CN113480844A - Preparation method of carbon nanotube reinforced polyurethane impact-resistant material - Google Patents
Preparation method of carbon nanotube reinforced polyurethane impact-resistant material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon nano tube reinforced polyurethane impact-resistant material, wherein the impact-resistant material is a PU-RIRM-CNT material, and the preparation method comprises the following steps: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube, by the above-mentioned three kinds of material complex. Compared with PU materials, the addition of RIRM and CNT materials obviously improves the storage modulus and the loss modulus of the PU materials, shows more excellent dynamic mechanical properties, and the vibration suppression effect of the PU-RIRM-CNT composite material under impact load is better than that of the traditional vibration suppression material.
Description
Technical Field
The invention relates to the technical field of impact-resistant protective materials, in particular to a preparation method and application of a carbon nano tube reinforced polyurethane impact-resistant material.
Background
Polyurethane (PU) is a complex high molecular compound polymerized from a variety of organic materials. As a buffering and energy absorbing material with excellent performance, the buffering and energy absorbing material shows excellent flexibility, thermal insulation, adhesion, rebound resilience, wear resistance, processability, elongation and chemical stability, and is widely used in the field of buffering and energy absorbing of various industries, but the buffering and energy absorbing material has the biggest defects of lower strength, poorer dynamic mechanical performance and larger deformation under the action of impact.
The Repairable Impact Reinforcement Material (RIRM) is a self-repairable energy-absorbing material with a shear thickening effect, which exhibits a flow transition state at a low strain rate, is transformed into a solid state to absorb energy when impacted, and can repair itself after being damaged by the impact. The composite material has good thermodynamic stability and viscoelasticity, and is widely applied to the fields of flame retardance, heat preservation, protection and the like, but the composite material has certain fluidity under the unstressed state, is difficult to be applied to industrial production, needs to be compounded with other polymers for use, and can improve the impact resistance of the polymers after being compounded.
Disclosure of Invention
In order to overcome the defects of strength and energy absorption of the polyurethane material, the invention provides a method for compounding a self-repairable energy-absorbing material and the polyurethane material, and the reinforcing effect of the self-repairable energy-absorbing material is improved by adding a carbon nanotube material, so that the problems of poor dynamic mechanical property and poor impact resistance of the polyurethane material are solved.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a carbon nano tube reinforced polyurethane impact-resistant material is characterized by comprising the following steps: the impact-resistant material is a PU-RIRM-CNT composite material; compounding RIRM and PU material into PU-RIRM material, and then adding CNT; wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube;
the preparation method of the PU comprises the following steps:
(1) putting polyester dihydric alcohol, diisocyanate and polytetrahydrofuran ether dihydric alcohol into a container, and uniformly mixing and reacting for 2-5h at the temperature of 75-90 ℃ to obtain a mixture A;
(2) adding 1, 4-butanediol into the mixture A, and uniformly mixing at the temperature of 75-90 ℃ to obtain a mixture B;
(3) heating the mould to 95-110 ℃, then pouring the mixture B into the mould, and demoulding after 1-2h to obtain a mixture C;
(4) the PU material is obtained after the mixture C is vulcanized for 10-15h at the temperature of 110-130 ℃.
Further, in the step (1) of the preparation method of PU, 10-30% of polyester diol, 20-30% of diisocyanate and 40-65% of polytetrahydrofuran ether diol are respectively weighed according to weight percentage;
in the step (2), adding 10-15 wt% of 1, 4-butanediol into the mixture A, and uniformly mixing at 75-85 ℃ to obtain a mixture B;
in the step (3), the mould is heated to 90-110 ℃, then the mixture B is poured into the mould, and demoulding treatment is carried out after 1-2h to obtain a mixture C;
in the step (4), the PU material is obtained after the mixture C is vulcanized for 10-15h at the temperature of 110-130 ℃.
Further, the weight ratio of PU, RIRM and CNT is 5-15: 0.2-3; the silicon-boron weight ratio of the RIRM is 1.2-5: 0.2-1.8.
Further, the weight ratio of PU, RIRM and CNT is 8-12: 0.6-2; the silicon-boron weight ratio of the RIRM is 1.8-3: 0.8-1.4.
The preparation steps of the RIRM comprise:
(1) sequentially adding water, petroleum ether, diphenyl silanediol, methyl triethoxysilane and hydroxyl silicone oil into a container, uniformly stirring, and heating to react at the temperature of 75-85 ℃ for 3-5h to obtain a mixture A;
(2) adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-90 ℃ for 5-9h to obtain a mixture B;
(3) cooling the mixture B to 23-28 ℃, and then washing with water for 5-8 times to obtain a mixture C;
(4) and (3) dehydrating and drying the mixture C to obtain the RIRM material.
Further, in the preparation step of the RIRM:
the water, the petroleum ether, the diphenyl silanediol, the methyl triethoxysilane and the hydroxyl silicone oil in the step (1) are 80-250: 60-200: 20-70: 5-30: 1-18 in parts by weight; the water is distilled water
In the step (2), the boric acid accounts for 5-25 parts by weight; adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-90 ℃ for 6-8h to obtain a mixture B;
in the step (3), the mixture B is cooled to room temperature and then is washed for 3-7 times by deionized water to obtain a mixture C;
in the step (4), the dehydration and drying treatment is performed by using a reduced pressure distillation apparatus.
The preparation method of the carbon nano tube reinforced polyurethane impact-resistant material comprises the following steps:
(1) uniformly mixing the PU material and the RIRM material to obtain a mixture A, namely a PU-RIRM material;
(2) adding CNT into the mixture A, and stirring uniformly to obtain a mixture B;
(3) placing the mixture B into a high-temperature internal mixer for internal mixing to obtain a mixture C;
(4) and granulating the mixture C to obtain the PU-RIRM-CNT impact-resistant reinforced material.
Further, in the step (3), the temperature of the high-temperature internal mixer is 180 ℃ and 250 ℃, and after internal mixing is carried out for 10-20min, a mixture C is obtained; in the step (4), granulating the mixture C by using a granulator at the temperature of 200-300 ℃ to obtain the PU-RIRM-CNT impact-resistant reinforced material; the preparation method of the carbon nanotube reinforced polyurethane impact-resistant material also comprises the following steps of: and taking a CNT raw material, and carrying out acid treatment and impurity removal treatment on the CNT raw material to obtain the CNT material.
The carbon nano tube reinforced polyurethane impact-resistant material is applied to the protection of fuze vibration in an impact environment.
The carbon nano tube reinforced polyurethane impact-resistant material is applied to the fine protection of structural vibration in an impact environment.
Carbon Nanotubes (CNTs) exhibit a wide range of applications in many fields, especially in the field of polymeric materials, due to their unique structure and excellent properties. As a high-strength and high-rigidity reinforced material with excellent mechanical properties, if a CNT reinforced material and a RIRM impact-resistant material are compounded with a PU material, various mechanical properties of the PU material can be well improved, and a novel impact-resistant reinforced material is obtained, so that the application field of the impact-resistant material is widened.
Based on a dynamic mechanical analyzer, the storage modulus and the loss modulus of the PU and PU-RIRM-CNT impact-resistant reinforced materials are measured, and the PU-RIRM-CNT impact-resistant reinforced materials are found to show more excellent dynamic mechanical properties. Then, the PU-RIRM-CNT impact-resistant reinforced material is used in the fuze vibration suppression field, the vibration suppression performance of the PU-RIRM-CNT impact-resistant reinforced material is researched by using an impact vibration test platform at the impact speed of 13m/s, and the shock suppression performance is compared with that of the traditional fuze vibration suppression material (epoxy resin).
The invention has the beneficial effects that: (1) compared with PU materials, the addition of RIRM and CNT materials obviously improves the storage modulus and loss modulus of the PU materials, has larger rigidity and damping, more excellent elasticity and viscosity and more excellent dynamic mechanical properties;
(2) the frequency domain curve of the epoxy resin shows a plurality of main frequencies, the PU-RIRM-CNT impact-resistant reinforced material only has one main frequency, and the vibration acceleration of the fuse under the protection of the PU-RIRM-CNT impact-resistant reinforced material is obviously reduced, so that the suppression effect of the PU-RIRM-CNT impact-resistant reinforced material on the fuse vibration under the impact load is more obvious.
(3) On the basis of the PU-RIRM-CNT impact-resistant reinforced material, the purposes of controlling the impact resistance and the reinforcing effect of the PU composite material can be achieved by adjusting the proportion of the RIRM material and the CNT material.
When the weight ratio of PU-RIRM-CNT is 5-15: 0.2-3, the addition of RIRM and CNT materials can obviously improve the dynamic mechanical property and vibration suppression property of PU materials.
When the weight ratio of PU-RIRM-CNT is beyond the range of 5-15: 0.2-3, the high proportion of RIRM can cause the composite material to become soft and even to be in a flowing state, which is not beneficial to molding application, and the low proportion of RIRM can reduce the agglomeration effect of the composite material to influence the enhancement effect of the composite material; high proportions of CNTs stiffen the composite reducing its flexibility, low proportions of CNTs softening the composite reducing its reinforcing effect, and finally significantly affecting the dynamic mechanical and vibration damping properties of the PU-RIRM-CNT composite.
Drawings
FIG. 1: storage modulus curves of PU material and PU-RIRM-CNT impact-resistant reinforced material;
FIG. 2: loss modulus curves for PU materials and PU-RIRM-CNT impact reinforcement materials;
FIG. 3: frequency domain curves for epoxy and PU-RIRM-CNT impact reinforcement:
FIG. 4: time domain curves of epoxy resin and PU-RIRM-CNT impact-resistant reinforcement material at 1.3-2.3kHz frequency;
FIG. 5: time domain plots of epoxy and PU-RIRM-CNT impact reinforcement at 12-13kHz frequencies;
FIG. 6: time domain plots of epoxy and PU-RIRM-CNT impact reinforcement at frequencies of 24.5-25.5 kHz.
The specific implementation mode is as follows:
the following description is only exemplary of the present invention and should not be construed as limiting the scope of the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Example 1:
(1) preparation of PU materials
Respectively weighing 25% of polyester dihydric alcohol, 30% of diisocyanate and 45% of polytetrahydrofuran ether dihydric alcohol by weight;
placing polyester dihydric alcohol, diisocyanate and polytetrahydrofuran ether dihydric alcohol into a round-bottom flask, and uniformly mixing and reacting for 3 hours at the temperature of 80 ℃ to obtain a mixture A;
③ adding 10 to 15 weight percent of 1, 4-butanediol into the mixture A, and uniformly mixing at the temperature of 80 ℃ to obtain a mixture B;
heating the mould to 100 ℃, pouring the mixture B into the mould, and demoulding after 1h to obtain a mixture C;
fifthly, vulcanizing the mixture C for 12 hours at the temperature of 120 ℃ to obtain a PU material;
sixthly, pouring part of the PU material into a mold at 120 ℃, pressing the PU material into a columnar PU material sample with the thickness of 0.63cm and the diameter of 1.46cm by using a pressing forming machine, and analyzing the dynamic mechanical properties.
(2) Preparation of RIRM materials
Weighing a certain amount of distilled water, diphenyl silanediol, methyl triethoxysilane, hydroxyl silicone oil and petroleum ether respectively;
adding 100mL of distilled water, 100g of petroleum ether, 48.8g of diphenyl silanediol, 17.8g of methyl triethoxysilane and 7.4g of hydroxyl silicone oil into a round-bottom flask in sequence, fully and uniformly stirring, and heating to react for 4 hours at the temperature of 80 ℃ in an oil bath to obtain a mixture A;
③ adding 12.4g of boric acid into the mixture A, fully and uniformly stirring, and then heating and reacting for 7 hours at the oil bath temperature of 85 ℃ to obtain a mixture B;
fourthly, cooling the mixture B to room temperature, and then washing the mixture B for 5 times by using deionized water to obtain a mixture C;
fifthly, placing the mixture C into a reduced pressure distillation device for dehydration and drying treatment to finally obtain the RIRM material with the silicon-boron ratio of 2: 1.
(3) Preparation of PU-RIRM-CNT impact-resistant reinforced material
Firstly, removing impurities from the carbon nano tube by adopting a chemical synthesis method combining acid treatment and gas phase to obtain a purified CNT material;
uniformly mixing the PU material and the RIRM material according to the proportion of 10:1 (the anti-impact effect of the RIRM material is controlled by adjusting the RIRM proportion) to obtain a mixture A;
③ adding a certain amount of CNT material into the mixture A according to the proportion of PU: RIRM: CNT: 10:1:1 (the reinforcing effect is controlled by adjusting the proportion of CNT), and fully and uniformly stirring to obtain a mixture B.
Fourthly, placing the mixture B into a high-temperature internal mixer at the temperature of 200 ℃ for internal mixing for 10min to obtain a mixture C;
and fifthly, granulating the mixture C on a granulator at the temperature of 250 ℃ to obtain the PU-RIRM-CNT impact-resistant reinforced material.
Sixthly, cooling the PU-RIRM-CNT impact-resistant reinforcing material, putting part of the PU-RIRM-CNT impact-resistant reinforcing material into a mould, pressing the material into a cylindrical sample with the thickness of 0.63cm and the diameter of 1.46cm by using a pressing forming machine, and analyzing the dynamic mechanical properties;
and seventhly, filling a part of PU-RIRM-CNT impact-resistant reinforcing material into the fuse for researching the vibration suppression effect of the fuse under the impact load.
Example 2:
respectively pouring a part of the PU material and the PU-RIRM-CNT impact-resistant reinforced material prepared in the example 1 into a mold at 120 ℃, pressing the materials into columnar PU material and PU-RIRM-CNT impact-resistant reinforced material samples with the thickness of 0.63cm and the diameter of 1.46cm by using a pressing forming machine, and analyzing the dynamic mechanical properties;
the specific method comprises the following steps:
experimental preparation: preparing PU and PU-RIRM-CNT samples, and opening the equipment and a control interface thereof;
correcting and installing: calibrating the experimental equipment, installing an experimental sample, and measuring the size of the experimental sample;
beginning the experiment: setting equipment parameters and experimental test parameters, and carrying out dynamic mechanical analysis experiments;
and fourthly, finishing the experiment: PU and PU-RIRM-CNT were analyzed for storage modulus and loss modulus.
The storage modulus (or elastic modulus) represents the energy stored by the material due to elastic deformation under an external force, and the larger the storage modulus is, the larger the rigidity of the material is, and the better the elasticity is; the loss modulus (or viscous modulus) characterizes the energy dissipated by a material in the form of heat due to viscous deformation under an external force, and the larger the loss modulus, the larger the material damping, and the better the viscosity. As can be seen from the trend of the curves shown in FIGS. 1 and 2, the storage modulus and the loss modulus of PU and PU-RIRM-CNT increase with the increase of frequency, and PU-RIRM-CNT is significantly higher than PU, so that the dynamic mechanical properties of PU-RIRM-CNT are more excellent. When the frequency is 1Hz, the storage modulus and the loss modulus of the PU-RIRM-CNT are respectively 15 times and 13 times of those of PU, and when the frequency is 50Hz, the storage modulus and the loss modulus of the PU-RIRM-CNT are respectively 43 times and 81 times of those of PU, which shows that the PU-RIRM-CNT can play a good role in inhibiting vibration and has a more remarkable effect in inhibiting high-frequency vibration.
Example 3:
a portion of the PU-RIRM-CNT impact-resistant reinforcement material prepared in example 1 was filled into a fuze, and the vibration-damping performance of the PU-RIRM-CNT impact-resistant reinforcement material was tested at an impact speed of 13m/s using an impact vibration test platform and compared with a conventional fuze vibration-damping material (epoxy resin).
The specific method comprises the following steps:
respectively filling epoxy resin and PU-RIRM-CNT into two fuse components;
secondly, an acceleration sensor is arranged in the fuse component, and a circuit is connected into an oscilloscope;
fixing a tooling structure of the fuse component, and fixing the fuse shell at the tail part of the incident rod;
fourthly, filling the bullets into the launching system according to the impact sequence, and pushing the bullets into the air gun tube;
installing a high-speed impact energy absorption device, and adjusting the position of the energy absorption device;
starting a high-speed photographing system and adjusting to prepare for capturing a high-speed impact process of the projectile body;
seventhly, shooting bullets after the air chamber of the shooting system is inflated, and recording test data;
and after the test is finished, storing and analyzing the test data.
As can be seen from FIG. 3, the vibration frequency curve under the epoxy resin protection has a plurality of dominant frequencies, while the PU-RIRM-CNT has only one dominant frequency. Meanwhile, it can be seen from FIGS. 4 to 6 that the vibration acceleration under the protection of PU-RIRM-CNT is reduced by 24.1%, 60.0%, 18.3% at frequencies of 1.3-2.3kHz, 12-13kHz and 24.5-25kHz, respectively, with respect to the epoxy resin. This makes it possible to obtain: the PU-RIRM-CNT material has more remarkable effect of inhibiting the vibration of the fuse under the impact load.
Example 4: a carbon nanotube reinforced polyurethane impact resistant material, which is a PU-RIRM-CNT composite material, wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube; the carbon nano tube reinforced polyurethane impact-resistant material is prepared by compounding RIRM and PU materials into a PU-RIRM material, and then adding CNT to prepare a PU-RIRM-CNT composite material; compared with PU materials, the addition of RIRM and CNT materials obviously improves the storage modulus and loss modulus of the PU materials, has larger rigidity and damping, more excellent elasticity and viscosity and more excellent dynamic mechanical properties; the weight ratio of PU, RIRM and CNT is 10:1: 2; the silicon-boron weight ratio of the RIRM is 2: 1. Example 5: a carbon nanotube reinforced polyurethane impact resistant material, which is a PU-RIRM-CNT composite material, wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube; the carbon nano tube reinforced polyurethane impact-resistant material is prepared by compounding RIRM and PU materials into a PU-RIRM material, and then adding CNT to prepare a PU-RIRM-CNT composite material; the frequency domain curve of the epoxy resin shows a plurality of main frequencies, the PU-RIRM-CNT impact-resistant reinforced material only has one main frequency, and the vibration acceleration of the fuse under the protection of the PU-RIRM-CNT impact-resistant reinforced material is obviously reduced, so that the PU-RIRM-CNT impact-resistant reinforced material has more obvious inhibition effect on the fuse vibration under the impact load;
the weight ratio of PU, RIRM and CNT is 6: 0.8: 1.5; the silicon-boron weight ratio of the RIRM is 1.5: 1.2.
Example 6: a carbon nanotube reinforced polyurethane impact resistant material, which is a PU-RIRM-CNT composite material, wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube; the carbon nano tube reinforced polyurethane impact-resistant material is prepared by compounding RIRM and PU materials into a PU-RIRM material, and then adding CNT to prepare a PU-RIRM-CNT composite material; on the basis of the PU-RIRM-CNT impact-resistant reinforced material, the purposes of controlling the impact resistance and the reinforcing effect of the PU composite material can be achieved by adjusting the proportion of the RIRM material and the CNT material;
the weight ratio of PU, RIRM and CNT is 9: 1: 1.2; the silicon-boron weight ratio of the RIRM is 1.9: 1.
Example 7: a carbon nanotube reinforced polyurethane impact resistant material, which is a PU-RIRM-CNT composite material, wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube; the carbon nano tube reinforced polyurethane impact-resistant material is prepared by compounding RIRM and PU materials into a PU-RIRM material, and then adding CNT to prepare a PU-RIRM-CNT composite material;
the weight ratio of PU, RIRM and CNT is 11: 1.5: 1; the silicon-boron weight ratio of the RIRM is 2: 1.3. The addition of the polymer can obviously improve the dynamic mechanical property and vibration suppression property of the PU material. When the weight ratio of PU-RIRM-CNT is beyond the range of 5-15: 0.2-3, the RIRM with high proportion can soften the composite material and even make the composite material in a flowing state, which is not beneficial to molding application, and the RIRM with low proportion can reduce the agglomeration effect of the composite material and influence the reinforcing effect of the composite material; high proportions of CNTs stiffen the composite reducing its flexibility, low proportions of CNTs softening the composite reducing its reinforcing effect, and finally significantly affecting the dynamic mechanical and vibration damping properties of the PU-RIRM-CNT composite.
Example 8: the raw materials are taken according to the proportion of the embodiment 4 to the embodiment 7 respectively, and the preparation is carried out as follows;
the preparation steps of the RIRM comprise:
(1) sequentially adding water, petroleum ether, diphenyl silanediol, methyl triethoxysilane and hydroxyl silicone oil into a container, uniformly stirring, and heating to react at 80 ℃ for 4 hours to obtain a mixture A;
(2) adding boric acid into the mixture A, uniformly stirring, and heating and reacting at 85 ℃ for 5 hours to obtain a mixture B;
(3) cooling the mixture B to 23-28 ℃, and then washing with water for 6 times to obtain a mixture C;
(4) dehydrating and drying the mixture C to obtain RIRM material;
the preparation method of the PU comprises the following steps:
(1) putting polyester dihydric alcohol, diisocyanate and polytetrahydrofuran ether dihydric alcohol into a container, and uniformly mixing and reacting for 3 hours at the temperature of 75-90 ℃ to obtain a mixture A;
(2) adding 1, 4-butanediol into the mixture A, and uniformly mixing at the temperature of 80 ℃ to obtain a mixture B;
(3) heating the mould to 100 ℃, then pouring the mixture B into the mould, and demoulding after 1h to obtain a mixture C;
(4) vulcanizing the mixture C for 11h at the temperature of 120 ℃ to obtain a PU material;
the preparation steps of the RIRM are as follows:
the water, the petroleum ether, the diphenyl silanediol, the methyl triethoxysilane and the hydroxyl silicone oil in the step (1) are 190: 100: 50: 20: 5 in parts by weight; the water is distilled water
In the step (2), the boric acid accounts for 15 parts by weight; adding boric acid into the mixture A, uniformly stirring, and heating to react for 7 hours at the temperature of 85 ℃ to obtain a mixture B;
in the step (3), the mixture B is cooled to room temperature and then is washed with deionized water for 4 times to obtain a mixture C;
in the step (4), the dehydration and drying treatment is carried out by using a reduced pressure distillation device;
further, in the preparation step of the PU:
in the step (1), 20% of polyester dihydric alcohol, 25% of diisocyanate and 50% of polytetrahydrofuran ether dihydric alcohol are weighed respectively;
in the step (2), 1, 4-butanediol with the weight percentage of 12% is added into the mixture A and is uniformly mixed at the temperature of 80 ℃ to obtain a mixture B;
in the step (3), the mould is heated to 100 ℃, then the mixture B is poured into the mould, and demoulding treatment is carried out after 1h to obtain a mixture C;
in the step (4), the PU material is obtained after the mixture C is vulcanized for 12 hours at the temperature of 120 ℃;
the preparation method of the carbon nano tube reinforced polyurethane impact-resistant material comprises the following steps:
(1) uniformly mixing the PU material and the RIRM material to obtain a mixture A, namely a PU-RIRM material;
(2) adding CNT into the mixture A, and stirring uniformly to obtain a mixture B;
(3) placing the mixture B into a high-temperature internal mixer for internal mixing to obtain a mixture C;
(4) granulating the mixture C to obtain a PU-RIRM-CNT impact-resistant reinforced material;
in the step (3), the temperature of the high-temperature internal mixer is 200 ℃, and after internal mixing is carried out for 15min, a mixture C is obtained;
in the step (4), the mixture C is granulated by using a granulator at the temperature of 250 ℃ to obtain the PU-RIRM-CNT impact-resistant reinforced material. The dynamic mechanical property and the vibration suppression property of the PU material can be obviously improved by adding the polyurethane; high proportions of CNTs stiffen the composite reducing its flexibility, low proportions of CNTs softening the composite reducing its reinforcing effect, and finally significantly affecting the dynamic mechanical and vibration damping properties of the PU-RIRM-CNT composite.
Example 9: the raw materials are taken according to the proportion of the embodiment 4 to the embodiment 7 respectively, and the preparation is carried out as follows;
the preparation steps of the RIRM comprise:
(1) sequentially adding water, petroleum ether, diphenyl silanediol, methyl triethoxysilane and hydroxyl silicone oil into a container, uniformly stirring, and heating to react for 5 hours at the temperature of 75-80 ℃ to obtain a mixture A;
(2) adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-85 ℃ for 6h to obtain a mixture B;
(3) cooling the mixture B to 23-28 ℃, and then washing with water for 6 times to obtain a mixture C;
(4) dehydrating and drying the mixture C to obtain RIRM material;
the preparation method of the PU comprises the following steps:
(1) putting polyester dihydric alcohol, diisocyanate and polytetrahydrofuran ether dihydric alcohol into a container, and uniformly mixing and reacting for 2 hours at the temperature of 75 ℃ to obtain a mixture A;
(2) adding 1, 4-butanediol into the mixture A, and uniformly mixing at the temperature of 75 ℃ to obtain a mixture B;
(3) heating the mould to 110 ℃, then pouring the mixture B into the mould, and demoulding after 2 hours to obtain a mixture C;
(4) vulcanizing the mixture C for 14 hours at the temperature of 130 ℃ to obtain a PU material;
the preparation steps of the RIRM are as follows:
the weight parts of water, petroleum ether, diphenyl silanediol, methyl triethoxysilane and hydroxyl silicone oil in the step (1) are 90: 100: 50: 6: 14; the water is distilled water
In the step (2), the boric acid accounts for 12 parts by weight; adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-90 ℃ for 7h to obtain a mixture B;
in the step (3), the mixture B is cooled to room temperature and then is washed for 3-7 times by deionized water to obtain a mixture C;
in the step (4), the dehydration and drying treatment is carried out by using a reduced pressure distillation device;
the preparation steps of the PU are as follows:
in the step (1), 25% of polyester dihydric alcohol, 20% of diisocyanate and 65% of polytetrahydrofuran ether dihydric alcohol are weighed respectively;
in the step (2), 15 weight percent of 1, 4-butanediol is added into the mixture A and is uniformly mixed at the temperature of 85 ℃ to obtain a mixture B;
in the step (3), the mould is heated to 90 ℃, then the mixture B is poured into the mould, and demoulding treatment is carried out after 2 hours to obtain a mixture C;
in the step (4), the PU material is obtained after the mixture C is vulcanized for 15 hours at the temperature of 110 ℃;
the preparation method of the carbon nano tube reinforced polyurethane impact-resistant material comprises the following steps:
(1) uniformly mixing the PU material and the RIRM material to obtain a mixture A, namely a PU-RIRM material;
(2) adding CNT into the mixture A, and stirring uniformly to obtain a mixture B;
(3) placing the mixture B into a high-temperature internal mixer for internal mixing to obtain a mixture C;
(4) and granulating the mixture C to obtain the PU-RIRM-CNT impact-resistant reinforced material.
In the step (3), the temperature of the high-temperature internal mixer is 180 ℃, and after internal mixing is carried out for 20min, a mixture C is obtained;
in the step (4), granulating the mixture C by using a granulator at the temperature of 200 ℃ to obtain the PU-RIRM-CNT impact-resistant reinforced material;
further comprising a purification step of the CNT material: and taking a CNT raw material, and carrying out acid treatment and impurity removal treatment on the CNT raw material to obtain the CNT material.
Claims (9)
1. A preparation method of a carbon nano tube reinforced polyurethane impact-resistant material is characterized by comprising the following steps: the impact-resistant material is a PU-RIRM-CNT composite material; compounding RIRM and PU material into PU-RIRM material, and then adding CNT; wherein: PU is polyurethane material, RIRM is repairable impact reinforcement material, CNT is carbon nanotube;
the preparation method of the PU comprises the following steps:
(1) putting polyester dihydric alcohol, diisocyanate and polytetrahydrofuran ether dihydric alcohol into a container, and uniformly mixing and reacting for 2-5h at the temperature of 75-90 ℃ to obtain a mixture A;
(2) adding 1, 4-butanediol into the mixture A, and uniformly mixing at the temperature of 75-90 ℃ to obtain a mixture B;
(3) heating the mould to 95-110 ℃, then pouring the mixture B into the mould, and demoulding after 1-2h to obtain a mixture C;
(4) the PU material is obtained after the mixture C is vulcanized for 10-15h at the temperature of 110-130 ℃.
2. The method for preparing the carbon nanotube reinforced polyurethane impact-resistant material of claim 1, comprising the following steps: in the step (1) of the PU preparation method, 10-30% of polyester dihydric alcohol, 20-30% of diisocyanate and 40-65% of polytetrahydrofuran ether dihydric alcohol are respectively weighed according to weight percentage;
in the step (2), adding 10-15 wt% of 1, 4-butanediol into the mixture A, and uniformly mixing at 75-85 ℃ to obtain a mixture B;
in the step (3), the mould is heated to 90-110 ℃, then the mixture B is poured into the mould, and demoulding treatment is carried out after 1-2h to obtain a mixture C;
in the step (4), the PU material is obtained after the mixture C is vulcanized for 10-15h at the temperature of 110-130 ℃.
3. The method of preparing a carbon nanotube-reinforced polyurethane impact-resistant material of claim 1, wherein: the weight ratio of PU, RIRM and CNT is 5-15: 0.2-3; the silicon-boron weight ratio of the RIRM is 1.2-5: 0.2-1.8.
4. The method of preparing a carbon nanotube-reinforced polyurethane impact-resistant material of claim 3, wherein: the weight ratio of PU, RIRM and CNT is 8-12: 0.6-2; the silicon-boron weight ratio of the RIRM is 1.8-3: 0.8-1.4.
5. The method of preparing a carbon nanotube-reinforced polyurethane impact-resistant material of any of claims 1 to 4, wherein: the preparation steps of the RIRM comprise:
(1) sequentially adding water, petroleum ether, diphenyl silanediol, methyl triethoxysilane and hydroxyl silicone oil into a container, uniformly stirring, and heating to react at the temperature of 75-85 ℃ for 3-5h to obtain a mixture A;
(2) adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-90 ℃ for 5-9h to obtain a mixture B;
(3) cooling the mixture B to 23-28 ℃, and then washing with water for 5-8 times to obtain a mixture C;
(4) and (3) dehydrating and drying the mixture C to obtain the RIRM material.
6. The method of preparing a carbon nanotube-reinforced polyurethane impact-resistant material of claim 5, wherein: the preparation steps of the RIRM are as follows:
the water, the petroleum ether, the diphenyl silanediol, the methyl triethoxysilane and the hydroxyl silicone oil in the step (1) are 80-250: 60-200: 20-70: 5-30: 1-18 in parts by weight; the water is distilled water
In the step (2), the boric acid accounts for 5-25 parts by weight; adding boric acid into the mixture A, uniformly stirring, and heating and reacting at the temperature of 80-90 ℃ for 6-8h to obtain a mixture B;
in the step (3), the mixture B is cooled to room temperature and then is washed for 3-7 times by deionized water to obtain a mixture C;
in the step (4), the dehydration and drying treatment is performed by using a reduced pressure distillation apparatus.
7. The method for preparing a carbon nanotube-reinforced polyurethane impact-resistant material according to any of claims 1 to 6, comprising the steps of:
(1) uniformly mixing the PU material and the RIRM material to obtain a mixture A, namely a PU-RIRM material;
(2) adding CNT into the mixture A, and stirring uniformly to obtain a mixture B;
(3) placing the mixture B into a high-temperature internal mixer for internal mixing to obtain a mixture C;
(4) and granulating the mixture C to obtain the PU-RIRM-CNT impact-resistant reinforced material.
8. The method of preparing a carbon nanotube-reinforced polyurethane impact-resistant material of claim 7, wherein: in the step (3), the temperature of the high-temperature internal mixer is 180-; in the step (4), granulating the mixture C by using a granulator at the temperature of 200-300 ℃ to obtain the PU-RIRM-CNT impact-resistant reinforced material; the preparation method of the carbon nanotube reinforced polyurethane impact-resistant material also comprises the following steps of: and taking a CNT raw material, and carrying out acid treatment and impurity removal treatment on the CNT raw material to obtain the CNT material.
9. Use of the carbon nanotube-reinforced polyurethane impact-resistant material of any one of claims 1 to 8 for protection against fuze vibration in an impact environment.
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