CN111440433A - Halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermoplastic polyurethane elastomer composite materials, and particularly relates to a halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material which comprises the following components in percentage by weight: 60% -90% of thermoplastic polyurethane elastomer; 10 to 35 percent of smoke suppressant wraps the hypophosphite (phosphonate) fire retardant; 1-3% of an anti-dripping agent; 0.1-1.5% of antioxidant; 0.1-1.5% of a lubricant; the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material prepared by the invention has a series of characteristics of high flame retardant property, small smoke generation amount, anti-dripping property, excellent mechanical property and the like through the synergistic effect of the hypophosphite flame retardant, the shell-layer hydroxyl stannate smoke inhibitor and the anti-dripping agent. In addition, the invention also discloses a preparation method of the halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomer composite materials, and particularly relates to a halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material.
Background
The thermoplastic polyurethane elastomer has the advantages of low density, corrosion resistance, strong flexibility, easy processing, high cost performance and the like, and is widely used in the fields of electronic and electric appliances, buildings, wires and cables, transportation and the like; the thermoplastic elastomer material has good mechanical property, chemical resistance and high cohesiveness on one hand, and can be processed by injection molding, calendering, extrusion, solution dissolution and the like on the other hand, and is the most common thermoplastic elastomer material in the plastic processing industry.
However, the thermoplastic polyurethane elastomer is rich in carbon, hydrogen, oxygen and nitrogen as an organic material, and has the following disadvantages: firstly, the flame is easy to burn, and simultaneously, the flame is easy to cause secondary ignition along with obvious melting and dripping, so that serious fire hazard is caused; secondly, a large amount of toxic smoke can be released in the combustion process of the thermoplastic polyurethane material, and serious harm is caused to personnel on the fire scene; the defects seriously restrict the use of the thermoplastic polyurethane elastomer material in the fields of electronics, buildings, wires and cables, transportation and the like; therefore, the polyurethane elastomer is modified to prepare the flame-retardant, smoke-inhibiting and anti-dripping polyurethane elastomer composite material, so that the use of the composite material in related fields can be effectively expanded, and the composite material has great economic and social values.
At present, the conventional halogen-containing flame retardant has adverse effects on human health and the surrounding environment due to the release of a large amount of corrosive hydrogen halide gas in the combustion process and the generation of carcinogenic dioxin substances, and is not in accordance with the current development concept of green environmental protection. Heretofore, the european union issued two instructions in 2003: the electronic appliance control method comprises the following steps of 'scrap electronic appliance instruction' (WEEE) and 'instruction about forbidding harmful substances in the electronic appliance' (RoHs), and forbidding adding the harmful substances such as polybrominated diphenyl ethers and the like in the electronic appliance; therefore, halogen-free flame retardance is an inevitable choice for the development of flame retardant technology.
At present, the commonly used halogen-free flame retardant for the thermoplastic polyurethane elastomer material mainly comprises a metal hydroxide flame retardant and a phosphorus-nitrogen compound flame retardant; the metal hydroxide flame retardant generally needs a very high addition amount (30 wt% -60 wt%) to achieve a good flame retardant property, and the high addition amount often causes severe deterioration of the mechanical property of the thermoplastic polyurethane elastomer material, so that the metal hydroxide flame retardant is not suitable for flame retardation of the thermoplastic polyurethane elastomer; the phosphorus-nitrogen compound flame retardant has the advantages of low addition amount, high flame retardant efficiency and good char formation, but has the defect of poor compatibility with the thermoplastic polyurethane elastomer, and simultaneously, the toxic smoke release in the combustion process of the thermoplastic polyurethane elastomer material is obviously increased.
The novel hypophosphite (phosphonate) flame retardant has the advantages of low addition amount, high flame retardant efficiency, strong char formation and the like; the aluminum hypophosphite flame-retardant thermoplastic polyurethane elastomer composite material is reported in the journal of China Polymer Science (Chinese Polymer Science, 2014, 32 vol., No. 1, 275 page 285), and the aluminum hypophosphite is found to effectively promote the formation of carbon in the combustion process of the thermoplastic polyurethane elastomer composite material, so that the flame-retardant property of the thermoplastic polyurethane elastomer composite material is obviously improved, and the heat release in the combustion process of the thermoplastic polyurethane elastomer composite material is reduced.
However, the thermoplastic polyurethane elastomer material has no effective smoke suppression effect, and the melting and dropping in the combustion process are still obvious; currently, molybdate, iron-containing compounds, metal oxides and other smoke inhibitors are generally adopted in the industry to be compounded with hypophosphorous acid (phosphonate); because the smoke suppressant particles and the flame retardant particles are randomly distributed in the thermoplastic polyurethane elastomer matrix, the interaction efficiency is lower, and the smoke suppression effect is poorer; the smoke suppressant and the hypophosphite flame retardant are effectively contacted to form a special core-shell structure, so that the smoke suppressant effect can be improved, and meanwhile, the core-shell structure is beneficial to the flame-retardant synergistic effect between the smoke suppressant and the flame retardant, and the flame-retardant efficiency is improved.
Disclosure of Invention
Aiming at the defects of low flame-retardant efficiency, poor anti-dripping performance and poor smoke suppression performance of the conventional flame-retardant thermoplastic polyurethane elastomer, the invention aims to provide a halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material and a preparation method thereof; the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material has good flame retardant property, smoke inhibiting property, anti-dripping property and mechanical property.
In order to achieve the purpose, the invention adopts the technical scheme that:
the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material is characterized by comprising the following components in percentage by weight:
the thermoplastic polyurethane elastomer is at least one of polyether type thermoplastic polyurethane elastomer and polyester type thermoplastic polyurethane elastomer.
The anti-dropping agent is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoroethylene, polytetrafluoroethylene coated by styrene-acrylonitrile copolymer, polyvinylidene fluoride coated by styrene-acrylonitrile copolymer and polyhexafluoroethylene coated by styrene-acrylonitrile copolymer.
The antioxidant is at least one of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300), dilauryl thiodipropionate (antioxidant D L TP), pentaerythritol tetra (3-lauryl thiopropionate) (antioxidant S4P) and tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168).
The lubricant is at least one of zinc stearate, paraffin, PE wax and silicone powder.
The smoke suppressant coated hypophosphite (phosphonate) fire retardant is a coated fire retardant taking a smoke suppressant as a shell layer and hypophosphite (phosphonate) as a core material, and the smoke suppressant and the hypophosphite (phosphonate) are combined in a chemical bond form through a silane coupling agent.
The smoke suppressant wraps the hypophosphite (phosphonate) flame retardant and comprises the following raw materials in percentage by mass:
the phosphinate flame retardant is at least one of aluminum phosphinate, calcium phosphinate, zinc phosphinate, aluminum diethylphosphinate, zinc diethylphosphinate and calcium diethylphosphinate.
The smoke suppressant is at least one of zinc hydroxystannate, iron hydroxystannate, cobalt hydroxystannate, calcium hydroxystannate, magnesium hydroxystannate and copper hydroxystannate.
The silane coupling agent is at least one of gamma-aminopropyltrimethoxysilane (KH540), gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560) and gamma-methacryloxypropyltrimethoxysilane (KH 570).
In the silane coupling agent, 1-15 parts by mass are used for carrying out hydrolytic modification on hypophosphite (phosphonate), and 1-5 parts by mass are used for carrying out hydrolytic modification on the smoke suppressant.
The mixed solvent is obtained by mixing ethanol and distilled water according to the mass ratio of 4: 1.
The pH regulator is at least one of ammonia water solution, sodium carbonate solution, potassium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.
The preparation method of the smoke suppressant coated hypophosphite (phosphonate) fire retardant comprises the following steps:
step 1: adding 100 parts by mass of hypophosphite flame retardant into a three-necked bottle provided with a stirrer and a reflux condenser pipe at the temperature of 30-60 ℃, dispersing the hypophosphite flame retardant into 300 parts by mass of a mixed solvent, adding 1-15 parts by mass of a silane coupling agent, dropwise adding 0.1-7.5 parts by mass of a pH regulator to adjust the pH to 8-12, and carrying out heat preservation reaction for 2-8 hours after dropwise adding is finished to obtain a modified hypophosphite flame retardant suspension;
step 2: adding 0.5-20 parts by mass of smoke suppressant into a three-necked bottle provided with a stirrer and a reflux condenser pipe at the temperature of 30-60 ℃, dispersing the smoke suppressant into 100 parts by mass of mixed solvent, adding 1-5 parts by mass of silane coupling agent, dropwise adding 0.1-2.5 parts by mass of pH regulator to adjust the pH to 8-12, and carrying out heat preservation reaction for 2-8 hours after dropwise adding is finished to obtain modified smoke suppressant suspension;
and step 3: adding the modified smoke suppressant suspension obtained in the step 2 into the modified hypophosphite (phosphonate) suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 10-40 minutes, then heating to 75 ℃, and reacting for 2-8 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol and drying the mixed suspension to obtain the smoke suppressant-coated hypophosphite (phosphonate) flame retardant.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps: according to the weight percentage, 60 to 90 percent of thermoplastic polyurethane elastomer is mixed in an internal mixer or an extruder at the temperature of 165 plus 210 ℃ to be uniform, then 10 to 35 percent of smoke suppressant is added to wrap the hypophosphite flame retardant, 0.1 to 3 percent of anti-dripping agent, 0.1 to 1.5 percent of antioxidant and 0.1 to 1.5 percent of lubricant, and the mixture is mixed uniformly at the temperature of 165 plus 210 ℃ and then granulated to form the halogen-free flame-retardant smoke-suppressing anti-dripping thermoplastic polyurethane elastomer composite material.
The smoke inhibitor used in the invention wraps the hypophosphite flame retardant, so that the effective flame retardant effect of the hypophosphite is exerted, and the shell smoke inhibitor and the hypophosphite flame retardant have synergistic effect in various aspects of flame retardance, smoke inhibition and the like, so that the flame retardance and the smoke inhibition effect can be effectively improved.
The anti-dripping agent used in the invention can effectively interact with the smoke suppressant wrapped hypophosphite (phosphonate), and the anti-dripping effect is obviously improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention solves the problem of weak interaction between the smoke suppressant and the flame retardant, and improves the flame retardant efficiency while enhancing the smoke suppression effect through the synergistic effect between the shell smoke suppressant and the core material hypophosphite (phosphonate).
2. By adding the anti-dripping agent and the interaction between the anti-dripping agent and the smoke suppressant wrapped hypophosphite (phosphonate) flame retardant, the anti-dripping effect can be obviously improved.
3. The processing process is simplified, and the production efficiency is improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing the aluminum hypophosphite wrapped by the zinc hydroxystannate:
step 1: adding 100g of aluminum hypophosphite into a three-necked bottle provided with a stirrer and a reflux condenser pipe at 45 ℃, dispersing into 300g of a mixed solvent (obtained by mixing absolute ethyl alcohol and distilled water according to a mass ratio of 4:1, the same below), adding 10g of a silane coupling agent KH540, then dropwise adding 3g of a sodium carbonate solution to adjust the pH value to 10, and carrying out heat preservation reaction for 3 hours after dropwise adding is finished to obtain a modified aluminum hypophosphite suspension;
step 2: adding 15g of zinc hydroxystannate into a three-mouth bottle provided with a stirrer and a reflux condenser pipe at the temperature of 45 ℃, dispersing the zinc hydroxystannate into 100g of mixed solvent, adding 3g of silane coupling agent KH550, dropwise adding 0.8g of sodium carbonate solution to adjust the pH value to 10, and after dropwise adding, keeping the temperature and reacting for 3 hours to obtain modified zinc hydroxystannate suspension;
and step 3: adding the modified zinc hydroxystannate suspension obtained in the step 2 into the modified aluminum hypophosphite suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 20 minutes, then heating to 75 ℃, and reacting for 2 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol, and drying at 80 ℃ for 12 hours to obtain the zinc hydroxystannate-coated aluminum hypophosphite.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps:
according to the weight percentage, 83.5 percent of polyester type thermoplastic polyurethane elastomer is mixed evenly in an extruder at 185 ℃, then 15 percent of hydroxyl zinc stannate coated aluminum hypophosphite, 0.5 percent of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5 percent of dilauryl thiodipropionate (antioxidant D L TP) and 0.5 percent of silicone powder are added, and after even mixing at 195 ℃, the mixture is granulated into the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material.
Comparative example 1
According to the weight percentage, 83.5 percent of polyester type thermoplastic polyurethane elastomer is mixed evenly in an extruder at 185 ℃, then 15 percent of aluminum hypophosphite, 0.5 percent of dilauryl thiodipropionate (antioxidant D L TP) and 0.5 percent of silicone powder are added, and after even mixing at 195 ℃, the mixture is granulated into the thermoplastic polyurethane elastomer composite material.
The results of the performance measurements are shown in Table 1
Example 2
Preparation of cobalt hydroxystannate-coated aluminum diethylphosphinate:
step 1: adding 100g of aluminum diethylphosphinate into a three-necked flask provided with a stirrer and a reflux condenser pipe at 50 ℃, dispersing in 300g of mixed solvent, adding 12.5g of silane coupling agent KH560, dropwise adding 2g of sodium hydroxide solution to adjust the pH to 11, and after dropwise adding, carrying out heat preservation reaction for 2.5 hours to obtain a modified aluminum diethylphosphinate suspension;
step 2: adding 10g of cobalt hydroxystannate into a three-mouth bottle provided with a stirrer and a reflux condenser pipe at the temperature of 45 ℃, dispersing the cobalt hydroxystannate into 100g of mixed solvent, adding 2.5g of silane coupling agent KH570, dropwise adding 0.6g of mixed solution of sodium carbonate and sodium hydroxide to adjust the pH value to 10, and carrying out heat preservation reaction for 3 hours after dropwise adding is finished to obtain modified cobalt hydroxystannate suspension;
and step 3: adding the modified cobalt hydroxystannate suspension obtained in the step 2 into the modified aluminum diethylphosphinate suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 25 minutes, then heating to 65 ℃, and reacting for 3 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol, and drying at 75 ℃ for 15 hours to obtain the cobalt hydroxystannate-coated aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps:
mixing 88.5 percent of polyether type thermoplastic polyurethane elastomer in percentage by weight in an extruder at 175 ℃ until the mixture is uniform, then adding 10 percent of cobalt hydroxystannate-coated diethyl aluminum phosphinate, 0.25 percent of polytetrafluoroethylene, 0.75 percent of tetra [ β - (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and 0.5 percent of zinc stearate, mixing uniformly at 185 ℃, and granulating to obtain the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material.
Comparative example 2
88.5 percent of polyether type thermoplastic polyurethane elastomer is mixed evenly in an extruder at 175 ℃, 10 percent of diethyl aluminum phosphinate, 0.75 percent of tetra [ β - (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and 0.5 percent of zinc stearate are added, and the mixture is mixed evenly at 185 ℃ and then granulated to form the thermoplastic polyurethane elastomer composite material.
The results of the performance measurements are shown in Table 2
Example 3
Preparation of iron hydroxystannate-coated zinc diethylphosphinate:
step 1: adding 100g of zinc diethylphosphinate into a three-necked bottle provided with a stirrer and a reflux condenser at the temperature of 35 ℃, dispersing into 300g of mixed solvent, adding 10g of silane coupling agent KH570, dropwise adding a mixed solution of 2g of sodium carbonate and sodium hydroxide to adjust the pH to 12, and after dropwise adding, carrying out heat preservation reaction for 2 hours to obtain a modified zinc diethylphosphinate suspension;
step 2: adding 15g of iron hydroxystannate into a three-mouth bottle provided with a stirrer and a reflux condenser pipe at the temperature of 45 ℃, dispersing the mixture into 100g of mixed solvent, adding 2.5g of silane coupling agent KH540, then dropwise adding 0.5g of mixed solution of potassium carbonate and potassium hydroxide to adjust the pH value to 10, and after dropwise adding is finished, carrying out heat preservation reaction for 3 hours to obtain modified iron hydroxystannate suspension;
and step 3: adding the modified iron hydroxystannate suspension obtained in the step 2 into the modified zinc diethylphosphinate suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 20 minutes, then heating to 70 ℃, and reacting for 3.5 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol, and drying at 90 deg.C for 3 hr to obtain zinc diethylphosphinate coated with iron hydroxystannate.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps:
mixing 80% of polyester type thermoplastic polyurethane elastomer in percentage by weight in an internal mixer at 190 ℃ until the mixture is uniform, then adding 18.5% of iron hydroxystannate to wrap diethyl zinc phosphinate, 0.45% of polyhexafluoroethylene, 0.25% of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300), 0.3% of pentaerythritol tetrakis (3-lauryl thiopropionate) (antioxidant S4P) and 0.5% of PE wax, mixing uniformly at 195 ℃, and granulating to obtain the halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material.
Comparative example 3
80 percent of polyester type thermoplastic polyurethane elastomer is mixed evenly in an internal mixer at 190 ℃, 18.5 percent of diethyl zinc phosphinate, 0.25 percent of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300), 0.3 percent of pentaerythritol tetra (3-lauryl thiopropionate) (antioxidant S4P) and 0.5 percent of PE wax are added, and the mixture is mixed evenly at 195 ℃ and then granulated to form the thermoplastic polyurethane elastomer composite material.
The results of the performance measurements are shown in Table 3
Example 4
Preparation of calcium hypophosphite coated with copper hydroxystannate:
step 1: adding 100g of calcium hypophosphite into a three-mouth bottle provided with a stirrer and a reflux condenser pipe at 50 ℃, dispersing into 300g of mixed solvent, adding 15g of silane coupling agent KH540, dropwise adding 1.5g of potassium hydroxide solution to adjust the pH value to 10, and after dropwise adding, carrying out heat preservation reaction for 3.5 hours to obtain modified calcium hypophosphite suspension;
step 2: under the condition of 35 ℃, adding 12g of copper hydroxystannate into a three-mouth bottle provided with a stirrer and a reflux condenser tube, dispersing the mixture in 100g of mixed solvent, adding 3g of silane coupling agent KH550, then dropwise adding 0.3g of potassium hydroxide mixed solution to adjust the pH value to 10, and after dropwise adding, carrying out heat preservation reaction for 3.5 hours to obtain modified copper hydroxystannate suspension;
and step 3: adding the modified copper hydroxystannate suspension obtained in the step 2 into the modified calcium hypophosphite suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 30 minutes, then heating to 75 ℃, and reacting for 4 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol, and drying at 85 deg.C for 8 hr to obtain calcium hypophosphite coated with copper hydroxystannate.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps:
78% of polyether type thermoplastic polyurethane elastomer is mixed evenly in an extruder at 180 ℃, 20% of hydroxyl stannic iron coated calcium hypophosphite, 0.6% of styrene-acrylonitrile copolymer coated polyvinylidene fluoride, 0.75% of tris [ 2.4-di-tert-butylphenyl ] phosphite (antioxidant 168) and 0.65% of paraffin are added, and the mixture is mixed evenly at 185 ℃ and then granulated into the halogen-free flame-retardant smoke-suppression anti-dripping thermoplastic polyurethane elastomer composite material.
Comparative example 4
78% of polyether type thermoplastic polyurethane elastomer is mixed evenly in an extruder at 180 ℃, 20% of calcium hypophosphite, 0.75% of tris [ 2.4-di-tert-butylphenyl ] phosphite (antioxidant 168) and 0.65% of paraffin are added, and after even mixing at 185 ℃, the mixture is granulated into the thermoplastic polyurethane elastomer composite material.
The results of the performance measurements are shown in Table 4
Example 5
Preparation of zinc hydroxystannate-coated calcium diethylphosphinate:
step 1: adding 100g of calcium diethylphosphinate into a three-necked flask provided with a stirrer and a reflux condenser at 45 ℃, dispersing in 300g of mixed solvent, adding 13.5g of silane coupling agent KH540, dropwise adding 3.5g of ammonia water solution to adjust the pH value to 11, and carrying out heat preservation reaction for 2.5 hours after dropwise adding is finished to obtain a modified calcium diethylphosphinate suspension;
step 2: adding 20g of zinc hydroxystannate into a three-mouth bottle provided with a stirrer and a reflux condenser pipe at the temperature of 45 ℃, dispersing the zinc hydroxystannate into 100g of mixed solvent, adding 3.5g of silane coupling agent KH540, dropwise adding 1.1g of ammonia water solution to adjust the pH value to 10, and after dropwise adding, carrying out heat preservation reaction for 4 hours to obtain modified zinc hydroxystannate suspension;
and step 3: adding the modified zinc hydroxystannate suspension obtained in the step 2 into the modified calcium diethylphosphinate suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 25 minutes, then heating to 65 ℃, and reacting for 3 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol, and drying at 80 ℃ for 10 hours to obtain zinc hydroxystannate-coated calcium diethylphosphinate.
The preparation method of the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material comprises the following steps:
82 percent of polyester type thermoplastic polyurethane elastomer is mixed evenly in an internal mixer at 180 ℃, then 16.5 percent of zinc hydroxystannate coated diethyl calcium phosphinate, 0.5 percent of styrene-acrylonitrile copolymer coated polyhexafluoroethylene, 0.25 percent of tetra [ β - (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), 0.25 percent of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300) and 0.5 percent of silicone powder are added, and the mixture is mixed evenly at 190 ℃ and then granulated into the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material.
Comparative example 5
82 percent of polyester type thermoplastic polyurethane elastomer is mixed evenly in an internal mixer at 180 ℃, then 16.5 percent of diethyl calcium phosphinate, 0.25 percent of tetra [ β - (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), 0.25 percent of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300) and 0.5 percent of silicone powder are added, and the mixture is mixed evenly at 190 ℃ and granulated to obtain the halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material.
The results of the performance measurements are shown in Table 5
The tensile strength and elongation at break of the samples of the above examples were tested according to ASTM D412; the limiting oxygen index test standard is ASTM D2863; the vertical burn test standard is ASTM D3801; smoke density test standard is ASATME 662.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are intended to be equivalent substitutions are included in the scope of the present invention.
Claims (14)
1. The halogen-free flame-retardant smoke-inhibiting anti-dripping thermoplastic polyurethane elastomer composite material is characterized by comprising the following components in percentage by weight:
2. the halogen-free flame retardant smoke suppressing drip resistant thermoplastic polyurethane elastomer composite of claim 1 wherein: the thermoplastic polyurethane elastomer is at least one of polyether type thermoplastic polyurethane elastomer and polyester type thermoplastic polyurethane elastomer.
3. The halogen-free flame retardant smoke suppressing drip resistant thermoplastic polyurethane elastomer composite of claim 1 wherein: the anti-dropping agent is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoroethylene, polytetrafluoroethylene coated by styrene-acrylonitrile copolymer, polyvinylidene fluoride coated by styrene-acrylonitrile copolymer and polyhexafluoroethylene coated by styrene-acrylonitrile copolymer.
4. The halogen-free flame retardant smoke suppression and drip resistance thermoplastic polyurethane elastomer composite material according to claim 1, wherein the antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300), dilauryl thiodipropionate (antioxidant D L TP), pentaerythritol tetrakis (3-laurylthiopropionate) (antioxidant S4P) and tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168).
5. The halogen-free flame retardant smoke suppressing drip resistant thermoplastic polyurethane elastomer composite of claim 1 wherein: the lubricant is at least one of zinc stearate, paraffin, PE wax and silicone powder.
6. The halogen-free flame retardant smoke suppressing drip resistant thermoplastic polyurethane elastomer composite of claim 1 wherein: the smoke suppressant coated hypophosphite (phosphonate) fire retardant is a coated fire retardant taking a smoke suppressant as a shell layer and hypophosphite (phosphonate) as a core material, and the smoke suppressant and the hypophosphite (phosphonate) are combined in a chemical bond form through a silane coupling agent.
7. The halogen-free flame-retardant smoke-suppressing anti-dripping thermoplastic polyurethane elastomer composite material according to claim 1 is characterized in that: the smoke suppressant wraps the hypophosphite (phosphonate) flame retardant and comprises the following raw materials in percentage by mass:
8. the halogen-free flame retardant smoke suppressing drip resistant thermoplastic polyurethane elastomer composite of claims 6 and 7 wherein: the hypophosphite flame retardant is at least one of aluminum hypophosphite, calcium hypophosphite, zinc hypophosphite, aluminum diethylphosphinate, zinc diethylphosphinate and calcium diethylphosphinate, and the smoke inhibitor is at least one of zinc hydroxystannate, iron hydroxystannate, cobalt hydroxystannate, calcium hydroxystannate, magnesium hydroxystannate and copper hydroxystannate.
9. The halogen-free flame retardant smoke suppression anti-drip thermoplastic polyurethane elastomer composite material according to claim 7, wherein: the silane coupling agent is at least one of gamma-aminopropyltrimethoxysilane (KH540), gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560) and gamma-methacryloxypropyltrimethoxysilane (KH 570).
10. The halogen-free flame retardant smoke suppression anti-drip thermoplastic polyurethane elastomer composite material according to claim 7, wherein: 1-15 parts by mass of the silane coupling agent are used for carrying out hydrolytic modification on hypophosphite (phosphonate), and 1-5 parts by mass of the silane coupling agent are used for carrying out hydrolytic modification on a smoke suppressant.
11. The halogen-free flame-retardant smoke-suppressing anti-dripping thermoplastic polyurethane elastomer composite material according to claim 7, wherein the mixed solvent is a mixed solvent obtained by mixing ethanol and distilled water according to a mass ratio of 4: 1.
12. The halogen-free flame retardant smoke suppression anti-drip thermoplastic polyurethane elastomer composite material according to claim 7, wherein the pH regulator is at least one of an ammonia solution, a sodium carbonate solution, a potassium carbonate solution, a sodium hydroxide solution and a potassium hydroxide solution.
13. The halogen-free flame-retardant smoke-suppressing anti-dripping thermoplastic polyurethane elastomer composite material according to claim 7, wherein the smoke suppressor is coated with a hypophosphite flame retardant, and the preparation method comprises the following steps: step 1: adding 100 parts by mass of hypophosphite flame retardant into a three-necked bottle provided with a stirrer and a reflux condenser pipe at the temperature of 30-60 ℃, dispersing the hypophosphite flame retardant into 300 parts by mass of a mixed solvent, adding 1-15 parts by mass of a silane coupling agent, dropwise adding 0.1-7.5 parts by mass of a pH regulator to adjust the pH to 8-12, and carrying out heat preservation reaction for 2-8 hours after dropwise adding is finished to obtain a modified hypophosphite flame retardant suspension;
step 2: adding 0.5-20 parts by mass of smoke suppressant into a three-necked bottle provided with a stirrer and a reflux condenser pipe at the temperature of 30-60 ℃, dispersing the smoke suppressant into 100 parts by mass of mixed solvent, adding 1-5 parts by mass of silane coupling agent, dropwise adding 0.1-2.5 parts by mass of pH regulator to adjust the pH to 8-12, and carrying out heat preservation reaction for 2-8 hours after dropwise adding is finished to obtain modified smoke suppressant suspension;
and step 3: adding the modified smoke suppressant suspension obtained in the step 2 into the modified hypophosphite (phosphonate) suspension obtained in the step 1 under the ultrasonic condition, continuing to perform ultrasonic treatment for 10-40 minutes, then heating to 55-85 ℃, and reacting for 2-8 hours to obtain a mixed suspension; and filtering, washing with water, washing with ethanol and drying the mixed suspension to obtain the smoke suppressant-coated hypophosphite (phosphonate) flame retardant.
14. The preparation method of the halogen-free flame-retardant smoke-suppressing drip-resistant thermoplastic polyurethane elastomer composite material according to claim 1, 2, 3, 4, 5, 6 or 7, which is characterized by comprising the following steps: according to the weight percentage, 60 to 90 percent of thermoplastic polyurethane elastomer is mixed in an internal mixer or an extruder at the temperature of 165 plus 210 ℃ to be uniform, then 10 to 35 percent of smoke suppressant is added to wrap the hypophosphite flame retardant, 0.1 to 3 percent of anti-dripping agent, 0.1 to 1.5 percent of antioxidant and 0.1 to 1.5 percent of lubricant, and the mixture is mixed uniformly at the temperature of 165 plus 210 ℃ and then granulated to form the halogen-free flame-retardant smoke-suppressing anti-dripping thermoplastic polyurethane elastomer composite material.
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