CN111019322A - High-performance high-flame-retardant halogen-free TPU material and preparation method thereof - Google Patents
High-performance high-flame-retardant halogen-free TPU material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/44—Polycarbonates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a high-performance high-flame-retardant halogen-free TPU material which comprises the following components: the flame-retardant polyurethane material comprises a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and the like, and is prepared from the following raw materials in parts by weight: 80-95 parts of polycarbonate material, 55-65 parts of polyether material, 45-55 parts of polyester material, 15-25 parts of flame retardant, 3-6 parts of antibacterial agent, 2-5 parts of mildew preventive, 5-9 parts of polyamide, 0.8-2.4 parts of wear-resistant reinforcing agent, 30-40 parts of plasticizer, 6-12 parts of organic bismuth, 2-4 parts of antistatic agent, 0.2-0.4 part of antioxidant, 5-9 parts of chain-extending cross-linking agent and the like. The invention has the following advantages: the TPU material disclosed by the invention has the characteristics of high wear resistance, good elastic toughness, oil resistance, high and low temperature resistance and the like.
Description
Technical Field
The invention relates to the field of TPU materials, in particular to a high-performance high-flame-retardant halogen-free TPU material and a preparation method thereof.
Background
The new material is one of ten fields, and attracts people's extensive attention. The field takes special metal functional materials, high-performance structural materials, functional high polymer materials, special inorganic non-metal materials and advanced composite materials as development focuses, the key technology and equipment for preparing the new materials such as advanced smelting, solidification forming, vapor deposition, section bar processing, high-efficiency synthesis and the like are quickened to be researched and developed, the basic research and the system construction are enhanced, and the bottleneck of industrial preparation is broken through. The special new materials shared by the military and the civil are actively developed, the bidirectional transfer and transformation of the technology are accelerated, and the integration and development of the military and the civil of the new material industry are promoted. The influence of subversive new materials on traditional materials is highly concerned, and the advance layout and development of materials such as superconducting materials, nano materials, graphene, bio-based materials and the like are well developed at the strategic front. And the upgrading and updating of the base material are accelerated.
Thermoplastic polyurethane elastomers (TPU) have high strength, high modulus and excellent mechanical properties due to their special soft and hard block copolymer structures, and are drawing attention in the fields of special inorganic non-metallic materials and advanced composite materials. Compared with other elastomer materials, the TPU has wide hardness range and better comprehensive performance in the aspects of wear resistance, elasticity, mechanical property and the like, and is used as a cable sheath material in many fields. However, the oxygen index of the common TPU is only 17.0-18.0 percent, the common TPU belongs to flammable materials, and the common TPU has low char yield and strong molten drop phenomenon during combustion, thereby limiting the application range of the common TPU; in order to enhance the flame retardant property of TPU, the prior general method is to add halogen-containing flame retardant into the TPU, but the chlorine-containing flame retardant achieves the flame retardant effect mainly through a gas-phase flame retardant mechanism, and can release a large amount of toxic and harmful gases during combustion, thereby not only polluting the environment, but also seriously affecting the life safety of people concerned; against this background, chlorine-containing flame retardants have been banned by the various national directives. And the TPU is applied to high-performance wire and cable sheaths, new energy automobiles, aerospace ship materials and the like. Therefore, in order to meet the requirements of the application occasions, the development of a TPU with the properties meeting the requirements of high physical properties, good flame retardance, antibiosis, high wear resistance and the like is urgently needed.
Disclosure of Invention
The invention aims to provide a high-performance high-flame-retardant halogen-free TPU material and a preparation method thereof, so as to solve the problems in the background art.
The technical problem solved by the invention is realized by adopting the following technical scheme: a high-performance high-flame-retardant halogen-free TPU material comprises the following components: the flame-retardant polyurethane material is characterized by comprising a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, wherein the specific formula comprises the following raw materials in parts by weight: 80-95 parts of polycarbonate material, 55-65 parts of polyether material, 45-55 parts of polyester material, 15-25 parts of flame retardant, 3-6 parts of antibacterial agent, 2-5 parts of mildew preventive, 5-9 parts of polyamide, 0.8-2.4 parts of wear-resistant reinforcing agent, 30-40 parts of plasticizer, 6-12 parts of organic bismuth, 2-4 parts of antistatic agent, 0.2-0.4 part of antioxidant, 5-9 parts of chain-extending cross-linking agent and 0.3-0.9 part of composite lubricant.
Preferably, the high-performance high-flame-retardant halogen-free TPU material comprises the following raw materials in parts by weight: 85 parts of polycarbonate material, 60 parts of polyether material, 50 parts of polyester material, 20 parts of flame retardant, 4 parts of antibacterial agent, 3 parts of mildew preventive, 7 parts of polyamide, 1.5 parts of wear-resistant reinforcing agent, 35 parts of plasticizer, 9 parts of organic bismuth, 3 parts of antistatic agent, 0.3 part of antioxidant, 7 parts of chain-extending cross-linking agent and 0.6 part of composite lubricant.
Preferably, the polycarbonate type material is one of polytetrahydrofuran and its copolymerized polyether polyol, polyether polyol and polypropylene oxide polyol.
Preferably, the polyether material is one of a co-polyether polyol and a polyether polyol, and the polyester material is a polyester polyol.
Preferably, the flame retardant is one or more of melamine, dicyandiamide, guanidine salt and phosphate derivatives thereof in the nitrogen-containing flame retardant.
Preferably, the plasticizer is a phthalate plasticizer.
Preferably, the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to the mass ratio of 10: 5.
Preferably, the chain extension crosslinking agent is one selected from ethylene glycol, propylene glycol, dimethylthiotoluenediamine DMTDA and diethanol amine.
Preferably, the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: 1, in a mixture of the components.
A preparation method of a high-performance high-flame-retardant halogen-free TPU material specifically comprises the following steps:
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 50-70rpm/min for 20-30min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying box, and drying for 3.5-4.5h at the drying temperature of 100-120 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of the feeding section of the double-screw granulator is 110-.
Compared with the prior art, the invention has the following advantages: the TPU material disclosed by the invention has the characteristics of high wear resistance, good elastic toughness, oil resistance, high and low temperature resistance and the like; the polyether material has the characteristics of hydrolysis resistance and high resilience, while the polyester material has the characteristics of oil resistance and solvent resistance, and the combination of the two ensures that the synthesized material is not easily influenced by the environment to cause the difference of sizes; the nitrogen-containing flame retardant is adopted, and after being heated and decomposed, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, and the generated gases and the decomposition of the flame retardant absorb heat to take away most of heat, so that the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, and a good flame retardant effect is achieved; the antibacterial agent and the mildew preventive are added, so that the antibacterial and mildew preventive properties are high; the organic bismuth enhances the hydrolysis resistance stability of the TPU material.
Detailed Description
In order to make the technical means, the creation features, the work flow and the using method of the present invention easily understand and understand the purpose and the efficacy, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but 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
A high-performance high-flame-retardant halogen-free TPU material comprises the following components: the flame-retardant polyurethane material is characterized by comprising a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, wherein the specific formula comprises the following raw materials in parts by weight: 80-95 parts of polycarbonate material, 55-65 parts of polyether material, 45-55 parts of polyester material, 15-25 parts of flame retardant, 3-6 parts of antibacterial agent, 2-5 parts of mildew preventive, 5-9 parts of polyamide, 0.8-2.4 parts of wear-resistant reinforcing agent, 30-40 parts of plasticizer, 6-12 parts of organic bismuth, 2-4 parts of antistatic agent, 0.2-0.4 part of antioxidant, 5-9 parts of chain-extending cross-linking agent and 0.3-0.9 part of composite lubricant.
Preferably, the polycarbonate-type material is one of polytetrahydrofuran and its copolymerized polyether polyol, polyether polyol and polyoxypropylene polyol, and has excellent mechanical property, hydrolysis resistance, heat resistance, oxidation resistance, wear resistance, in-vivo oxidation resistance and microbial degradability.
Preferably, the polyether material is one of a co-polyether polyol and a polyether polyol, the co-polyether polyol and the polyether polyol have the characteristics of low toxicity, hydrolysis resistance and high resilience, the polyester material is a polyester polyol, and the polyester polyol contains more ester groups and other polar groups in molecules, has strong cohesive strength and adhesive force, and has high strength and wear resistance.
Preferably, the flame retardant is one or more of melamine, dicyandiamide, guanidine salt and phosphate derivatives thereof in the nitrogen-containing flame retardant, after the flame retardant is heated and decomposed, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, most of heat is taken away by the generation of the gases and the decomposition and heat absorption of the flame retardant, the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, so that a good flame retardant effect is achieved.
Preferably, the plasticizer is a phthalate plasticizer, which is an esterified derivative of phthalic acid, is the most common plasticizer, is a colorless liquid with little or no odor, and is nontoxic, medium in viscosity, high in stability, low in volatility, low in cost and easily soluble in most organic solvents.
Preferably, the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to the mass ratio of 10: 5, the composite antistatic agent has small addition amount and good effect, and greatly reduces the surface resistivity of the material.
Preferably, the chain extension crosslinking agent is selected from one of ethylene glycol, propylene glycol, dimethylthiotoluenediamine DMTDA and diethanol amine, and the heat resistance, hardness and elasticity of the product are higher than those of the commonly used chain extension crosslinking agent.
Preferably, the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: the mixture of 1 does not decompose, volatilize, corrode equipment, pollute products and have no toxicity in the processing process.
A preparation method of a high-performance high-flame-retardant halogen-free TPU material specifically comprises the following steps:
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 50-70rpm/min for 20-30min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying box, and drying for 3.5-4.5h at the drying temperature of 100-120 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of the feeding section of the double-screw granulator is 110-.
Example 2
A high-performance high-flame-retardant halogen-free TPU material comprises the following components: the flame-retardant polyurethane material is characterized by comprising a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, wherein the specific formula comprises the following raw materials in parts by weight: 80 parts of polycarbonate material, 55 parts of polyether material, 45 parts of polyester material, 15 parts of flame retardant, 3 parts of antibacterial agent, 2 parts of mildew preventive, 5 parts of polyamide, 0.8 part of wear-resistant reinforcing agent, 30 parts of plasticizer, 6 parts of organic bismuth, 2 parts of antistatic agent, 0.2 part of antioxidant, 5 parts of chain-extending cross-linking agent and 0.3 part of composite lubricant.
Preferably, the polycarbonate-type material is one of polytetrahydrofuran and its copolymerized polyether polyol, polyether polyol and polyoxypropylene polyol, and has excellent mechanical property, hydrolysis resistance, heat resistance, oxidation resistance, wear resistance, in-vivo oxidation resistance and microbial degradability.
Preferably, the polyether material is polyether polyol, the polyether polyol has the characteristics of low toxicity, hydrolysis resistance and high resilience, the polyester material is polyester polyol, and polyester polyol molecules contain more ester groups and other polar groups, so that the polyether material is high in cohesive strength and adhesive force and high in strength and wear resistance.
Preferably, the flame retardant is one or more of guanidine salt and phosphate derivatives thereof in the nitrogen-containing flame retardant, after the flame retardant is decomposed by heating, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, most of heat is taken away by the generation of the gases and the decomposition and heat absorption of the flame retardant, the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, so that a good flame retardant effect is achieved.
Preferably, the plasticizer is a phthalate plasticizer, which is an esterified derivative of phthalic acid, is the most common plasticizer, is a colorless liquid with little or no odor, and is nontoxic, medium in viscosity, high in stability, low in volatility, low in cost and easily soluble in most organic solvents.
Preferably, the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to the mass ratio of 10: 5, the composite antistatic agent has small addition amount and good effect, and greatly reduces the surface resistivity of the material.
Preferably, the chain-extending cross-linking agent is diethanolamine, and the heat resistance, hardness and elasticity of the product are higher than those of the commonly used chain-extending cross-linking agent.
Preferably, the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: the mixture of 1 does not decompose, volatilize, corrode equipment, pollute products and have no toxicity in the processing process.
A preparation method of a high-performance high-flame-retardant halogen-free TPU material specifically comprises the following steps:
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 50rpm/min for 20min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying oven, and drying for 3.5 hours at the drying temperature of 100 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of a feeding section of the double-screw granulator is 100 ℃, the temperature of a mixing section of the double-screw granulator is 125 ℃, the temperature of an extruding section of the double-screw granulator is 150 ℃, and the temperature of a machine head of the double-screw granulator is 130 ℃, so as to obtain the TPU material.
Example 3
A high-performance high-flame-retardant halogen-free TPU material comprises the following components: the flame-retardant polyurethane material is characterized by comprising a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, wherein the specific formula comprises the following raw materials in parts by weight: 95 parts of polycarbonate material, 65 parts of polyether material, 55 parts of polyester material, 25 parts of flame retardant, 6 parts of antibacterial agent, 5 parts of mildew preventive, 9 parts of polyamide, 2.4 parts of wear-resistant reinforcing agent, 40 parts of plasticizer, 12 parts of organic bismuth, 4 parts of antistatic agent, 0.4 part of antioxidant, 9 parts of chain-extending cross-linking agent and 0.9 part of composite lubricant.
Preferably, the polycarbonate-type material is one of polytetrahydrofuran and its copolymerized polyether polyol, polyether polyol and polyoxypropylene polyol, and has excellent mechanical property, hydrolysis resistance, heat resistance, oxidation resistance, wear resistance, in-vivo oxidation resistance and microbial degradability.
Preferably, the polyether material is polyether polyol, the polyether polyol has the characteristics of low toxicity, hydrolysis resistance and high resilience, the polyester material is polyester polyol, and polyester polyol molecules contain more ester groups and other polar groups, so that the polyester material is high in cohesive strength and adhesive force and high in strength and wear resistance.
Preferably, the flame retardant is dicyandiamide in a nitrogen-containing flame retardant, after the flame retardant is heated and decomposed, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, most of heat is taken away by the generation of the gases and the decomposition and heat absorption of the flame retardant, the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, so that a good flame retardant effect is achieved.
Preferably, the plasticizer is a phthalate plasticizer, which is an esterified derivative of phthalic acid, is the most common plasticizer, is a colorless liquid with little or no odor, and is nontoxic, medium in viscosity, high in stability, low in volatility, low in cost and easily soluble in most organic solvents.
Preferably, the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to the mass ratio of 10: 5, the composite antistatic agent has small addition amount and good effect, and greatly reduces the surface resistivity of the material.
Preferably, the chain extension crosslinking agent is one of propylene glycol and dimethylthiotoluenediamine DMTDA, and the heat resistance, hardness and elasticity of the product are higher than those of the commonly used chain extension crosslinking agent.
Preferably, the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: the mixture of 1 does not decompose, volatilize, corrode equipment, pollute products and have no toxicity in the processing process.
A preparation method of a high-performance high-flame-retardant halogen-free TPU material specifically comprises the following steps:
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 50-70rpm/min for 20-30min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying oven, and drying for 4.5 hours at the drying temperature of 120 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of a feeding section of the double-screw granulator is 110 ℃, the temperature of a mixing section of the double-screw granulator is 135 ℃, the temperature of an extruding section of the double-screw granulator is 160 ℃, and the temperature of a machine head of the double-screw granulator is 140 ℃, so as to obtain the TPU material.
Example 4
A high-performance high-flame-retardant halogen-free TPU material comprises the following components: the flame-retardant polyurethane material is characterized by comprising a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, wherein the specific formula comprises the following raw materials in parts by weight: 85 parts of polycarbonate material, 60 parts of polyether material, 50 parts of polyester material, 20 parts of flame retardant, 4 parts of antibacterial agent, 3 parts of mildew preventive, 7 parts of polyamide, 1.5 parts of wear-resistant reinforcing agent, 35 parts of plasticizer, 9 parts of organic bismuth, 3 parts of antistatic agent, 0.3 part of antioxidant, 7 parts of chain-extending cross-linking agent and 0.6 part of composite lubricant.
Preferably, the polycarbonate-type material is one of polytetrahydrofuran and its copolymerized polyether polyol, polyether polyol and polyoxypropylene polyol, and has excellent mechanical property, hydrolysis resistance, heat resistance, oxidation resistance, wear resistance, in-vivo oxidation resistance and microbial degradability.
Preferably, the polyether material is polyether polyol, the polyether polyol and the polyether polyol have the characteristics of low toxicity, hydrolysis resistance and high resilience, the polyester material is polyester polyol, and the polyester polyol contains more ester groups and other polar groups in molecules, so that the polyester material is high in cohesive strength and adhesive force and high in strength and wear resistance.
Preferably, the flame retardant is melamine in a nitrogen-containing flame retardant, after the flame retardant is heated and decomposed, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, most of heat is taken away by the generation of the gases and the decomposition and heat absorption of the flame retardant, the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, so that a good flame retardant effect is achieved.
Preferably, the plasticizer is a phthalate plasticizer, which is an esterified derivative of phthalic acid, is the most common plasticizer, is a colorless liquid with little or no odor, and is nontoxic, medium in viscosity, high in stability, low in volatility, low in cost and easily soluble in most organic solvents.
Preferably, the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to the mass ratio of 10: 5, the composite antistatic agent has small addition amount and good effect, and greatly reduces the surface resistivity of the material.
Preferably, the chain-extending cross-linking agent is ethylene glycol, and the heat resistance, hardness and elasticity of the product are higher than those of the commonly used chain-extending cross-linking agent.
Preferably, the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: the mixture of 1 does not decompose, volatilize, corrode equipment, pollute products and have no toxicity in the processing process.
A preparation method of a high-performance high-flame-retardant halogen-free TPU material specifically comprises the following steps:
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 60rpm/min for 25min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying box, and drying for 4 hours at a drying temperature of 110 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of a feeding section of the double-screw granulator is 105 ℃, the temperature of a mixing section of the double-screw granulator is 130 ℃, the temperature of an extruding section of the double-screw granulator is 155 ℃, and the temperature of a machine head of the double-screw granulator is 135 ℃, so as to obtain the TPU material.
The TPU material disclosed by the invention has the characteristics of high wear resistance, good elastic toughness, oil resistance, high and low temperature resistance and the like; the polyether material has the characteristics of hydrolysis resistance and high resilience, while the polyester material has the characteristics of oil resistance and solvent resistance, and the combination of the two ensures that the synthesized material is not easily influenced by the environment to cause the difference of sizes; the nitrogen-containing flame retardant is adopted, and after being heated and decomposed, non-combustible gases such as ammonia gas, nitrogen gas, deep nitrogen oxide, water vapor and the like are easily released, and the generated gases and the decomposition of the flame retardant absorb heat to take away most of heat, so that the surface temperature of the polymer is greatly reduced, and meanwhile, oxygen on the surface of the material is consumed, and a good flame retardant effect is achieved; the antibacterial agent and the mildew preventive are added, so that the antibacterial and mildew preventive properties are high; the organic bismuth enhances the hydrolysis resistance stability of the TPU material.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A high-performance high-flame-retardant halogen-free TPU material is characterized in that: the flame-retardant polyurethane resin comprises a polycarbonate material, a polyether material, a polyester material, a flame retardant, an antibacterial agent, a mildew inhibitor, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant, and the specific formula is prepared from the following raw materials in parts by weight: 80-95 parts of polycarbonate material, 55-65 parts of polyether material, 45-55 parts of polyester material, 15-25 parts of flame retardant, 3-6 parts of antibacterial agent, 2-5 parts of mildew preventive, 5-9 parts of polyamide, 0.8-2.4 parts of wear-resistant reinforcing agent, 30-40 parts of plasticizer, 6-12 parts of organic bismuth, 2-4 parts of antistatic agent, 0.2-0.4 part of antioxidant, 5-9 parts of chain-extending cross-linking agent and 0.3-0.9 part of composite lubricant.
2. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the high-performance high-flame-retardant halogen-free TPU material comprises the following raw materials in parts by weight: 85 parts of polycarbonate material, 60 parts of polyether material, 50 parts of polyester material, 20 parts of flame retardant, 4 parts of antibacterial agent, 3 parts of mildew preventive, 7 parts of polyamide, 1.5 parts of wear-resistant reinforcing agent, 35 parts of plasticizer, 9 parts of organic bismuth, 3 parts of antistatic agent, 0.3 part of antioxidant, 7 parts of chain-extending cross-linking agent and 0.6 part of composite lubricant.
3. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the polycarbonate material is one of polytetrahydrofuran and polyether polyol, polyether polyol and polypropylene oxide polyol.
4. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the polyether material is one of a copolymerized polyether polyol and a polyether polyol, and the polyester material is a polyester polyol.
5. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the flame retardant is one or more of melamine, dicyandiamide, guanidine salt and phosphate derivatives thereof in the nitrogen-containing flame retardant.
6. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the plasticizer is phthalate plasticizer.
7. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the antistatic agent is prepared from glycerol monostearate and ethoxylated amine according to a mass ratio of 10: 5.
8. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the chain extension crosslinking agent is one selected from ethylene glycol, propylene glycol, dimethyl sulfur toluene diamine DMTDA and diethanol amine.
9. The high-performance high-flame-retardant halogen-free TPU material as claimed in claim 1, wherein: the composite lubricant is polyethylene wax, calcium stearate or a mixture of the polyethylene wax and the calcium stearate according to a mass ratio of 1: 1, in a mixture of the components.
10. A preparation method of a high-performance high-flame-retardant halogen-free TPU material is characterized by comprising the following steps: the method specifically comprises the following steps of,
step 1, respectively weighing a carbonate type material, a polyether type material, a polyester type material, a flame retardant, an antibacterial agent, a mildew preventive, polyamide, a wear-resistant reinforcing agent, a plasticizer, organic bismuth, an antistatic agent, an antioxidant, a chain-extending cross-linking agent and a composite lubricant in parts by weight, and putting the materials into a mixing stirrer;
step 2, stirring the mixing stirrer in the step 1 at a rotating speed of 50-70rpm/min for 20-30min, and uniformly mixing;
step 3, putting the mixture obtained in the step 2 into a drying box, and drying for 3.5-4.5h at the drying temperature of 100-120 ℃;
and 4, adding the dried material obtained in the step 3 into a double-screw granulator from a side feeding port, and extruding, wherein the temperature of the feeding section of the double-screw granulator is 110-.
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