CN113861664A - Wear-resistant flame-retardant TPU material and preparation method thereof - Google Patents
Wear-resistant flame-retardant TPU material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of TPU materials, and particularly discloses a wear-resistant flame-retardant TPU material and a preparation method thereof. The TPU material is prepared from the following raw materials in parts by weight: 60-100 parts of polyurethane, 15-30 parts of epoxy resin, 3-10 parts of di-o-chlorodiphenylamine methane, 20-50 parts of polyethylene, 10-28 parts of modified calcium sulfate dihydrate whisker, 10-28 parts of a composite flame retardant and 2-6 parts of silicone oil; the preparation method comprises the following steps: uniformly mixing silicon oil and the modified calcium sulfate dihydrate whisker to obtain a mixture A, uniformly mixing polyurethane, epoxy resin, di-o-chlorodiphenylamine methane and polyethylene to obtain a mixture B, adding the composite flame retardant into the mixture B, uniformly stirring to obtain a mixture C, and finally uniformly mixing the mixture A and the mixture C to obtain the wear-resistant flame-retardant TPU material. The application discloses wear-resisting fire-retardant TPU material, it has high wearability and high flame retardant's advantage.
Description
Technical Field
The application relates to the technical field of TPU materials, in particular to a wear-resistant flame-retardant TPU material and a preparation method thereof.
Background
The TPU is named as thermoplastic polyurethane elastomer rubber, and is a high molecular material formed by jointly reacting and polymerizing diisocyanate molecules such as diphenylmethane diisocyanate or toluene diisocyanate and the like with macromolecular polyol and low-molecular polyol. The TPU material has a relatively special soft-hard segment block copolymer structure, high strength and excellent mechanical properties, compared with other elastic materials, the TPU material has a wider hardness range, can be processed again, and has outstanding bearing capacity, impact resistance and shock absorption performance.
At present, the TPU in the related art generally has good comprehensive properties in the aspects of elasticity, mechanics and the like, but the surface of the TPU is abraded in the long-term use process of the TPU, so that the service life of the TPU is influenced.
Disclosure of Invention
In order to improve the wear resistance and the flame retardance of the TPU material, the application provides a wear-resistant flame-retardant TPU material and a preparation method thereof.
In a first aspect, the application provides a wear-resistant flame-retardant TPU material, which adopts the following technical scheme:
a wear-resistant flame-retardant TPU material is prepared from the following raw materials in parts by weight: 60-100 parts of polyurethane, 15-30 parts of epoxy resin, 3-10 parts of di-o-chlorodiphenylamine methane, 20-50 parts of polyethylene, 10-28 parts of modified calcium sulfate dihydrate whisker, 10-28 parts of a composite flame retardant and 2-6 parts of silicone oil;
the modified calcium sulfate dihydrate crystal whisker is obtained by modifying calcium sulfate dihydrate crystal whisker with tetrabutyl titanate.
By adopting the technical scheme, the wear-resistant flame-retardant TPU material has the advantages that the prepared TPU material has good wear resistance, tensile strength and flame retardance through the synergistic effect of the raw materials, and the volume abrasion loss is 48-60mm3The tensile strength is 41.9-45.6MPa,the flame retardant rating was V-0.
The polyurethane is an environment-friendly base material, is an elastomer which can be plasticized by heating and can be dissolved by a solvent, has excellent mechanical properties such as high strength, high toughness and oil resistance, and has good processability and good miscibility. The epoxy resin is a thermosetting resin, has good chemical activity of epoxy groups, can be subjected to ring opening by using a plurality of compounds containing active hydrogen, is cured and crosslinked to form a net structure, has excellent alkali resistance and good heat resistance and electrical insulation, can be used as a curing agent when being applied to the raw materials of TPU materials, and can also improve the heat resistance. The di-o-chlorodiphenylamine methane is used as a vulcanizing agent of polyurethane, and can also be used for curing epoxy resin, and the epoxy resin is added into the raw material of the TPU material, so that the curing of the polyurethane can be accelerated, and the forming can be accelerated. The polyethylene is thermoplastic resin, has excellent low-temperature resistance, good chemical stability, resistance to most of acid and alkali erosion and excellent electrical insulation, and can improve the insulation and wear resistance of the TPU material when being applied to the raw material of the TPU material.
The calcium sulfate dihydrate whisker has uniform cross section, complete appearance and fibrous structure, is a single crystal fibrous material, has good rigidity, stability and thermal stability, also has high strength, can enhance the tensile strength of the TPU material, and has good toughness, high insulativity, acid and alkali resistance and wear resistance. The calcium sulfate dihydrate crystal whisker is modified and then applied to the raw material of the TPU material, and the tensile strength and the wear resistance of the TPU material can be enhanced through the synergistic effect between the calcium sulfate dihydrate crystal whisker and polyurethane. The composite flame retardant has good flame retardant property, and can increase the flame retardance of the TPU material by being added into the raw materials of the TPU material, so that the TPU material has good high-temperature resistance. The silicone oil has good chemical stability, insulativity, hydrophobicity, physiological inertia, smaller surface tension and higher compression resistance, is applied to the raw materials of the TPU material, and can better enhance the wear resistance and flame retardance of the TPU material through the synergistic effect with other raw materials.
Preferably, the feed additive is prepared from the following raw materials in parts by weight: 65-85 parts of polyurethane, 18-26 parts of epoxy resin, 5-8 parts of di-o-chlorodiphenylamine methane, 30-40 parts of polyethylene, 15-23 parts of modified calcium sulfate dihydrate whisker, 15-23 parts of a composite flame retardant and 3-5 parts of silicone oil.
By adopting the technical scheme, the weight ratio of the polyurethane, the epoxy resin, the di-o-chlorodiphenylamine methane, the polyethylene, the modified calcium sulfate dihydrate whisker, the composite flame retardant and the silicone oil is optimized, and the wear resistance and the flame retardance of the TPU material can be improved.
Preferably, the modified calcium sulfate dihydrate whisker is prepared by the following method:
s1: mixing calcium oxide and water uniformly to obtain calcium hydroxide suspension, and stirring at 70-80 deg.C for 25-35 min;
s2: heating the calcium hydroxide suspension to 90-100 ℃, stirring, simultaneously dripping concentrated sulfuric acid into the calcium hydroxide suspension at the flow rate of 1-3mL/min for 30-40min, then preserving the temperature for 35-45min, cooling, carrying out suction filtration, and drying filter residues to constant weight to obtain calcium sulfate dihydrate whiskers;
s3: putting the calcium sulfate dihydrate crystal whisker into an ethanol solution to prepare calcium sulfate dihydrate crystal whisker suspension with the concentration of 8-10 percent, then heating to 75-85 ℃, then adding tetrabutyl titanate into the calcium sulfate dihydrate crystal whisker suspension, stirring for 55-65min, then filtering, and drying filter residue at the temperature of (-10) -0KPa and 180-220 ℃ for 10-14h to prepare the modified calcium sulfate dihydrate crystal whisker.
By adopting the technical scheme, firstly, calcium oxide, water and concentrated sulfuric acid are used for preparing the calcium sulfate dihydrate crystal whisker, then tetrabutyl titanate is used for modifying the calcium sulfate dihydrate crystal whisker, the tetrabutyl titanate is used as a coupling agent, and the wear resistance of the calcium sulfate dihydrate crystal whisker is improved by modifying fibers in the calcium sulfate dihydrate crystal whisker; the modified calcium sulfate dihydrate crystal whisker is prepared by using the raw materials, has the advantage of simple and convenient preparation, and can better play a role.
Preferably, the calcium oxide: the weight ratio of water is (10-12): (90-100), wherein the mass concentration of the ethanol solution is 70-75%, and the addition amount of the tetrabutyl titanate is 1-2wt% of the calcium sulfate dihydrate whisker in the step S3.
By adopting the technical scheme, the weight of the calcium oxide, the water and the tetrabutyl titanate is limited, so that the operation of operators is facilitated, and the modified calcium sulfate dihydrate crystal whisker can be better played.
Preferably, the composite flame retardant is prepared by the following method: respectively drying ammonium polyphosphate, graphite powder and pentaerythritol to remove water, then mixing the ammonium polyphosphate and the pentaerythritol, stirring for 10-15min at the temperature of 170-180 ℃, then adding the graphite powder, continuously stirring for 15-25min, and cooling to obtain the composite flame retardant;
wherein, ammonium polyphosphate: graphite powder: the weight ratio of the pentaerythritol is (10-15): (2-5): (5-10).
By adopting the technical scheme, the ammonium polyphosphate is an acid source, has high flame retardance, dimensional stability, hydrolysis resistance and heat resistance, has the function of expansion flame retardance, can be used as an acid source and an air source of an expansion system, belongs to an expansion type fireproof material, and is a high-efficiency phosphorus non-halogen smoke-eliminating flame retardant which is safe to use. The graphite powder is a synergistic flame-retardant smoke inhibitor, and a protective layer can be formed on the surface of the TPU material by adding the graphite powder, so that the diffusion and the release of pyrolysis products to the outside are slowed down, and the flame retardant property of the TPU material can be enhanced. Pentaerythritol is used as a carbon source, a carbon layer can be formed during heating, and the flame retardance can be improved through the synergistic effect of the pentaerythritol, ammonium polyphosphate and graphite powder. The composite flame retardant is prepared by using the raw materials, so that the composite flame retardant not only has the advantage of simple and convenient preparation, but also can better play a role.
Preferably, the raw materials of the TPU material also comprise 2 to 5 weight parts of nano alumina and 0.6 to 2 weight parts of fly ash floating beads.
By adopting the technical scheme, the nano-alumina has good dispersibility and good adsorbability, can promote the vulcanization, activation and reinforcement anti-aging effects of TPU, is applied to the raw materials of TPU materials, and can improve the tearing resistance and the wear resistance. The fly ash floating bead is a hollow sphere, has strong heat shielding capability and is filled with inert gas, the luminous flux can be increased under the flameless or flame condition, the generation of substances such as smoke particles is inhibited, and the fly ash floating bead has the characteristics of high temperature resistance, heat insulation, flame retardance and the like, and can improve the flame retardance through the synergistic effect with other raw materials.
In a second aspect, the application provides a preparation method of a wear-resistant flame-retardant TPU material, which adopts the following technical scheme: a preparation method of a wear-resistant flame-retardant TPU material comprises the following steps:
s1: adding silicone oil into the modified calcium sulfate dihydrate crystal whisker, uniformly mixing, and stirring for 10-20min to obtain a mixture A;
s2: uniformly mixing polyurethane, epoxy resin, polyethylene and di-o-chlorodiphenylamine methane, and stirring at the temperature of 220-240 ℃ for 2.5-3.5h to obtain a mixture B;
s3: adding the composite flame retardant into the mixture B, cooling to 150-160 ℃, and stirring for 1-2h to obtain a mixture C;
s4: and adding the mixture A into the mixture C, keeping the temperature, stirring for 1-2h, and cooling to obtain the wear-resistant flame-retardant TPU material.
Through adopting above-mentioned technical scheme, at first mix silicon oil and modified calcium sulfate dihydrate whisker, silicon oil can coat on the surface of modified calcium sulfate dihydrate whisker, further strengthen the wearability of modified calcium sulfate dihydrate, then mix polyurethane, epoxy, polyethylene, di o-chloro diphenylamine methane, add compound fire retardant again, help making the raw materials mixed more evenly, finally add the silicon oil and the modified calcium sulfate dihydrate whisker that accomplish of mixing again, can make the more even that each raw materials mixes, be convenient for modified calcium sulfate dihydrate whisker and compound fire retardant better performance, can strengthen the wearability and the fire resistance of TPU material more.
Preferably, when the mixture A is added into the mixture C, 2 to 5 weight parts of nano alumina and 0.6 to 2 weight parts of fly ash floating bead are added together.
By adopting the technical scheme, the nano alumina can improve the wear resistance, the fly ash floating bead can improve the flame retardance and enhance the comprehensive performance.
In summary, the present application has the following beneficial effects:
1. because this application adopts modified calcium sulfate dihydrate whisker, modified calcium sulfate dihydrate whisker has fibrous structure, has good rigidity, intensity, through with the polyurethane between the synergistic effect, has improved the wear resistance of TPU material more.
2. The composite flame retardant is an intumescent flame retardant, achieves better flame retardant effect through the synergistic effect of ammonium polyphosphate, graphite powder and pentaerythritol, has good high temperature resistance, and can improve the flame retardant property of the TPU material.
3. The nano-alumina and the fly ash floating bead are added in the application, the tensile strength and the wear resistance are improved through the synergistic effect between the nano-alumina and the polyurethane, the main component of the fly ash floating bead is silicate, the fly ash floating bead is a hollow sphere, the heat insulation is strong, the interior of the fly ash floating bead is filled with inert gas, the fly ash floating bead is applied to the raw material of the TPU material, the performance of the TPU material can be greatly improved, and the TPU material has better flame retardance and high temperature resistance.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
The polyurethane is selected from the group consisting of porch bohai polyurethane ltd; the epoxy resin is selected from the group consisting of Jinan oasis composite materials, Inc.; the di-o-chlorodiphenylamine methane is selected from Hefei Tianjian chemical company Limited; the polyethylene is selected from Sichuan Jinsen rubber Co., Ltd; the silicone oil is selected from Shandongxin Runjin chemical Co., Ltd; the tetrabutyl titanate is selected from the chemical industry Co., Ltd of tin-free commercial department; the ammonium polyphosphate is selected from Shandong Kepler Biotech limited; the graphite powder is selected from the good resource chemical liability company of Dongying city; pentaerythritol is selected from Shandong Maojun chemical technology Co., Ltd; the nano alumina is selected from Nantong Runfeng petrochemical company; the fly ash floating bead is selected from Hebei Hemiguang mineral products Co.
Preparation example
Preparation example 1
A modified calcium sulfate dihydrate whisker is prepared by the following method:
s1: uniformly mixing 10kg of calcium oxide and 90kg of water to obtain a calcium hydroxide suspension, and stirring the calcium hydroxide suspension at the temperature of 70 ℃ at the rotating speed of 150r/min for 25 min;
s2: heating the calcium hydroxide suspension to 90 ℃, stirring at a rotating speed of 380r/min, simultaneously dropwise adding concentrated sulfuric acid into the calcium hydroxide suspension at a flow rate of 1mL/min for 30min, then preserving heat for 35min, cooling, performing suction filtration, and drying filter residues at a temperature of 80 ℃ to constant weight to obtain calcium sulfate dihydrate whiskers;
s3: putting the calcium sulfate dihydrate crystal whiskers into an ethanol solution to prepare calcium sulfate dihydrate crystal whisker suspension with the concentration of the calcium sulfate dihydrate crystal whiskers being 8%, heating to 75 ℃, adding tetrabutyl titanate into the calcium sulfate dihydrate crystal whisker suspension, stirring for 55min, then filtering, washing filter residues for 3 times by using the ethanol solution, and drying the filter residues at the temperature of-10 KPa and 180 ℃ for 10h to prepare modified calcium sulfate dihydrate crystal whiskers;
wherein the mass concentration of the ethanol solution is 70 percent, and the addition amount of the tetrabutyl titanate is 1 weight percent of the calcium sulfate dihydrate crystal whisker in the step S3.
Preparation example 2
A modified calcium sulfate dihydrate whisker is prepared by the following method:
s1: uniformly mixing 11kg of calcium oxide and 95kg of water to obtain a calcium hydroxide suspension, and stirring the calcium hydroxide suspension at the temperature of 75 ℃ at the rotating speed of 200r/min for 30 min;
s2: heating the calcium hydroxide suspension to 95 ℃, stirring at the rotating speed of 400r/min, simultaneously dripping concentrated sulfuric acid into the calcium hydroxide suspension at the flow rate of 2mL/min for 35min, then preserving heat for 40min, cooling, performing suction filtration, and drying filter residues at the temperature of 90 ℃ to constant weight to prepare calcium sulfate dihydrate whiskers;
s3: putting the calcium sulfate dihydrate crystal whiskers into an ethanol solution to prepare a calcium sulfate dihydrate crystal whisker suspension with the concentration of the calcium sulfate dihydrate crystal whiskers being 9%, heating to 80 ℃, adding tetrabutyl titanate into the calcium sulfate dihydrate crystal whisker suspension, stirring for 60min, then filtering, washing filter residues for 4 times by using the ethanol solution, and drying the filter residues at the temperature of-5 KPa and 200 ℃ for 12h to prepare modified calcium sulfate dihydrate crystal whiskers;
wherein the mass concentration of the ethanol solution is 73 percent, and the addition amount of the tetrabutyl titanate is 1.5 percent by weight of the calcium sulfate dihydrate whisker in the step S3.
Preparation example 3
A modified calcium sulfate dihydrate whisker is prepared by the following method:
s1: uniformly mixing 12kg of calcium oxide with 100kg of water to obtain a calcium hydroxide suspension, and stirring the calcium hydroxide suspension at the temperature of 80 ℃ at the rotating speed of 250r/min for 35 min;
s2: heating the calcium hydroxide suspension to 100 ℃, stirring at a rotating speed of 420r/min, simultaneously dripping concentrated sulfuric acid into the calcium hydroxide suspension at a flow rate of 3mL/min for 40min, then preserving heat for 45min, cooling, performing suction filtration, and drying filter residues at a temperature of 100 ℃ to constant weight to obtain calcium sulfate dihydrate whiskers;
s3: putting the calcium sulfate dihydrate crystal whiskers into an ethanol solution to prepare a calcium sulfate dihydrate crystal whisker suspension with the concentration of 10 percent, heating to 85 ℃, adding tetrabutyl titanate into the calcium sulfate dihydrate crystal whisker suspension, stirring for 65min, then filtering, washing filter residues for 5 times by using the ethanol solution, and drying the filter residues for 14h at the temperature of 0KPa and 220 ℃ to prepare modified calcium sulfate dihydrate crystal whiskers;
wherein the mass concentration of the ethanol is 75 percent, and the addition amount of the tetrabutyl titanate is 2 weight percent of the calcium sulfate dihydrate crystal whisker in the step S3.
Preparation example 4
A composite flame retardant is prepared by the following steps:
respectively drying 10kg of ammonium polyphosphate, 2kg of graphite powder and 5kg of pentaerythritol at the temperature of 70 ℃ for 8h, then mixing the ammonium polyphosphate and the pentaerythritol, stirring at the temperature of 170 ℃ at the rotating speed of 140r/min for 10min, then adding the graphite powder, continuously stirring for 15min, and then cooling to obtain the composite flame retardant.
Preparation example 5
A composite flame retardant is prepared by the following steps:
respectively drying 13kg of ammonium polyphosphate, 3kg of graphite powder and 7kg of pentaerythritol at the temperature of 75 ℃ for 10h, then mixing the ammonium polyphosphate and the pentaerythritol, stirring at the temperature of 175 ℃ for 13min at the rotating speed of 150r/min, then adding the graphite powder, continuously stirring for 20min, and then cooling to obtain the composite flame retardant.
Preparation example 6
A composite flame retardant is prepared by the following steps:
respectively drying 15kg of ammonium polyphosphate, 5kg of graphite powder and 10kg of pentaerythritol at the temperature of 90 ℃ for 12h, mixing the ammonium polyphosphate and the pentaerythritol, stirring at the temperature of 180 ℃ at the rotating speed of 160r/min for 15min, adding the graphite powder, continuously stirring for 25min, and then cooling to obtain the composite flame retardant.
Examples
TABLE 1 weight of each raw material (unit: Kg) of TPU materials in examples 1-6
Example 1
The wear-resistant flame-retardant TPU material comprises the raw materials in the proportion shown in Table 1.
The modified calcium sulfate dihydrate whisker is prepared by the method in preparation example 1, and the composite flame retardant is prepared by the method in preparation example 4.
A preparation method of a wear-resistant flame-retardant TPU material comprises the following steps:
s1: adding silicone oil into the modified calcium sulfate dihydrate crystal whisker, uniformly mixing, and stirring for 10min to obtain a mixture A;
s2: uniformly mixing polyurethane, epoxy resin, polyethylene and di-o-chlorodiphenylamine methane, and stirring at the temperature of 220 ℃ for 2.5 hours to obtain a mixture B;
s3: adding the composite flame retardant into the mixture B, cooling to 150 ℃, and stirring for 1h to obtain a mixture C;
s4: and adding the mixture A into the mixture C, keeping the temperature, stirring for 1h, and cooling to room temperature to obtain the wear-resistant flame-retardant TPU material.
Examples 2 to 6
The wear-resistant flame-retardant TPU material is different from the TPU material in the raw material ratio shown in the table 1.
Example 7
The wear-resistant flame-retardant TPU material is different from the TPU material in example 3 in the source of modified calcium sulfate dihydrate whiskers, and is prepared by adopting the preparation example 2.
Example 8
The wear-resistant flame-retardant TPU material is different from the TPU material in example 3 in the source of modified calcium sulfate dihydrate whiskers, and is prepared by adopting the preparation example 3.
Example 9
The wear-resistant flame-retardant TPU material is different from the TPU material in example 8 in the source of the composite flame retardant in the raw materials of the TPU material, and is prepared by adopting the preparation example 5.
Example 10
The wear-resistant flame-retardant TPU material is different from the TPU material in example 8 in the source of the composite flame retardant in the raw materials of the TPU material, and is prepared by adopting the preparation example 6.
Example 11
An abrasion-resistant flame-retardant TPU material which differs from that of example 9 in the method of preparation of the TPU material.
A preparation method of a wear-resistant flame-retardant TPU material comprises the following steps:
s1: adding silicone oil into the modified calcium sulfate dihydrate crystal whisker, uniformly mixing, and stirring for 15min to obtain a mixture A;
s2: uniformly mixing polyurethane, epoxy resin, polyethylene and di-o-chlorodiphenylamine methane, and stirring at the temperature of 230 ℃ for 3 hours to obtain a mixture B;
s3: adding the composite flame retardant into the mixture B, cooling to 155 ℃, and stirring for 1.5h to obtain a mixture C;
s4: and adding the mixture A into the mixture C, keeping the temperature, stirring for 1.5h, and cooling to room temperature to obtain the wear-resistant flame-retardant TPU material.
Example 12
An abrasion-resistant flame-retardant TPU material which differs from that of example 9 in the method of preparation of the TPU material.
A preparation method of a wear-resistant flame-retardant TPU material comprises the following steps:
s1: adding silicone oil into the modified calcium sulfate dihydrate crystal whisker, uniformly mixing, and stirring for 20min to obtain a mixture A;
s2: uniformly mixing polyurethane, epoxy resin, polyethylene and di-o-chlorodiphenylamine methane, and stirring at the temperature of 240 ℃ for 3.5 hours to obtain a mixture B;
s3: adding the composite flame retardant into the mixture B, cooling to 160 ℃, and stirring for 2 hours to obtain a mixture C;
s4: and adding the mixture A into the mixture C, keeping the temperature, stirring for 2 hours, and cooling to room temperature to obtain the wear-resistant flame-retardant TPU material.
TABLE 2 weight of each raw material (unit: Kg) of TPU materials in examples 13-15
| Raw materials | Example 13 | Example 14 | Example 15 |
| Polyurethane | 100 | 100 | 100 |
| Epoxy resin | 30 | 30 | 30 |
| Di-o-chloro-diphenylamine methane | 10 | 10 | 10 |
| Polyethylene | 50 | 50 | 50 |
| Modified calcium sulfate dihydrate whisker | 28 | 28 | 28 |
| Composite flame retardant | 28 | 28 | 28 |
| Silicone oil | 6 | 6 | 6 |
| Nano alumina | 2 | 4 | 5 |
| Flyash floating bead | 0.6 | 1.3 | 2 |
Example 13
The wear-resistant flame-retardant TPU material is different from the TPU material in the embodiment 12 in that the raw materials of the TPU material are added with nano alumina and fly ash floating beads, and the preparation methods are different: when the mixture A is added into the mixture C, nano alumina and fly ash floating beads are added together, and the raw material ratio is shown in Table 2.
Wherein, the modified calcium sulfate dihydrate crystal whisker is prepared by the preparation example 3, and the composite flame retardant is prepared by the preparation example 5.
Examples 14 to 15
The wear-resistant flame-retardant TPU material is different from the TPU material in the raw material ratio shown in Table 2.
Comparative example
Comparative example 1
An abrasion-resistant flame-retardant TPU material which differs from that of example 12 in that the modified calcium sulfate dihydrate whiskers are replaced with an equal amount of polyurethane in the raw material of the TPU material.
Comparative example 2
An abrasion-resistant flame-retardant TPU material which differs from that of example 12 in that the composite flame retardant is replaced by an equal amount of polyurethane in the raw materials of the TPU material.
Comparative example 3
A wear-resistant flame-retardant TPU material, which differs from that of example 12 in that the modified calcium sulfate dihydrate whisker and the composite flame retardant are replaced with the same amount of polyurethane in the raw material of the TPU material.
Comparative example 4
A wear-resistant flame-retardant TPU material, which differs from that of example 12 in that the modified calcium sulfate dihydrate whisker is replaced with an equal amount of calcium sulfate dihydrate whisker in the raw material of the TPU material;
wherein, the calcium sulfate dihydrate crystal whisker is prepared by the following method:
s1: uniformly mixing 12kg of calcium oxide with 100kg of water to obtain a calcium hydroxide suspension, and stirring the calcium hydroxide suspension at the temperature of 80 ℃ at the rotating speed of 250r/min for 35 min;
s2: heating the calcium hydroxide suspension to 100 ℃, stirring at the rotating speed of 420r/min, simultaneously dripping concentrated sulfuric acid into the calcium hydroxide suspension at the flow rate of 3mL/min for 40min, then preserving the heat for 45min, then cooling, carrying out suction filtration, and drying the filter residue at the temperature of 100 ℃ to constant weight to obtain the calcium sulfate dihydrate whisker.
Performance test
The following property tests were carried out on the TPU materials obtained in examples 1 to 15 and comparative examples 1 to 4, and the test results are shown in Table 3.
Carrying out abrasion resistance detection on the TPU material according to GB/T9867-2008 'determination of abrasion resistance of vulcanized rubber or thermoplastic rubber (rotary drum type abrasion machine method)'; testing the tensile strength of the TPU material according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber; the TPU material was tested for combustion performance according to UL94 flame retardant rating test Standard and method, with the test results shown in Table 3.
TABLE 3 test results
As can be seen from Table 3, the wear-resistant flame-retardant TPU material disclosed by the application can enable the prepared TPU material to have good wear resistance, tensile strength and flame retardance through the synergistic effect of the raw materials, and the volume abrasion loss is 48-60mm3The tensile strength is 41.9-45.6MPa, and the flame retardant rating is V-0.
Comparing with the embodiment 12 and the comparative example 1, it can be seen that, the modified calcium sulfate dihydrate whisker is not added in the raw material of the TPU material, so that the volume abrasion loss and the tensile strength are obviously reduced, and the modified calcium sulfate dihydrate whisker can improve the wear resistance of the TPU material.
Comparing with the example 12 and the comparative example 2, it can be seen that, in the raw materials of the TPU material, the flame retardant grade is obviously reduced without adding the composite flame retardant, and the volume abrasion and the tensile strength are also reduced, so that the composite flame retardant can improve the flame retardant property of the TPU material.
Comparing with the embodiment 12 and the comparative example 3, it can be seen that, the modified calcium sulfate dihydrate whisker and the composite flame retardant are not added in the raw materials of the TPU material, so that the volume abrasion loss and the tensile strength of the TPU material are obviously reduced, the flame retardant grade is reduced, and the wear resistance and the flame retardancy of the TPU material can be further improved through the synergistic effect between the modified calcium sulfate dihydrate whisker and the composite flame retardant.
Comparing with the embodiment 12 and the comparative example 4, it can be seen that, compared with the calcium sulfate dihydrate whisker, the modified calcium sulfate dihydrate whisker added to the raw material of the TPU material has lower volume abrasion loss and better tensile strength, thereby showing that the modified calcium sulfate dihydrate whisker can improve the wear resistance of the TPU material.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A wear-resistant flame-retardant TPU material is characterized in that: the composition is prepared from the following raw materials in parts by weight: 60-100 parts of polyurethane, 15-30 parts of epoxy resin, 3-10 parts of di-o-chlorodiphenylamine methane, 20-50 parts of polyethylene, 10-28 parts of modified calcium sulfate dihydrate whisker, 10-28 parts of a composite flame retardant and 2-6 parts of silicone oil;
the modified calcium sulfate dihydrate crystal whisker is obtained by modifying calcium sulfate dihydrate crystal whisker with tetrabutyl titanate.
2. A wear resistant flame retardant TPU material as set forth in claim 1 wherein: the composition is prepared from the following raw materials in parts by weight: 65-85 parts of polyurethane, 18-26 parts of epoxy resin, 5-8 parts of di-o-chlorodiphenylamine methane, 30-40 parts of polyethylene, 15-23 parts of modified calcium sulfate dihydrate whisker, 15-23 parts of a composite flame retardant and 3-5 parts of silicone oil.
3. A wear resistant flame retardant TPU material as set forth in claim 1 wherein: the modified calcium sulfate dihydrate whisker is prepared by the following method:
s1: mixing calcium oxide and water uniformly to obtain calcium hydroxide suspension, and stirring at 70-80 deg.C for 25-35 min;
s2: heating the calcium hydroxide suspension to 90-100 ℃, stirring, simultaneously dripping concentrated sulfuric acid into the calcium hydroxide suspension at the flow rate of 1-3mL/min for 30-40min, then preserving the temperature for 35-45min, cooling, carrying out suction filtration, and drying filter residues to constant weight to obtain calcium sulfate dihydrate whiskers;
s3: putting the calcium sulfate dihydrate crystal whisker into an ethanol solution to prepare calcium sulfate dihydrate crystal whisker suspension with the concentration of 8-10 percent, then heating to 75-85 ℃, then adding tetrabutyl titanate into the calcium sulfate dihydrate crystal whisker suspension, stirring for 55-65min, then filtering, and drying filter residue at the temperature of (-10) -0KPa and 180-220 ℃ for 10-14h to prepare the modified calcium sulfate dihydrate crystal whisker.
4. A wear resistant flame retardant TPU material as set forth in claim 3 wherein: the calcium oxide: the weight ratio of water is (10-12): (90-100), wherein the mass concentration of the ethanol solution is 70-75%, and the addition amount of the tetrabutyl titanate is 1-2wt% of the calcium sulfate dihydrate whisker in the step S3.
5. A wear resistant flame retardant TPU material as set forth in claim 1 wherein: the composite flame retardant is prepared by the following method: respectively drying ammonium polyphosphate, graphite powder and pentaerythritol to remove water, then mixing the ammonium polyphosphate and the pentaerythritol, stirring for 10-15min at the temperature of 170-180 ℃, then adding the graphite powder, continuously stirring for 15-25min, and cooling to obtain the composite flame retardant;
wherein, ammonium polyphosphate: graphite powder: the weight ratio of the pentaerythritol is (10-15): (2-5): (5-10).
6. A wear resistant flame retardant TPU material as set forth in claim 1 wherein: the TPU material also comprises 2-5 parts by weight of nano alumina and 0.6-2 parts by weight of fly ash floating beads.
7. A method of making a wear resistant flame retardant TPU material as set forth in any one of claims 1 to 5 wherein:
s1: adding silicone oil into the modified calcium sulfate dihydrate crystal whisker, uniformly mixing, and stirring for 10-20min to obtain a mixture A;
s2: uniformly mixing polyurethane, epoxy resin, polyethylene and di-o-chlorodiphenylamine methane, and stirring at the temperature of 220-240 ℃ for 2.5-3.5h to obtain a mixture B;
s3: adding the composite flame retardant into the mixture B, cooling to 150-160 ℃, and stirring for 1-2h to obtain a mixture C;
s4: and adding the mixture A into the mixture C, keeping the temperature, stirring for 1-2h, and cooling to obtain the wear-resistant flame-retardant TPU material.
8. The preparation method of claim 7, wherein 2-5 parts by weight of nano alumina and 0.6-2 parts by weight of fly ash floating bead are added together when the mixture A is added into the mixture C.
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