CN109988411B - Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof - Google Patents
Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material and a preparation method thereof, wherein the antistatic composite material is prepared from the following raw materials: TPU resin, tricresyl phosphate, melamine polyphosphate, functionalized graphene, an antioxidant 1076, an ultraviolet absorber UV-24, conductive carbon black, stearic acid and 8-hydroxyquinolinone. The surface of the functionalized graphene is doped with nitrogen and is chemically modified by molybdate radicals, so that good dispersibility in TPU can be realized under high addition, and meanwhile, the smoke suppression performance and the mechanical property of the TPU antistatic composite material can be improved; the device is suitable for popularization and use in industries such as electronic appliances, automobiles, buildings, precision instruments and the like.
Description
Technical Field
The invention belongs to the technical field of antistatic material preparation, and particularly relates to a flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material and a preparation method thereof.
Background
Thermoplastic Polyurethane (TPU) resin is a common polymer material, has good mechanical properties, processability and chemical resistance, and is widely applied to the fields of electronics, automobiles, machinery and the like. The antistatic composite material obtained by the TPU through a modification method is easy to burn, has large smoke generation amount and has a limit oxygen index of only 18 percent, so that the application of the antistatic composite material in actual production is limited. How to improve the flame retardant and smoke suppression performance of the TPU antistatic composite material once becomes a focus of attention of people, and the main solution at present is to add a halogen flame retardant. With the growing concern about environmental protection, the halogen-based flame retardant is abandoned by some countries because the combustion products pollute the environment. However, flame-retardant smoke-inhibiting TPU antistatic composite materials are lacked in the market, and the demand for novel high-performance TPU antistatic composite materials is increasingly strong.
Graphene is a novel carbonaceous material with a single-layer two-dimensional honeycomb lattice structure formed by tightly stacking carbon atoms, and has the characteristics of high strength, high conductivity, high specific surface area and the like. The continuous development of the preparation method of the graphene provides a raw material guarantee for the wide application and development of the graphene in the field of polymer composite materials. However, how to improve the controllability of graphene surface modification is still a difficult problem to be solved in academia and industry. The surface state of graphene is very stable, inert as a whole, and each single-layer graphene sheet is bound by strong interlayer van der waals forces, resulting in poor lipophilicity and hydrophilicity, inefficient complexation with a polymer matrix, and easy formation of aggregates in the polymer matrix. In order to solve the above problems, graphene must be surface-modified to improve its handling and enhance its interaction with a polymer. The graphene functional modification method widely used at home and abroad at present mainly comprises two methods of covalent modification and non-covalent modification. Most of the existing methods adopt covalent bond construction modification methods to modify the graphene surface. Since graphene oxide contains a large number of active oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups, these functional groups can be utilized to react with other molecular chains to form a graft taking a covalent bond as a bridge, thereby realizing covalent modification of the graphene surface. Stankovich and the like successfully realize covalent modification of graphene by reacting isocyanate with carboxyl and hydroxyl on the surface of graphene oxide, prepare completely stripped functionalized graphene oxide which can be dispersed in an organic solvent for the first time, and provide possibility for application of graphene as a filler in the field of composite materials (Carbon, 2006, volume 44). Lee et al prepared functionalized graphene conductive composites by an in situ method. Since the modified graphene particles are uniformly dispersed in the polymer matrix and form a stable conductive network, the conductivity of the composite material is increased by 105 times compared with that of a pure polymer (Macromolecular Chemistry and Physics, 2009, volume 210). Huang et al graft polypiperazine double spiro phosphate amide (PPSPB) to graphene through chemical reaction to obtain a novel intumescent flame retardant functionalized graphene (CRG-PPSPB). The organic modification of the PPSPB not only improves the dispersibility of the graphene in a polymer matrix and the mechanical property of the material, but also can obviously enhance the synergistic flame-retardant effect of the intumescent flame retardant and the graphene. The EVA composite heat release rate Peak (PHRR) with 1 wt% CRG-PPSPB addition decreased by about 56% compared to pure EVA resin (Mater Chem Phys, 2012, volume 135). Researchers also modify the surface of graphene with epoxy resin, the compatibility between the modified graphene and an epoxy matrix is greatly improved, and the young modulus of the graphene/epoxy composite material with the volume fraction of only 1% is improved by 24% compared with that of pure epoxy resin, which indicates that the interface bonding force between the modified graphene and the epoxy resin is stronger, the compatibility is good, and effective stress transfer is promoted (Nanotechnology, 2014, vol 25).
The flame-retardant smoke-suppressing agent is grafted to the surface of the graphene through chemical modification of the surface of the graphene to obtain a novel conductive agent with the flame-retardant smoke-suppressing function, and the flame-retardant smoke-suppressing TPU antistatic composite material is prepared through melt blending with TPU, so that a new way is provided for solving the problems of single function and low technical content of the conventional polymer antistatic material.
Disclosure of Invention
The invention aims to provide a functionalized graphene modified TPU antistatic composite material with flame-retardant and smoke-suppressing functions.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the functionalized graphene is prepared by nitriding oxidized graphene, ionizing molybdate radicals and the like, and has a structural formula shown in figure 1.
The preparation method of the functionalized graphene is characterized by comprising the following steps:
(1) nitridation of Graphene Oxide (GO)
Adding GO into Dimethylformamide (DMF), carrying out ultrasonic treatment for 40 minutes at room temperature, adding an amine compound, uniformly mixing, transferring into a high-pressure kettle containing a polytetrafluoroethylene lining, sealing and storing in an oven, heating to 120-220 ℃, and reacting for 3-9 hours; after the reaction is finished, carrying out suction filtration, washing the precipitate for multiple times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene (N-GO);
(2) modification of molybdate radical by ionization
Adding N-GO powder into deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding molybdate into the suspension, stirring and reacting at room temperature for 5 hours, performing suction filtration on a product, and washing with deionized water for multiple times to remove redundant reagents to obtain the functionalized graphene product.
In the above technical solution, further, the mass ratio of DMF, GO and amine compound in step (1) is 1: 0.005-0.03: 0.05 to 0.6.
The amine compound in the step (1) is p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, ethylenediamine or hexamethylenediamine.
The mass ratio of the deionized water to the N-GO to the molybdate in the step (2) is 1: 0.001-0.02: 0.005-0.04.
The molybdate in the step (2) is ammonium octamolybdate, zinc molybdate, calcium molybdate and cobalt molybdate.
The flame-retardant smoke-inhibiting TPU antistatic composite material is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 3-8 parts of tricresyl phosphate, 5-15 parts of melamine polyphosphate, 0.5-2 parts of functionalized graphene, 0.2-2 parts of antioxidant 1076, 0.1-1 part of ultraviolet absorbent (UV-24), 2-8 parts of conductive carbon black, 0.5-2 parts of stearic acid and 0.1-0.3 part of 8-hydroxyquinolinone.
The preparation method of the flame-retardant smoke-suppressing TPU antistatic composite material comprises the steps of adding the raw materials into a plastic vertical stirrer, stirring and dispersing for 1 hour, adding the mixture into an extruder through an automatic feeding machine, and extruding and granulating at the processing temperature of 180-230 ℃ to obtain granules which are the flame-retardant smoke-suppressing TPU antistatic composite material.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. according to the functional graphene modified TPU antistatic composite material prepared by the invention, nitrogen is doped on the surface of the used functional graphene, wherein the nitrogen-doped functional group increases the compatibility with a TPU substrate, the good dispersibility in the TPU under the condition of high addition is realized, the interaction of the interface of the functional graphene and the TPU is enhanced, and the mechanical property of the TPU antistatic composite material is improved;
2. according to the functional graphene modified TPU antistatic composite material prepared by the invention, the used functional graphene is chemically modified by molybdate radicals, so that the smoke suppression performance of the TPU antistatic composite material is improved, meanwhile, the molybdate radicals anchored on the surface of the graphene are not easy to separate out in the using process, and the secondary pollution of a smoke suppressor is reduced;
3. the functionalized graphene modified TPU antistatic composite material disclosed by the invention adopts a halogen-free flame retardant system, and has the advantages of environmental friendliness;
4. the functionalized graphene modified TPU antistatic composite material disclosed by the invention adopts a melt blending preparation method, so that the preparation process is simple, the production cost is low, and the energy consumption and the pollutant emission are reduced;
5. the functionalized graphene modified TPU antistatic composite material prepared by the invention has the characteristics of good flame-retardant smoke suppression effect, high mechanical strength, good antistatic performance and the like, and is suitable for being used in industries such as electronic appliances, automobiles, buildings, precision instruments and the like.
Drawings
Fig. 1 is a schematic diagram of a structure of functionalized graphene.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
Preparing functionalized graphene:
(1) nitridation of Graphene Oxide (GO)
Adding 0.5g of GO into 100g of DMF, carrying out ultrasonic treatment for 40 minutes at room temperature, adding 5g of ethylenediamine, uniformly mixing, transferring into a high-pressure kettle with a polytetrafluoroethylene liner, sealing and storing in an oven, and heating to 120 ℃ for reaction for 9 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate for 3 times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene (N-GO).
(2) Modification of molybdate radical by ionization
Adding 0.5g N-GO powder into 500mL of deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding 0.25g of ammonium octamolybdate into the suspension, stirring at room temperature for reaction for 5 hours, performing suction filtration on a product, and washing with deionized water for 3 times to remove redundant reagents to obtain the functionalized graphene product.
Example 2
Preparing functionalized graphene:
(1) nitridation of Graphene Oxide (GO)
Adding 3g of GO into 100g of DMF, performing ultrasonic treatment at room temperature for 40 minutes, adding 60g of p-phenylenediamine, uniformly mixing, transferring into a high-pressure kettle with a polytetrafluoroethylene lining, sealing and storing in an oven, and heating to 220 ℃ for reaction for 3 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate for 3 times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene (N-GO).
(2) Modification of molybdate radical by ionization
Adding 2g N-GO powder into 100mL of deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding 4g of calcium molybdate into the suspension, stirring at room temperature for reaction for 5 hours, performing suction filtration on a product, and washing with deionized water for 3 times to remove redundant reagents to obtain the functionalized graphene product.
Example 3
Preparing functionalized graphene:
(1) nitridation of Graphene Oxide (GO)
Adding 1.5g of GO into 100g of DMF, carrying out ultrasonic treatment for 40 minutes at room temperature, adding 35g of p-o-phenylenediamine, uniformly mixing, transferring into a high-pressure kettle with a polytetrafluoroethylene liner, sealing and storing in an oven, and heating to 180 ℃ for reaction for 5 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate for 3 times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene (N-GO).
(2) Modification of molybdate radical by ionization
Adding 1.5g N-GO powder into 300mL of deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding 2.5g of zinc molybdate into the suspension, stirring at room temperature for reaction for 5 hours, performing suction filtration on a product, and washing with deionized water for 3 times to remove redundant reagents to obtain the functionalized graphene product.
Example 4
Preparing functionalized graphene:
(1) nitridation of Graphene Oxide (GO)
Adding 1.8g of GO into 100g of DMF, carrying out ultrasonic treatment for 40 minutes at room temperature, adding 30g of p-hexamethylenediamine, uniformly mixing, transferring into an autoclave with a polytetrafluoroethylene liner, sealing and storing in an oven, and heating to 160 ℃ for reaction for 7 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate for 3 times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene (N-GO).
(2) Modification of molybdate radical by ionization
Adding 1.6g N-GO powder into 200mL of deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding 2.8g of cobalt molybdate into the suspension, stirring at room temperature for reaction for 5 hours, performing suction filtration on a product, and washing with deionized water for 3 times to remove redundant reagents to obtain the functionalized graphene product.
Example 5
Preparing a TPU antistatic composite material:
the functionalized graphene was prepared in the same manner as in example 1. 100 parts of TPU resin, 3 parts of tricresyl phosphate, 15 parts of melamine polyphosphate, 0.5 part of functionalized graphene, 0.2 part of antioxidant 1076, 0.1 part of ultraviolet absorbent (UV-24), 2 parts of conductive carbon black, 0.5 part of stearic acid and 0 part of conductive carbon blackAdding 1 part of 8-hydroxyquinolinone into a plastic vertical stirrer, stirring and dispersing for 1 hour, adding into an extruder through an automatic feeder, and extruding and granulating at the processing temperature of 180-230 ℃ to obtain the functionalized graphene modified TPU antistatic composite material. The tensile strength of the material is 57.8MPa, and the surface resistance is 5.6 multiplied by 106 Omega, an oxygen index of 27.9%, smoke density grade 94。
Example 6
Preparing a TPU antistatic composite material:
the functionalized graphene was prepared in the same manner as in example 2. Adding 100 parts of TPU resin, 8 parts of tricresyl phosphate, 5 parts of melamine polyphosphate, 2 parts of functionalized graphene, 2 parts of antioxidant 1076, 1 part of ultraviolet absorber (UV-24), 8 parts of conductive carbon black, 2 parts of stearic acid and 0.3 part of 8-hydroxyquinolinone into a plastic vertical stirrer, stirring and dispersing for 1 hour, adding into an extruder through an automatic feeder, and extruding and granulating at the processing temperature of 180-230 ℃ to obtain the functionalized graphene modified TPU antistatic composite material. The tensile strength of the material is measured to be 68.4MPa, and the surface resistance is measured to be 3.1 multiplied by 103Omega, oxygen index 30.2%, smoke density grade 61.
Example 7
Preparing a TPU antistatic composite material:
the functionalized graphene was prepared in the same manner as in example 3. Adding 100 parts of TPU resin, 6 parts of tricresyl phosphate, 10 parts of melamine polyphosphate, 1 part of functionalized graphene, 1 part of antioxidant 1076, 0.5 part of ultraviolet absorber (UV-24), 6 parts of conductive carbon black, 2 parts of stearic acid and 0.1 part of 8-hydroxyquinolinone into a plastic vertical stirrer, stirring and dispersing for 1 hour, adding into an extruder through an automatic feeder, and extruding and granulating at the processing temperature of 180-230 ℃ to obtain the functionalized graphene modified TPU antistatic composite material. The tensile strength of the material is measured to be 63.7MPa, and the surface resistance is measured to be 4.2 multiplied by 104 Omega, oxygen index 29.2%, smoke density Degree rating of 72。
For comparison, the functionalized graphene in the formulation of the functionalized graphene modified TPU antistatic composite material of example 7 is replaced by ammonium octamolybdate with the same amount of common smoke suppressant, and the obtained TPU antistatic composite material has the following performance test results:
the preparation process of the TPU antistatic composite material is the same as that of the embodiment 7, wherein the TPU antistatic composite material comprises 100 parts of TPU resin, 6 parts of tricresyl phosphate, 10 parts of melamine polyphosphate, 1 part of ammonium octamolybdate, 1 part of antioxidant 1076, 0.5 part of ultraviolet absorbent (UV-24), 6 parts of conductive carbon black, 2 parts of stearic acid and 0.1 part of 8-hydroxyquinolinone; the functionalized graphene modified TPU antistatic composite material comprises the following components in parts by weight: the formulation and preparation were the same as in example 7.
Compared with the conventional smoke suppressant ammonium octamolybdate, the functionalized graphene used in the invention has a better reinforcing effect on the TPU antistatic composite material; from the aspect of conductivity, compared with the conventional smoke suppressant ammonium octamolybdate, the functionalized graphene used in the invention has a better conductive modification effect on the TPU antistatic composite material, so that a better antistatic effect can be obtained; compared with the smoke suppressant ammonium octamolybdate, the functionalized graphene used in the invention has better flame retardant and smoke suppressant effects on TPU antistatic composite materials. The functionalized graphene has the advantages of good flame-retardant smoke suppression effect, high mechanical strength, good antistatic property and the like on TPU antistatic composite materials, and plays an important role in widening the application of the TPU antistatic composite materials in the industries of electronic appliances, automobiles, buildings, precision instruments and the like.
Claims (6)
1. The flame-retardant smoke-inhibiting thermoplastic polyurethane antistatic composite material is characterized by being prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 3-8 parts of tricresyl phosphate, 5-15 parts of melamine polyphosphate, 0.5-2 parts of functionalized graphene, 0.2-2 parts of antioxidant 1076, 0.1-1 part of ultraviolet absorbent UV-24, 2-8 parts of conductive carbon black, 0.5-2 parts of stearic acid and 0.1-0.3 part of 8-hydroxyquinolinone; the functionalized graphene is prepared by the following method:
(1) nitridation of graphene oxide GO
Adding GO into dimethylformamide DMF, carrying out ultrasonic treatment for 40 minutes at room temperature, adding an amine compound, uniformly mixing, transferring into a high-pressure kettle containing a polytetrafluoroethylene lining, sealing and storing in an oven, heating to 120-220 ℃, and reacting for 3-9 hours; after the reaction is finished, carrying out suction filtration, washing the precipitate for multiple times by using methanol, and then carrying out vacuum filtration and drying to obtain a product, namely the nitrogenated graphene N-GO;
(2) modification of molybdate radical by ionization
Adding N-GO powder into deionized water, performing ultrasonic dispersion at room temperature for 3 hours to obtain a suspension, adding molybdate into the suspension, stirring and reacting at room temperature for 5 hours, performing suction filtration on a product, and washing with deionized water for multiple times to remove redundant reagents to obtain the functionalized graphene.
2. The flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material according to claim 1, wherein the mass ratio of DMF, GO and amine compounds in step (1) is 1: 0.005-0.03: 0.05 to 0.6.
3. The flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material according to claim 1, wherein the amine compound in the step (1) is p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, ethylenediamine or hexamethylenediamine.
4. The flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material according to claim 1, wherein the mass ratio of the deionized water, the N-GO and the molybdate in the step (2) is 1: 0.001-0.02: 0.005-0.04.
5. The flame retardant, smoke suppressing thermoplastic polyurethane antistatic composite of claim 1 wherein the molybdate in step (2) is ammonium octamolybdate, zinc molybdate, calcium molybdate, or cobalt molybdate.
6. The method for preparing the flame-retardant smoke-suppressing thermoplastic polyurethane antistatic composite material as claimed in any one of claims 1 to 5, wherein all the raw materials are added into a plastic vertical stirrer according to the proportion, stirred and dispersed for 1 hour, added into an extruder through an automatic feeder, extruded and granulated at the processing temperature of 180 ℃ to 230 ℃, and the obtained granules are the flame-retardant smoke-suppressing TPU antistatic composite material.
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| CN104479339A (en) * | 2014-12-22 | 2015-04-01 | 东莞市安高瑞新材料科技有限公司 | Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof |
| CN105153564A (en) * | 2015-10-21 | 2015-12-16 | 山东科技大学 | Graphene-molybdenum oxide nano flame-retardant composite material |
| CN108410161A (en) * | 2018-01-15 | 2018-08-17 | 东莞市安拓普塑胶聚合物科技有限公司 | A kind of fire-retardant TPU cable jacket materials and preparation method thereof with electro-magnetic screen function |
| CN108503895A (en) * | 2018-04-26 | 2018-09-07 | 台州学院 | Lanthanum loads the preparation method of organophosphor modification nitrogen-doped graphene and its flame-retardant modified ABS |
| CN109065874A (en) * | 2018-08-22 | 2018-12-21 | 深圳市创世达实业有限公司 | A kind of MoO3/ rGO-N nanocomposite and its preparation method and application |
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