CN114437535B - Flame-retardant environment-friendly polyurethane elastomer and preparation method thereof - Google Patents

Flame-retardant environment-friendly polyurethane elastomer and preparation method thereof Download PDF

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CN114437535B
CN114437535B CN202210295217.4A CN202210295217A CN114437535B CN 114437535 B CN114437535 B CN 114437535B CN 202210295217 A CN202210295217 A CN 202210295217A CN 114437535 B CN114437535 B CN 114437535B
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polyurethane elastomer
aluminum isopropoxide
ammonium polyphosphate
flame
tpu
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CN114437535A (en
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王超
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Shengding High Tech Materials Co ltd
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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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 belongs to the technical field of polyurethane elastomers, and particularly relates to a flame-retardant environment-friendly polyurethane elastomer and a preparation method thereof. Firstly preparing a thermoplastic polyurethane elastomer, then preparing an aluminum isopropoxide-sodium polyphosphate nano compound, and finally preparing a flame-retardant environment-friendly polyurethane elastomer. Compared with the prior art, the aluminum isopropoxide-sodium polyphosphate nano-composite flame retardant prepared from aluminum isopropoxide and sodium polyphosphate is added in the production process of the flame-retardant environment-friendly polyurethane elastomer, so that the problems that ammonium polyphosphate is poor in water resistance, organic matter miscibility is poor, flame retardance is low in a humid environment, the surface is smooth and flat, and stable interface connection between a polymer matrix and the particle surface is not facilitated are solved, the UL94V-0 grade is achieved, and better protective carbon can be formed to prevent melting and dripping.

Description

Flame-retardant environment-friendly polyurethane elastomer and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a flame-retardant environment-friendly polyurethane elastomer and a preparation method thereof.
Background
Thermoplastic polyurethane elastomers (TPU) are a class of polymeric materials that are characterized by both rubber elasticity and plastic rigidity. The polyurethane material is prepared by taking polymer polyol, diisocyanate, a chain extender, a cross-linking agent and a small amount of auxiliary agents as raw materials, wherein a molecular chain contains more carbamate groups (-NHCOO-). The thermoplastic elastomer has the characteristics of high strength, high toughness, oil resistance, wear resistance, good processability and the like, is widely applied to the industries of national defense, medical treatment, food and the like, and is one of important thermoplastic elastomer materials.
However, conventional TPUs still have the disadvantage that the Limiting Oxygen Index (LOI) of the conventional TPU is very low, namely about 19%, which makes the TPU flammable and extremely combustible, and the combustion process is accompanied by the release of smoke, toxic gases and a large amount of heat, and the generation of a melt dripping phenomenon can cause secondary ignition.
To solve the above problems, it is generally possible to add conventional flame retardants such as Al (OH) to the TPU 3 、Mg(OH) 2 However, these physical flame retardants have low flame retardant efficiency, large addition amount, poor compatibility, and greatly deteriorate the mechanical properties of TPU. Ammonium polyphosphate (APP) as a phosphorus-containing flame retardant contains abundant nitrogen and phosphorus elements, has the characteristics of low cost, low toxicity, good flame retardant effect and the like, and unfortunately, due to some defects of the APP, a P-N Intumescent Flame Retardant (IFR) system based on the APP is not sustainable, such as water resistance and organic matter miscibilityAnd a low flame retardancy in a humid environment. In addition, APP has low roughness, low interfacial force with polyurethane elastomers, and poor compatibility. Therefore, the flame-retardant environment-friendly polyurethane elastomer and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a flame-retardant environment-friendly polyurethane elastomer and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a flame-retardant environment-friendly polyurethane elastomer comprises the following steps:
s1, preparing a thermoplastic polyurethane elastomer;
s2, carrying out melt blending on the thermoplastic polyurethane elastomer and the flame retardant A, and carrying out compression molding and cooling to prepare a polyurethane elastomer sheet;
the flame retardant A comprises an aluminum isopropoxide-ammonium polyphosphate nano compound.
Further, the preparation method of the aluminum isopropoxide-ammonium polyphosphate nano compound comprises the following steps: firstly, adding ammonium polyphosphate into absolute ethyl alcohol to obtain an ammonium polyphosphate solution, and dissolving aluminum isopropoxide in isopropanol to obtain an aluminum isopropoxide solution; then adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating; adding water and stirring the solution at 80 ℃; and filtering the obtained product, washing the product with absolute ethyl alcohol, and drying to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Further, the flame retardant A also comprises decabromodiphenylethane and antimony trioxide.
Furthermore, the flame retardant A comprises, by mass, 17-23% of an aluminum isopropoxide-ammonium polyphosphate nano-composite, 52-64% of decabromodiphenylethane and 14-30% of antimony trioxide.
Further, the preparation method of the thermoplastic polyurethane elastomer comprises the following steps: heating and stirring polyether polyol in a reactor, performing vacuum dehydration, cooling, adding diisocyanate and a chain extender, stirring and heating, adding a catalyst and a lubricant, and uniformly mixing; controlling the isocyanate index to be 1.00-1.05, and adding the mixed materials into a double-screw extruder to prepare the thermoplastic polyurethane elastomer.
Further, the polyether polyol is polytetrahydrofuran diol with molecular weight of 2000; the diisocyanate is toluene diisocyanate or 4,4-diphenylmethane diisocyanate; the chain extender is 1,4-butanediol; the catalyst is CUCAT-DG01; the lubricant is polyethylene wax.
Furthermore, the polyurethane elastomer comprises the following raw materials in percentage by mass: 70-80% of polyether polyol, 15-20% of diisocyanate, 3-7% of chain extender, 0.1-0.5% of catalyst and 1.0-2.5% of lubricant.
The flame-retardant environment-friendly polyurethane elastomer prepared by the method.
According to the invention, a novel fire retardant aluminum isopropoxide-ammonium polyphosphate nano compound (NSAPP) is prepared by hydrolyzing Aluminum Isopropoxide (AIP) on ammonium polyphosphate (APP), and because a large amount of aluminum isopropoxide nano particles are arranged on the surface of the aluminum isopropoxide-ammonium polyphosphate nano compound, the aluminum isopropoxide-ammonium polyphosphate nano compound has a rough surface, the Water Contact Angle (WCA) of the aluminum isopropoxide-ammonium polyphosphate nano compound is improved, and the problem of poor water resistance of ammonium polyphosphate is improved. The aluminum isopropoxide-ammonium polyphosphate nano compound is coarser, so that the aluminum isopropoxide-ammonium polyphosphate nano compound is better miscible with a polyurethane elastomer, and the problems of poor miscibility and smooth surface of the traditional ammonium polyphosphate are solved. Because aluminum isopropoxide is attached to the surface of the aluminum isopropoxide-ammonium polyphosphate nano compound, in a humid environment, aluminum isopropoxide can be hydrolyzed to generate aluminum hydroxide which is attached to the rough surface of the aluminum isopropoxide-ammonium polyphosphate nano compound, the aluminum hydroxide is also a flame retardant, the flame retardance can be effectively realized, and the problem of low flame retardance of the traditional ammonium polyphosphate in the humid environment is solved.
In the invention, aluminum isopropoxide-ammonium polyphosphate nano compound (NSAPP), decabromodiphenylethane (DBDPE) and antimony trioxide (Sb) are added in the production process 2 O 3 ) The three flame retardants achieve a better flame retardant effect by utilizing the synergistic effect. Ten pieces of clothThe bromide diphenylethane can generate hard covering and HBr in the thermal decomposition process, aluminum hydroxide attached to the surface of the aluminum isopropoxide-ammonium polyphosphate nano compound generates aluminum oxide and water vapor in the thermal decomposition process, the aluminum oxide and the hard covering generated in the decabromide diphenylethane decomposition process are mixed to generate a synergistic effect, the condensation phase flame retardant, the char formation and the smoke suppression effects are realized, the water vapor and the HBr generated in the decabromide diphenylethane decomposition process are mixed to generate a synergistic effect, and the gas phase flame retardant effect is realized. The added antimony trioxide can be sublimated when being heated to bring a large amount of heat, and has the functions of heat absorption and temperature reduction. Because the aluminum isopropoxide-ammonium polyphosphate nano compound has a rougher surface than the traditional ammonium polyphosphate, the three flame retardants of the aluminum isopropoxide-ammonium polyphosphate nano compound, decabromodiphenylethane and antimony trioxide can be better dispersed in a polymer, so that the prepared flame-retardant environment-friendly polyurethane elastomer has better compatibility, thermal stability and flame retardance.
Compared with the prior art, the invention has the following beneficial effects: the aluminum isopropoxide-sodium polyphosphate nano-composite flame retardant prepared from aluminum isopropoxide and sodium polyphosphate is added in the production process of the polyurethane elastomer, so that the problems of poor water resistance, poor organic matter miscibility, low flame retardance in a humid environment and enhanced roughness of ammonium polyphosphate are solved, the interfacial force with the polyurethane elastomer is increased, the problem of poor compatibility is solved, the UL94V-0 grade is achieved, and better protective carbon is formed.
Detailed Description
The invention is further described with reference to specific examples.
Preparation of thermoplastic polyurethane elastomer: heating polyether polyol in a reactor, stirring to 100-110 ℃, carrying out vacuum dehydration for 1-2 h, cooling to 45-50 ℃, adding diisocyanate and a chain extender, stirring, heating, adding a catalyst and a lubricant, and uniformly mixing; by mass percent, evenly mixing 70-80 percent of polyether polyol, 15-20 percent of diisocyanate, 3-7 percent of chain extender, 0.1-0.5 percent of catalyst and 1.0-2.5 percent of lubricant, controlling the isocyanate index to be 1.00-1.05, adding the mixed materials into a double-screw extruder, heating and stirring, and reacting by the double-screw extruder to obtain the thermoplastic polyurethane elastomer particles.
Preparation of aluminum isopropoxide-ammonium polyphosphate Nanocomposite (NSAPP): firstly, 50-60 g of ammonium polyphosphate is added into 300-360 mL of absolute ethanol, and then aluminum isopropoxide is dissolved in 100mL of isopropanol. Adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25-30 min. 50-60 mL of distilled water is added into the solution, and the solution is stirred for 8-10 h at 80 ℃. Filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at the temperature of between 100 and 105 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Preparation of polyurethane elastomer: heating the torque rheometer to 170-180 ℃, wherein the rotating speed is 65-75 r/min, and adding the thermoplastic polyurethane elastomer and the flame retardant A into the torque rheometer according to a certain proportion for melt blending for 10-15 min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 170-190 ℃, keeping the pressure for 10-12 min at 8-10 MPa, then forming the TPU thin slice, and cooling at room temperature to obtain the TPU thin slice.
Example 1
Polytetrahydrofuran diol (PTMG 2000, M = 2000) is heated and stirred to 110 ℃, vacuum-pumping is carried out for dehydration for 1h, the temperature is reduced to 50 ℃, toluene Diisocyanate (TDI) and 1,4-Butanediol (BDO) are added, CUCAT-DG01 and polyethylene wax are added for uniform mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol, and then 2g of aluminum isopropoxide was dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 81.3g of the thermoplastic polyurethane elastomer and 18.7g of the aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure at 10MPa for 10min, forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 1.
Example 2
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Polytetrahydrofuran glycol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 81.3g of the thermoplastic polyurethane elastomer and 18.7g of the aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 1.
Example 3
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 6g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 81.3g of the thermoplastic polyurethane elastomer and 18.7g of the aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 1.
Example 4
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. Then 8g of aluminum isopropoxide was dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product by using absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 81.3g of the thermoplastic polyurethane elastomer and 18.7g of the aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure at 10MPa for 10min, forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 1.
Example 5
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 70g of thermoplastic polyurethane elastomer, 6.4g of decabromodiphenylethane, 19.2g of antimony trioxide and 4.4g of aluminum isopropoxide-ammonium polyphosphate nano compound into the mixture, and carrying out melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (4) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Example 6
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 70g of thermoplastic polyurethane elastomer, 6g of decabromodiphenylethane, 18g of antimony trioxide and 6g of aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Example 7
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 70g of thermoplastic polyurethane elastomer, 5.6g of decabromodiphenylethane, 16.8g of antimony trioxide and 7.6g of aluminum isopropoxide-ammonium polyphosphate nano compound into the mixture, and carrying out melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Example 8
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was maintained at 80 ℃ with stirring for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 70g of thermoplastic polyurethane elastomer, 5.2g of decabromodiphenylethane, 15.6g of antimony trioxide and 9.2g of aluminum isopropoxide-ammonium polyphosphate nano compound into the mixture, and carrying out melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Comparative example 1
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Polytetrahydrofuran glycol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Comparative example 2
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared through reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol, and then 4g of aluminum isopropoxide was dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 81.3g of the thermoplastic polyurethane elastomer and 18.7g of the aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (4) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Comparative example 3
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared through reaction of the double-screw extruder.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 77g of thermoplastic polyurethane elastomer, 5.7g of decabromodiphenylethane and 17.3g of antimony trioxide into the torque rheometer for melting and blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Comparative example 4
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared by the reaction of the double-screw extruder.
50g of ammonium polyphosphate was added to 300mL of absolute ethanol, and then 4g of aluminum isopropoxide was dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was maintained at 80 ℃ with stirring for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 83g of thermoplastic polyurethane elastomer, 6.1g of decabromodiphenylethane and 10.9g of aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
Comparative example 5
Heating polytetrahydrofuran diol (PTMG 2000, M = 2000), stirring to 110 ℃, vacuumizing and dehydrating for 1h, reducing the temperature to 50 ℃, adding toluene diisocyanate and 1,4-butanediol, adding CUCAT-DG01 and polyethylene wax, and uniformly mixing. Adding polytetrahydrofuran diol: 100g, toluene diisocyanate 19.2g:1,4 butanediol: 6.4g, CUCAT-DG01:0.5g, polyethylene wax: 2.0g of the mixture is uniformly mixed, the isocyanate index is controlled to be 1.03, the mixture is added into a double-screw extruder, heated and stirred, and the thermoplastic polyurethane elastomer particles are prepared through reaction of the double-screw extruder.
50g of ammonium polyphosphate (APP) was added to 300mL of absolute ethanol. 4g of aluminum isopropoxide was then dissolved in 100mL of isopropanol. And adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating to 80 ℃, and stirring for 25min. 50mL of distilled water was added and the solution was stirred at 80 ℃ for 8h. And filtering the obtained product, washing the product with absolute ethyl alcohol, and drying the product at 100 ℃ to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
Heating a torque rheometer to 180 ℃, adjusting the rotating speed to 70r/min, adding 73.8g of thermoplastic polyurethane elastomer, 16.4g of antimony trioxide and 9.8g of aluminum isopropoxide-ammonium polyphosphate nano compound into the torque rheometer to perform melt blending for 15min. And (3) carrying out compression molding by using a flat vulcanizing machine, setting the temperature of an upper template and a lower template to be 180 ℃, keeping the pressure for 10min at 10MPa, then forming the TPU slices, and cooling at room temperature to obtain the TPU slices.
And (3) performance testing: the tensile properties and elongation at break of the TPU were tested according to GB/T528-2009, the vertical burning of the TPU was tested according to GB/T2408-2021, and the oxygen index of the TPU was tested according to GB/T2406.2-2008. The combustion properties and mechanical properties are shown in Table 2.
TABLE 1 flame retardant property and mechanical property performance of polyurethane elastomers with different AIP dosages
Tensile Property/MPa Percentage of growth at break/%) UL-94 LOI/％
Example 1 23.8 12.1 Class V-1 28.7
Example 2 25.2 12.7 Class V-0 30.9
Example 3 25.3 13.6 Class V-0 29.6
Example 4 25.6 14.0 Class V-0 28.5
TABLE 2 flame retardant property and mechanical property performance of polyurethane elastomer with different flame retardant dosages
Tensile Property/MPa Percentage of growth at break/%) UL-94 LOI/％
Example 5 25.2 12.8 Class V-0 31.1
Example 6 25.6 13.2 Class V-0 31.8
Example 7 25.8 13.8 Class V-0 31.8
Example 8 26.2 14.1 Class V-0 31.3
Comparative example 1 19.8 11.8 Class V-2 19.2
Comparative example 2 25.2 12.7 Class V-0 30.9
Comparative example 3 20.7 12.1 Class V-0 22.8
Comparative example 4 22.7 12.6 Class V-0 24.2
Comparative example 5 22.9 12.6 Class V-0 26.1
And (4) conclusion: the flame-retardant environment-friendly polyurethane elastomer prepared by the examples 1-4 and the aluminum isopropoxide-ammonium polyphosphate nano compound prepared by using different aluminum isopropoxide dosages has good flame retardant property and mechanical property, the LOI is improved to 30.9%, and the UL94 is improved to the V-0 level.
Comparing the data of examples 5 to 8 with the data of comparative examples 1 to 5, it can be found that: in comparative example 1, no aluminum isopropoxide-ammonium polyphosphate nanocomposite, decabromodiphenylethane, and antimony trioxide were added, resulting in a decrease in performance due to: flame retardant is not added, so that the flame retardant is difficult to retard flame, suppress smoke and form carbon; comparative example 2, in which decabromodiphenylethane and antimony trioxide were not added, performance was decreased because: the hard covering generated by decomposition of the added decabromodiphenylethane enhances the smoke suppression and condensed phase flame retardant effect, HBr generated by decomposition enhances the gas phase flame retardant effect, and antimony trioxide enhances the heat absorption and temperature reduction effects; the aluminum isopropoxide-ammonium polyphosphate nanocomposite was not added in comparative example 3, resulting in a decrease in performance due to: the addition of the aluminum isopropoxide-ammonium polyphosphate nano compound enhances the dispersibility of the polyurethane elastomer, and enhances the water resistance and organic matter miscibility of the polyurethane elastomer; (ii) a In comparative example 4, antimony trioxide was not added, so that the performance was decreased because antimony trioxide enhances the heat absorption and temperature reduction effects of the polyurethane elastomer; in comparative example 5, decabromodiphenylethane was not added, so that the properties were degraded because: the addition of decabromodiphenylethane can raise smoke-inhibiting, condensed phase flame-retarding and gas phase flame-retarding effects.

Claims (7)

1. The preparation method of the flame-retardant environment-friendly polyurethane elastomer is characterized by comprising the following steps of:
s1, preparing a thermoplastic polyurethane elastomer;
s2, carrying out melt blending on the thermoplastic polyurethane elastomer and the flame retardant A, and carrying out compression molding and cooling to prepare a polyurethane elastomer sheet;
the flame retardant A comprises an aluminum isopropoxide-ammonium polyphosphate nano compound, decabromodiphenylethane and antimony trioxide.
2. The preparation method according to claim 1, wherein the aluminum isopropoxide-ammonium polyphosphate nano-composite is prepared by the following steps: firstly, adding ammonium polyphosphate into absolute ethyl alcohol to obtain an ammonium polyphosphate solution, and dissolving aluminum isopropoxide in isopropanol to obtain an aluminum isopropoxide solution; then adding the aluminum isopropoxide solution into the ammonium polyphosphate solution, stirring and heating; adding water and stirring the solution at 80 ℃; and filtering the obtained product, washing the product with absolute ethyl alcohol, and drying to obtain the aluminum isopropoxide-ammonium polyphosphate nano compound.
3. The preparation method according to claim 1, wherein the flame retardant A comprises, by mass, 17-23% of an aluminum isopropoxide-ammonium polyphosphate nanocomposite, 52-64% of decabromodiphenylethane, and 14-30% of antimony trioxide.
4. The method for preparing the thermoplastic polyurethane elastomer according to claim 1, wherein the thermoplastic polyurethane elastomer is prepared by: heating polyether polyol in a reactor, stirring, performing vacuum dehydration, cooling, adding diisocyanate and a chain extender, stirring, heating, adding a catalyst and a lubricant, and uniformly mixing; controlling the isocyanate index to be 1.00-1.05, and adding the mixed materials into a double-screw extruder to prepare the thermoplastic polyurethane elastomer.
5. The method according to claim 4, wherein the polyether polyol is polytetrahydrofuran glycol having a molecular weight of 2000; the diisocyanate is toluene diisocyanate or 4,4-diphenylmethane diisocyanate; the chain extender is 1,4-butanediol; the catalyst is CUCAT-DG01; the lubricant is polyethylene wax.
6. The preparation method of the polyurethane elastomer according to claim 4, wherein the raw materials of the polyurethane elastomer are as follows by mass percent: 70-80% of polyether polyol, 15-20% of diisocyanate, 3-7% of chain extender, 0.1-0.5% of catalyst and 1.0-2.5% of lubricant.
7. The flame-retardant environment-friendly polyurethane elastomer prepared by the method according to any one of claims 1 to 6.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001234082A (en) * 1999-08-03 2001-08-28 Ishizuka Glass Co Ltd Method for producing flame-retardant polymeric- composite material and molded material of flameretardant polymeric composite material
CN101608060A (en) * 2009-07-09 2009-12-23 中国科学技术大学 Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and method for making thereof
CN105111837A (en) * 2015-08-13 2015-12-02 蚌埠南自仪表有限公司 Flame-retardant heat-dissipation paint and preparation method therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001234082A (en) * 1999-08-03 2001-08-28 Ishizuka Glass Co Ltd Method for producing flame-retardant polymeric- composite material and molded material of flameretardant polymeric composite material
CN101608060A (en) * 2009-07-09 2009-12-23 中国科学技术大学 Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and method for making thereof
CN105111837A (en) * 2015-08-13 2015-12-02 蚌埠南自仪表有限公司 Flame-retardant heat-dissipation paint and preparation method therefor

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