PP composite material D1.
The performance data of the PP composite material prepared in the above application example 1 and comparative example 1 are shown in the following table:
| test item | Test standard | X1 | D1 |
| Flame retardant rating (1.6 mm) | UL94 | V-0 | Non-conforming V-level decision |
As can be seen from the table, the flame retardant property of X1 is better than that of D1, which shows that the flame retardant property of the PP composite material is better after the flame retardant filler prepared by the application is added.
Preparation example 2
(1) 30g of dioctadecyl dimethyl ammonium bromide, 300g of tetra-n-butyl titanate, 2.4kg of deionized water and 400g of phosphoric acid solution are weighed, and put into a reaction vessel to react for 8 hours at room temperature to obtain solution A;
(2) Weighing 1.0kg of solution A and 300g of phosphomolybdic acid solution, and putting the solution A and the solution into a reaction vessel to react for 28 hours at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 360 ℃ for 7 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain the titanium dioxide-loaded phosphomolybdic acid flame retardant;
(5) 300g of boehmite with the particle size of 480nm, 600g of tri (chloroisopropyl) phosphate and 160g of titanium dioxide-loaded phosphomolybdic acid flame retardant are weighed, fully mixed for 60min in a high-speed stirrer with the rotating speed of 280r/min, and cooled to room temperature, so as to obtain the flame retardant filler P2.
Application example 2
15 parts of flame retardant filler P2 is added into 85 parts of polybutylene terephthalate (PBT), stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain the PBT composite material X2.
The twin-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first temperature area is 200 ℃, the temperature of the second temperature area is 230 ℃, the temperature of the third temperature area is 230 ℃, the temperature of the fourth temperature area is 230 ℃, the temperature of the fifth temperature area is 230 ℃, the temperature of the sixth temperature area is 230 ℃, the temperature of the head of the twin-screw extruder is 230 ℃, and the screw rotating speed is 300r/min.
Comparative example 2
85 parts of PBT is taken, stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain the PBT composite material D2.
The performance data of the PBT composite material prepared in the application example 2 and the comparative example 2 are shown in the following table:
| test item | Test standard | X2 | D2 |
| Flame retardant rating (1.6 mm) | UL94 | V-0 | Non-conforming V-level decision |
As can be seen from the table, the flame retardant property of X2 is better than that of D2, which indicates that the flame retardant property of the PBT composite material X2 prepared by adding the flame retardant filler P2 of the application into PBT is better.
Preparation example 3
(1) Weighing 20g of dioctadecyl dimethyl ammonium bromide, 250g of tetra-n-butyl titanate, 2.2kg of deionized water and 350g of phosphoric acid solution, and putting the solution into a reaction vessel to react for 7 hours at room temperature to obtain a solution A;
(2) Weighing 900g of solution A and 250g of phosphomolybdic acid solution, and putting the solutions into a reaction vessel to react for 24 hours at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 330 ℃ for 6 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain the titanium dioxide-loaded phosphomolybdic acid flame retardant;
(5) 250g of boehmite with the particle size of 420nm, 500g of tri (chloroisopropyl) phosphate and 130g of titanium dioxide-loaded phosphomolybdic acid flame retardant are weighed, fully mixed in a high-speed stirrer with the rotating speed of 240r/min, stirred for 50min, and cooled to room temperature to obtain the flame retardant filler P3.
Application example 3
19 parts of flame retardant filler P3 is added into 81 parts of Polyethylene (PE), stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain PE composite material X3.
The twin-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first temperature area is 120 ℃, the temperature of the second temperature area is 180 ℃, the temperature of the third temperature area is 180 ℃, the temperature of the fourth temperature area is 180 ℃, the temperature of the fifth temperature area is 180 ℃, the temperature of the sixth temperature area is 180 ℃, the temperature of the head of the twin-screw extruder is 180 ℃, and the screw rotating speed is 300r/min.
Comparative example 3
And taking 81 parts of PE, stirring for 10min by a high-speed mixer, and then adding the PE into a double-screw extruder for blending extrusion to obtain the PE composite material D3.
The performance data of the PE composite material prepared in the above application example 3 and comparative example 3 are shown in the following table:
| test item | Test standard | X3 | D3 |
| Flame retardant rating (1.6 mm) | UL94 | V-0 | Non-conforming V-level decision |
As can be seen from the above table, the flame retardant property of X3 is better than that of D3, which indicates that the flame retardant property of PE is better after the flame retardant filler is added.
Preparation example 4
(1) 25g of dioctadecyl dimethyl ammonium bromide, 280g of tetra-n-butyl titanate, 2.3kg of deionized water and 380g of phosphoric acid solution are weighed and put into a reaction vessel to react for 8 hours at room temperature, so as to obtain solution A;
(2) Weighing 950g of solution A and 280g of phosphomolybdic acid solution, and putting the solution A and the solution into a reaction vessel to react for 26 hours at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 340 ℃ for 5 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain a titanium dioxide-loaded phosphomolybdic acid flame retardant;
(5) 260g of boehmite with the particle size of 440nm, 440g of tri (chloroisopropyl) phosphate and 110g of titanium dioxide-loaded phosphomolybdic acid flame retardant are weighed, fully mixed in a high-speed mixer with the rotating speed of 230r/min, stirred for 45min, and cooled to room temperature, so as to obtain the flame retardant filler P4.
Application example 4
10 parts of flame retardant filler P4 is added into 90 parts of polyamide 6 (PA 6), stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain PA6 composite material X4.
The twin-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first temperature area is 200 ℃, the temperature of the second temperature area is 230 ℃, the temperature of the third temperature area is 230 ℃, the temperature of the fourth temperature area is 230 ℃, the temperature of the fifth temperature area is 230 ℃, the temperature of the sixth temperature area is 230 ℃, the temperature of the head of the twin-screw extruder is 230 ℃, and the screw rotating speed is 320r/min.
Comparative example 4
90 parts of PA6 are taken and stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain PA6 composite material D4.
Comparative example 5
10 parts of titanium dioxide loaded phosphomolybdic acid flame retardant is added into 90 parts of PA6, stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain PA6 composite material D5.
The performance data of the PA6 composites prepared in application example 4 and comparative examples 4 and 5 are shown in the following table:
| test item | Test standard | X4 | D4 | D5 |
| Flame retardant rating (1.6 mm) | UL94 | V-0 | V-2 | V-1 |
As can be seen from the table, the flame retardant property of X4 is better than that of D4 and also better than that of D5, which shows that after the flame retardant filler is added, the flame retardant property of the PA6 composite material X4 is obviously improved, and is better than that of the PA6 composite material D5 added with a single flame retardant.
Preparation example 5
(1) 22g of dioctadecyl dimethyl ammonium bromide, 290g of tetra-n-butyl titanate, 2.4kg of deionized water and 390g of phosphoric acid solution are weighed, and put into a reaction vessel to react for 7 hours at room temperature to obtain solution A;
(2) 880g of solution A and 290g of phosphomolybdic acid solution are weighed and put into a reaction vessel to react for 21 hours at room temperature, so as to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 350 ℃ for 5 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain a titanium dioxide-loaded phosphomolybdic acid flame retardant;
(5) 290g of boehmite with the particle size of 460nm, 480g of tri (chloroisopropyl) phosphate and 150g of titanium dioxide-loaded phosphomolybdic acid flame retardant are weighed, fully mixed for 45min in a high-speed stirrer with the rotating speed of 260r/min, and cooled to room temperature, so as to obtain the flame retardant filler P5.
Application example 5
18 parts of flame retardant filler P5 is added into 82 Parts of Styrene (PS), stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain the PS composite material X5.
The twin-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first temperature area is 160 ℃, the temperature of the second temperature area is 200 ℃, the temperature of the third temperature area is 200 ℃, the temperature of the fourth temperature area is 200 ℃, the temperature of the fifth temperature area is 200 ℃, the temperature of the sixth temperature area is 200 ℃, the temperature of the head of the twin-screw extruder is 200 ℃, and the screw rotating speed is 280r/min.
Comparative example 6
82 parts of PS is taken, stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain the PS composite material D6.
Comparative example 7
18 parts of tri (chloroisopropyl) phosphate is added into 82 Parts of Styrene (PS), stirred for 10min by a high-speed mixer, and then added into a double-screw extruder for blending extrusion, so as to obtain PS composite material D7.
The performance data of PS composites prepared in the above application example 5 and comparative example 6, comparative example 7 are shown in the following table:
| test item | Test standard | X5 | D6 | D7 |
| Flame retardant rating (1).6mm) | UL94 | V-0 | Non-conforming V-level decision | V-1 |
As can be seen from the table, the flame retardant property of X5 is better than that of D6 and D7, which shows that the flame retardant property of PS composite material X5 is better when the flame retardant filler is added into styrene.
Therefore, the application describes a flame-retardant filler and a preparation method thereof, and the polymer material prepared by the flame-retardant filler has a great significance in improving the flame-retardant property to a certain extent.
The above disclosure is only a few specific embodiments of the present application, but the present application is not limited thereto, and any changes that can be thought by those skilled in the art should fall within the protection scope of the present application.
Claims (7)
1. A flame retardant filler, characterized by: the composite material is prepared from the following components in percentage by mass: the mass ratio of boehmite, tri (chloroisopropyl) phosphate and titanium dioxide loaded phosphomolybdic acid flame retardant is (20-30): (40-60): (10-16);
the titanium dioxide loaded phosphomolybdic acid flame retardant is prepared by the following steps: firstly, mixing dioctadecyl dimethyl ammonium bromide, tetrabutyl titanate, deionized water and phosphoric acid solution for reaction, then adding phosphomolybdic acid solution for continuous reaction, and then drying reactants and calcining in a muffle furnace to obtain the catalyst;
the preparation method of the flame-retardant filler comprises the following steps:
(1) Putting dioctadecyl dimethyl ammonium bromide, tetrabutyl titanate, deionized water and phosphoric acid solution into a reaction vessel for reaction for 6-8h at room temperature to obtain solution A;
(2) Adding phosphomolybdic acid solution, and reacting for 20-28h at room temperature to obtain solution B;
(3) Filtering, washing and drying the solution B to obtain a solid C;
(4) Calcining the solid C in a muffle furnace at a high temperature of 300-360 ℃ for 5-7 hours, cooling, grinding and sieving with a 500-mesh sieve to obtain the titanium dioxide-loaded phosphomolybdic acid flame retardant with the particle size of not more than 25 mu m;
(5) And (3) fully mixing boehmite, tri (chloroisopropyl) phosphate and titanium dioxide loaded phosphomolybdic acid flame retardant in a high-speed stirrer, and cooling to room temperature to obtain the flame retardant filler.
2. The flame retardant filler of claim 1, wherein: the particle size of the boehmite is 400-480nm.
3. The flame retardant filler of claim 1, wherein: the mass ratio of dioctadecyl dimethyl ammonium bromide, tetra-n-butyl titanate, deionized water and phosphoric acid solution in the step (1) is (1-3): (20-30): (200-240): (30-40).
4. The flame retardant filler of claim 1, wherein: the mass ratio of the solution A to the phosphomolybdic acid solution in the step (2) is (80-100): (20-30).
5. The flame retardant filler of claim 1, wherein: the mass ratio of the boehmite, the tri (chloroisopropyl) phosphate and the titanium dioxide loaded phosphomolybdic acid flame retardant in the step (5) is (20-30): (40-60): (10-16), the rotating speed of the high-speed stirrer is 200-280r/min, and the stirring time is 40-60min.
6. A flame retardant polymer, characterized by: the flame-retardant polymer comprises a matrix resin and the flame-retardant filler according to any one of claims 1 to 5, wherein the amount of the flame-retardant filler is 10 to 20 percent of the total mass of the flame-retardant polymer.
7. The flame retardant polymer according to claim 6, wherein: the matrix resin is one of polyethylene, polypropylene, polystyrene, polybutylene terephthalate and polyamide 6.
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| CN113861553B (en) * | 2021-09-07 | 2023-08-08 | 江西华立源锂能科技股份有限公司 | High-flame-retardance polypropylene composite material for lithium battery shell |
| CN114316372A (en) * | 2021-12-30 | 2022-04-12 | 蚌埠壹石通聚合物复合材料有限公司 | Smoke suppressant and preparation method thereof |
| CN116120637A (en) * | 2023-03-14 | 2023-05-16 | 中国科学院长春应用化学研究所 | Composite flame retardant, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003292819A (en) * | 2002-04-05 | 2003-10-15 | Kawai Sekkai Kogyo Kk | Flame-retardant filler |
| CN102633282A (en) * | 2012-05-14 | 2012-08-15 | 哈尔滨工业大学 | Method for preparing mesoporous titanium silicon molecular sieve nanoparticles |
| CN108822506A (en) * | 2018-07-18 | 2018-11-16 | 安徽江淮汽车集团股份有限公司 | A kind of heat conductive flame-retarding PET composite material and preparation method thereof |
| CN109232990A (en) * | 2018-07-18 | 2019-01-18 | 安徽江淮汽车集团股份有限公司 | A kind of heat conductive flame-retarding compounded mix and preparation method thereof |
| CN109294155A (en) * | 2018-09-20 | 2019-02-01 | 安徽江淮汽车集团股份有限公司 | A kind of low VOC flame-proof abrasion-resistant ABS composite material and preparation method thereof |
| CN109503027A (en) * | 2018-10-22 | 2019-03-22 | 东莞理工学院 | A kind of anti-flaming transparent concrete |
-
2019
- 2019-10-29 CN CN201911040050.1A patent/CN112745525B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003292819A (en) * | 2002-04-05 | 2003-10-15 | Kawai Sekkai Kogyo Kk | Flame-retardant filler |
| CN102633282A (en) * | 2012-05-14 | 2012-08-15 | 哈尔滨工业大学 | Method for preparing mesoporous titanium silicon molecular sieve nanoparticles |
| CN108822506A (en) * | 2018-07-18 | 2018-11-16 | 安徽江淮汽车集团股份有限公司 | A kind of heat conductive flame-retarding PET composite material and preparation method thereof |
| CN109232990A (en) * | 2018-07-18 | 2019-01-18 | 安徽江淮汽车集团股份有限公司 | A kind of heat conductive flame-retarding compounded mix and preparation method thereof |
| CN109294155A (en) * | 2018-09-20 | 2019-02-01 | 安徽江淮汽车集团股份有限公司 | A kind of low VOC flame-proof abrasion-resistant ABS composite material and preparation method thereof |
| CN109503027A (en) * | 2018-10-22 | 2019-03-22 | 东莞理工学院 | A kind of anti-flaming transparent concrete |
Non-Patent Citations (1)
| Title |
|---|
| 赵利."功能化空心玻璃微珠阻燃TPU的作用机理研究".《工程科技I辑》.2017,第26-41页. * |
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