CN115716985A - Halogen-free flame-retardant polyurethane elastomer and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of polyurethane, in particular to a halogen-free flame retardant polyurethane elastomer and a preparation method thereof, wherein the halogen-free flame retardant polyurethane elastomer is obtained by melting and mixing a thermoplastic polyurethane elastomer, modified ammonium polyphosphate, cerium oxide-boron nitride nanosheets and an antioxidant, the flame retardance and low smoke characteristics of the material are improved on the basis of ensuring the mechanical properties of the material, and meanwhile, as the added flame retardant does not contain halogen and heavy metal elements such as lead, cadmium, mercury, chromium and the like, the halogen-free flame retardant polyurethane elastomer meets the halogen-free environment-friendly requirement, is safe and environment-friendly, is harmless to the environment, reaches the V-0 level in vertical combustion level and the limiting oxygen index of 31 percent, and the mechanical properties are improved relative to those of a pure polyurethane elastomer.
Description
Technical Field
The invention relates to the field of polyurethane, in particular to a halogen-free flame-retardant polyurethane elastomer and a preparation method thereof.
Background
Thermoplastic polyurethane is widely applied to a plurality of fields such as cables, automobiles, aerospace and the like due to the characteristics of excellent wear resistance, high mechanical property, ozone resistance, radiation resistance, obvious low-temperature flexibility, good biocompatibility and the like. However, pure thermoplastic polyurethane is easy to burn, and during the burning process, serious droplet phenomena exist, and meanwhile, a great amount of smoke toxicity (especially carbon monoxide and nitric oxide) is generated, so that the life safety of people is seriously threatened, and the wide application of the pure thermoplastic polyurethane is greatly limited. Therefore, the development of highly effective flame retardant thermoplastic polyurethane based composite materials is of great importance.
Halogen-containing flame retardants have been widely used for a long time. Although good flame retardant effect is achieved, the irritant and corrosive hydrogen halide gas generated during combustion severely harms the environment and human health. Therefore, the development of a flame retardant with high efficiency, no halogen, no toxicity and low smoke is urgently needed. At present, in the field of halogen-free flame retardants, there are two ways to improve the flame retardant performance of thermoplastic polyurethane, namely, an additive flame retardant and a reactive flame retardant, especially, the additive flame retardant, which has the advantages of wide sources, simple synthesis process and high flame retardant efficiency. Among them, ammonium polyphosphate and its derivatives are most widely used because of its excellent flame retardant properties, low smoke and no generation of corrosive gases (ammonia, water, etc.), and at the same time, through the catalytic action of the generated phosphoric acid, an expanding and continuous carbon structure is formed on the surface of the material, which is beneficial to heat insulation, oxygen isolation, smoke suppression and drip prevention.
Indian patent IN2013DN05373A discloses a flame retardant composition for thermoplastic polyurethane polymers comprising i) at least one metal or metalloid oxide particle selected from magnesium oxide, magnesium hydroxide, silica or alumina; ii) at least one phosphate component selected from ammonium polyphosphate, melamine phosphate, melamine pyrophosphate and melamine polyphosphate or mixtures thereof, and iii) at least one oligomeric phosphate. In some embodiments, a large amount of ammonium polyphosphate is added to achieve good flame retardancy, which necessarily results in a reduction in the mechanical properties of the thermoplastic polyurethane.
Chinese patent CN113278276B discloses a preparation method of a high-flame-retardant polyurethane composite material, which comprises the steps of controlling the temperature of an internal mixer at 175-185 ℃, adding a thermoplastic polyurethane elastomer, melting, adding chitosan, modified ammonium polyphosphate, a flame-retardant synergist, aramid fiber, 1-ethyl-3-methylimidazole hexafluorophosphate and a composite filler, blending, taking out, and performing compression molding to obtain the polyurethane composite material. Although flame-retardant silicon, nitrogen, phosphorus and the like are introduced into ammonium polyphosphate through modification, the process is complex, a large amount of organic reactions are involved, and the ammonium polyphosphate is not suitable for industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a halogen-free flame-retardant polyurethane elastomer, the vertical combustion grade of which reaches V0 grade, the limiting oxygen index of which reaches 31 percent, and the mechanical property of which is improved compared with that of a pure polyurethane elastomer.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a halogen-free flame retardant polyurethane elastomer, which comprises the following components in parts by weight: 60-90 parts of thermoplastic polyurethane elastomer, 5-10 parts of modified ammonium polyphosphate, 1-3 parts of boron nitride loaded with cerium oxide and 0.1-1 part of antioxidant.
Further, the thermoplastic polyurethane elastomer is a polyester type thermoplastic polyurethane elastomer or a polyether type thermoplastic polyurethane elastomer.
Further, the modified ammonium polyphosphate is prepared from glutamic acid and ammonium polyphosphate by ion exchange.
Further, the cerium oxide-boron nitride nanosheets are formed by hydrothermal reaction of cerium nitrate and boron nitride nanosheets.
Further, the antioxidant is one of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester, triethylene glycol bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 2, 6-di-tert-butyl-4-methylphenol and 2, 6-di-tert-butyl-p-cresol.
In a second aspect, the invention provides a preparation method of the halogen-free flame retardant polyurethane elastomer, which comprises the following steps:
(1) Adding ammonium polyphosphate into a mixed solvent consisting of ethanol and deionized water, adding glutamic acid, performing ion exchange, washing and drying to obtain modified ammonium polyphosphate;
(2) Adding boron nitride nanosheets, cerium nitrate and hexadecyl trimethyl ammonium bromide into deionized water, mechanically stirring and ultrasonically treating for 30-50min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, carrying out hydrothermal reaction, washing and drying after the reaction is finished, and thus obtaining cerium oxide-boron nitride nanosheets;
(3) Adding a thermoplastic polyurethane elastomer, modified ammonium polyphosphate, cerium oxide-boron nitride nanosheets and an antioxidant into a stirring pot, and mixing for 1-3min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 150-165 ℃ and the screw rotation speed at 200-280 r/min, and carrying out melt extrusion, granulation and drying to obtain the halogen-free flame-retardant polyurethane elastomer.
Further, the weight part ratio of the ammonium polyphosphate, the glutamic acid, the ethanol and the deionized water in the step (1) is 10: 4-6: 80-120: 3-8.
Further, the ion exchange conditions in the step (1) are as follows: keeping at 80-90 deg.C for 3-4h.
Further, the weight part ratio of the boron nitride nanosheet, the cerium nitrate, the hexadecyl trimethyl ammonium bromide and the deionized water in the step (2) is 10: 50-70: 1.5-2: 300-500.
Further, the conditions of the hydrothermal reaction in the step (2) are as follows: reacting for 24-30h at 180-190 ℃.
Compared with the prior art, the method has the beneficial effects that:
(1) The halogen-free flame-retardant polyurethane elastomer is obtained by melting and mixing the thermoplastic polyurethane elastomer, the modified ammonium polyphosphate, the cerium oxide-boron nitride nanosheets and the antioxidant, the flame retardance and the low-smoke characteristic of the material are improved on the basis of ensuring the mechanical property of the material, and meanwhile, the flame retardant added in the invention does not contain halogen and heavy metal elements such as lead, cadmium, mercury, chromium and the like, so that the halogen-free flame-retardant polyurethane elastomer meets the halogen-free environment-friendly requirement, is safe and environment-friendly, is harmless to the environment, has the vertical combustion grade reaching V-0 grade, has the limiting oxygen index reaching 31 percent, and has the mechanical property improved relative to a pure polyurethane elastomer.
(2) According to the halogen-free flame retardant polyurethane elastomer and the preparation method thereof, the modified ammonium polyphosphate is prepared by ion exchange of glutamic acid and ammonium polyphosphate, the glutamic acid is used as an effective carbon source, and the carbon forming capability of the modified ammonium polyphosphate is remarkably improved. Glutamic acid promotes to form a carbon layer with a remarkable expansion structure and a higher carbonization degree, and the boron nitride nanosheets in the cerium oxide-boron nitride nanosheets have a physical barrier effect, so that the flame retardant capability of thermoplastic polyurethane can be further improved, and meanwhile, cerium oxide has a catalytic effect, so that the formation of the carbon layer can be promoted, and the dripping phenomenon in the combustion process can be reduced.
(3) According to the halogen-free flame retardant polyurethane elastomer and the preparation method thereof, the preparation method is simple in process, the preparation process is easy to operate, the practical application value is high, the environment is friendly, the production efficiency is high, the prepared product is good in stability, and the halogen-free flame retardant polyurethane elastomer is suitable for industrial large-scale production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheets, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, washing and drying after the reaction is finished, and obtaining cerium oxide-boron nitride nanosheets;
(3) Adding 75 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of eastern aster and lark), 7 parts of modified ammonium polyphosphate, 2 parts of cerium oxide-boron nitride nanosheets and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Example 2
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheet, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, and washing and drying after the reaction is finished to obtain cerium oxide-boron nitride nanosheet;
(3) Adding 75 parts of polyether type thermoplastic polyurethane elastomer (65A, a new Dongwan lark material), 7 parts of modified ammonium polyphosphate, 2 parts of cerium oxide-boron nitride nanosheet and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Example 3
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheets, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, washing and drying after the reaction is finished, and obtaining cerium oxide-boron nitride nanosheets;
(3) Adding 60 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of Dongyuan lark), 5 parts of modified ammonium polyphosphate, 1 part of cerium oxide-boron nitride nanosheet and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol into a stirring pot, and mixing for 1min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 150 ℃, carrying out melt extrusion under the condition that the screw rotation speed is 200 r/min, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Example 4
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheet, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, and washing and drying after the reaction is finished to obtain cerium oxide-boron nitride nanosheet;
(3) Adding 90 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of eastern aster and lark), 10 parts of modified ammonium polyphosphate, 3 parts of cerium oxide-boron nitride nanosheet and 1 part of 2, 6-di-tert-butyl-p-cresol into a stirring pot, and mixing for 3min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 165 ℃ and the screw rotation speed at 280 rpm, melting and extruding, and granulating and drying to obtain the halogen-free flame-retardant polyurethane elastomer.
Example 5
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheet, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, and washing and drying after the reaction is finished to obtain cerium oxide-boron nitride nanosheet;
(3) Adding 75 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of Dongwan lark), 5 parts of modified ammonium polyphosphate, 2 parts of cerium oxide-boron nitride nanosheets and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Example 6
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water to obtain a suspension, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 10 parts of boron nitride nanosheet, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, and washing and drying after the reaction is finished to obtain cerium oxide-boron nitride nanosheet;
(3) Adding 75 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of Dongwan lark), 10 parts of modified ammonium polyphosphate, 2 parts of cerium oxide-boron nitride nanosheets and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Comparative example 1
(1) Adding 10 parts of boron nitride nanosheet, 60 parts of cerium nitrate and 1.7 parts of hexadecyl trimethyl ammonium bromide into 400 parts of deionized water, mechanically stirring and ultrasonically treating for 40min, then adjusting the pH to 10 by using ammonia water, transferring into a stainless steel autoclave with a Teflon lining, reacting for 27h at 185 ℃, and washing and drying after the reaction is finished to obtain cerium oxide-boron nitride nanosheet;
(2) Adding 75 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of Dongwan lark), 7 parts of ammonium polyphosphate, 2 parts of cerium oxide-boron nitride nanosheets and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(3) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Comparative example 2
(1) Adding 10 parts of ammonium polyphosphate into a mixed solvent consisting of 100 parts of ethanol and 5 parts of deionized water, dissolving 50 parts of glutamic acid into the suspension, performing ion exchange, keeping the solution at 85 ℃ for 4 hours, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding 75 parts of thermal polyester type thermoplastic polyurethane elastomer (85A, a new material of Dongwan lark), 7 parts of modified ammonium polyphosphate and 0.5 part of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester into a stirring pot, and mixing for 2min to form a premix;
(3) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 160 ℃, carrying out melt extrusion under the condition that the rotating speed of the screws is 240 revolutions per minute, and carrying out granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
Examples 1-6 and comparative examples 1, 2 were subjected to performance tests:
the tensile property and elongation at break of the TPU are tested according to GB/T528-2009, the vertical burning of the TPU is tested according to GB/T2408-2021, and the limiting oxygen index of the TPU is tested according to GB/T2406.2-2008.
TABLE 1 flame retardance and mechanical Properties of polyurethane elastomers prepared in examples 1-6 and comparative examples 1 and 2
The data above show that:
the halogen-free flame-retardant polyurethane elastomer prepared in the examples 1 to 6 has a vertical combustion level of V0, a limiting oxygen index of 31% and improved mechanical properties compared with pure polyurethane elastomers, and compared with the conventional ammonium polyphosphate in the example 1 and the comparative examples 1 and 2, the modified ammonium polyphosphate has obviously improved mechanical properties and flame retardant properties compared with the conventional ammonium polyphosphate, and the cerium oxide-boron nitride nanosheet and the modified ammonium polyphosphate have a synergistic flame retardant effect.
The present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make various modifications without creative efforts from the above-described conception, and fall within the scope of the present invention.
Claims (8)
1. The halogen-free flame-retardant polyurethane elastomer is characterized by comprising the following components in parts by weight: 60-90 parts of thermoplastic polyurethane elastomer, 5-10 parts of modified ammonium polyphosphate, 1-3 parts of boron nitride loaded with cerium oxide and 0.1-1 part of antioxidant; the modified ammonium polyphosphate is prepared from glutamic acid and ammonium polyphosphate through ion exchange; the cerium oxide-boron nitride nanosheet is formed by performing hydrothermal reaction on cerium nitrate and the boron nitride nanosheet.
2. The halogen-free flame retardant polyurethane elastomer of claim 1, wherein the thermoplastic polyurethane elastomer is a polyester type thermoplastic polyurethane elastomer or a polyether type thermoplastic polyurethane elastomer.
3. The halogen-free flame retardant polyurethane elastomer according to claim 1, wherein the antioxidant is one of tetramethylene (3, 5-di-tert-butyl-4-hydroxy phenylpropionic acid) methyl ester, triethylene glycol bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 2, 6-di-tert-butyl-4-methylphenol, and 2, 6-di-tert-butyl-p-cresol.
4. A method for preparing the halogen-free flame retardant polyurethane elastomer according to any one of claims 1 to 3, comprising the steps of:
(1) Adding ammonium polyphosphate into a mixed solvent consisting of ethanol and deionized water, adding glutamic acid, performing ion exchange, and then washing and drying to obtain modified ammonium polyphosphate;
(2) Adding boron nitride nanosheets, cerium nitrate and hexadecyl trimethyl ammonium bromide into deionized water, mechanically stirring and ultrasonically treating for 30-50min, then adjusting the pH to 10 by using ammonia water, then transferring into a stainless steel autoclave with a Teflon lining, carrying out hydrothermal reaction, washing and drying after the reaction is finished, and thus obtaining cerium oxide-boron nitride nanosheets;
(3) Adding a thermoplastic polyurethane elastomer, modified ammonium polyphosphate, cerium oxide-boron nitride nanosheets and an antioxidant into a stirring pot, and mixing for 1-3min to form a premix;
(4) And (4) placing the premix in the step (3) into a double-screw extruder, controlling the temperature at 150-165 ℃ and the screw rotation speed at 200-280 r/min, and carrying out melt extrusion, granulation and drying to obtain the halogen-free flame retardant polyurethane elastomer.
5. The preparation method of the halogen-free flame retardant polyurethane elastomer according to claim 4, wherein the mass ratio of the ammonium polyphosphate, the glutamic acid, the ethanol and the deionized water in the step (1) is 10: 4-6: 80-120: 3-8.
6. The method for preparing the halogen-free flame retardant polyurethane elastomer according to claim 4, wherein the ion exchange conditions in the step (1) are as follows: keeping at 80-90 deg.C for 3-4h.
7. The preparation method of the halogen-free flame retardant polyurethane elastomer according to claim 4, wherein the mass ratio of the boron nitride nanosheets, the cerium nitrate, the cetyl trimethylammonium bromide and the deionized water in the step (2) is 10: 50-70: 1.5-2: 300-500.
8. The method for preparing the halogen-free flame retardant polyurethane elastomer according to claim 4, wherein the hydrothermal reaction conditions in the step (2) are as follows: reacting for 24-30h at 180-190 ℃.
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