Preparation process of polyurethane foaming high polymer material

Abstract

The invention belongs to the field of manufacturing of automobile parts, and particularly relates to a preparation process of a polyurethane foaming high polymer material, which comprises the following steps: uniformly mixing polyether polyol, a copper-plated graphite-graphene material, a foaming agent, dibutyltin dilaurate and silicone oil, then adding isophorone diisocyanate, uniformly mixing, and carrying out extrusion molding to obtain the polyurethane foaming high polymer material. Pouring into a mold, foaming in a megasonic environment, and after foaming is finished, feeding into a drying oven for curing; the polyurethane foaming high polymer material is obtained; the material is good in heat-conducting property, and the heat-conducting property cannot be obviously reduced even after long-term repeated extrusion and rebounding; even if the material is dried after absorbing moisture / water, the heat-conducting property and the sound-absorbing property are not obviously reduced; the invention has high application value and is especially suitable for the automobile field.

Description

Technical Field

[0001] The invention belongs to the technical field of automobile accessories, and particularly relates to a preparation process of a polyurethane foaming polymer material. Background Art

[0002] Polyurethane foam is widely used in the automotive industry, encompassing a wide range of vehicle body components, including interior trim, seats, instrument panels, steering wheels, armrests, roofs, and chassis damping. Polyurethane foam typically provides multiple functions, including thermal insulation, sound insulation, and energy absorption and vibration reduction.

[0003] However, with the development of technology, the application of polyurethane foam materials is also constantly expanding. For example, in the field of new energy vehicles, polyurethane foam materials require higher thermal conductivity, better sound insulation performance, etc. However, the thermal conductivity of existing pure polyurethane (unfoamed) is 0.022-0.025W / (m·K), and the thermal conductivity of polyurethane foam materials is usually 0.015-0.020W / (m·K); if 5% graphene is added, the thermal conductivity of polyurethane foam materials will increase to 0.055W / (m·K), but the more graphene is added, the more the sound absorption performance of polyurethane foam materials will decrease significantly; in addition, the direct addition of graphene has limited effect on the combination of graphene and polyurethane foam materials, which makes the thermal conductivity of polyurethane foam materials decrease significantly after long-term repeated extrusion and rebound.

[0004] Based on this, the present invention is proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation process of polyurethane foam polymer material to solve the above problems.

[0006] A preparation process of a polyurethane foam polymer material comprises the following steps:

[0007] The polyether polyol, copper-plated graphite-graphene material, foaming agent, dibutyltin dilaurate, and silicone oil are evenly mixed, and isophorone diisocyanate is added. After mixing evenly, the mixture is poured into a mold for foaming under a megasonic environment. After the foaming is completed, the mixture is placed in an oven for aging to obtain the polyurethane foam polymer material.

[0008] For further improvement, the polyether polyol, copper-plated graphite-graphene material, foaming agent, dibutyltin dilaurate, silicone oil, and isophorone diisocyanate are prepared in a mass ratio of 100:(5-6):(8-10):(0.9-1.1):(6-7):(11-13).

[0009] In a further improvement, the foaming agent is a carbonate or a bicarbonate.

[0010] In a further improvement, the foaming agent is sodium bicarbonate or potassium bicarbonate.

[0011] As a further improvement, the method for preparing the copper-plated graphite-graphene material comprises the following steps:

[0012] Step 1, mixing and dispersing an alcohol organic solvent, graphene, graphite and copper nitrate to obtain a suspension; adding a glucose solution dropwise to the suspension, and then adding an alkali solution dropwise after the addition is completed, while mixing while adding dropwise; after the reaction is completed, filtering, washing and drying to obtain a copper-plated graphite-graphene primary powder;

[0013] Step 2: Grinding the copper-plated graphite-graphene powder in a low eutectic solvent, ultrasonically dispersing it, and drying it to obtain a copper-plated graphite-graphene material.

[0014] A further improvement is that the alcohol organic solvent is ethanol, the alkali solution is sodium hydroxide or potassium hydroxide solution, and the molar ratio of the alcohol organic solvent, graphene, graphite, copper nitrate, glucose, and hydroxide ions in the alkali solution is 85:1.6:1.6:0.5:11.7:20.8.

[0015] A further improvement is that the mass ratio of the copper-plated graphite-graphene primary powder to the low eutectic solvent is 1:(7-10), and the low eutectic solvent is a mixture of choline chloride and urea in a molar ratio of 1:2.

[0016] As a further improvement, foaming in a megasonic environment means foaming at a megasonic frequency of 1.27 MHz by a megasonic vibrator.

[0017] As a further improvement, the temperature in the oven is 103±1°C.

[0018] For further improvement, the aging time is 2 to 21 hours.

[0019] In the present invention, the hydroxyl groups in the ether polyol react with the isocyanate groups in isophorone diisocyanate to release carbon dioxide. Dibutyltin dilaurate serves as a catalyst. After the reaction is complete, the resulting prepolymer can be further cured to obtain the final product.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The polyurethane foam polymer material prepared by the present invention has good thermal conductivity, especially the good bonding effect between the copper-plated graphite-graphene material and the polyurethane, so that the thermal conductivity of the polyurethane foam polymer material will not be significantly reduced after long-term repeated extrusion and rebound; even if it is dried after absorbing moisture / water, the thermal conductivity and sound absorption properties will not be significantly reduced. It has high application value and is particularly suitable for the automotive field. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a curve diagram of the change of ultrasonic frequency and sound absorption coefficient mean value in ultrasonic environment;

[0023] Figure 2 It is a curve diagram of the change of mega-sound frequency and the mean value of sound absorption coefficient in mega-sound environment;

[0024] Figure 3 This is an electron microscope image of the copper-plated graphite-graphene material described in Example 3. DETAILED DESCRIPTION

[0025] The present invention will be further described in detail below through specific embodiments in conjunction with the accompanying drawings.

[0026] Example 1

[0027] 1. 85 mol of ethanol, 1.6 mol of graphene, 1.6 mol of graphite, and 0.5 mol of copper nitrate were stirred and mixed in a beaker to obtain a suspension; a glucose solution prepared by 11.7 mol of glucose was added dropwise to the suspension, and a sodium hydroxide solution prepared by 20.8 mol of sodium hydroxide was added dropwise after the addition was completed, while mixing. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a copper-coated graphite-graphene powder. 100 g of the copper-coated graphite-graphene powder was ground in 700 g of a deep eutectic solvent (choline chloride and urea were mixed in a molar ratio of 1:2), ultrasonically dispersed, and dried to obtain a copper-coated graphite-graphene material.

[0028] 2. 1000g of polyether polyol, 50g of copper-plated graphite-graphene material, 80g of sodium bicarbonate, 9g of dibutyltin dilaurate, and 60g of silicone oil were mixed evenly, and 110g of isophorone diisocyanate was added. After mixing evenly, the mixture was poured into a mold and foamed in a megasonic environment (a megasonic oscillator was installed outside the mold, and the megasonic frequency was 1.27MHz). After foaming, the mixture was sent to an oven for aging at 103±1°C for 2h. After aging, the polyurethane foam polymer material was obtained.

[0029] Example 2

[0030] 1. 85 mol of ethanol, 1.6 mol of graphene, 1.6 mol of graphite, and 0.5 mol of copper nitrate were stirred and mixed in a beaker to obtain a suspension; a glucose solution prepared by 11.7 mol of glucose was added dropwise to the suspension, and a sodium hydroxide solution prepared by 20.8 mol of sodium hydroxide was added dropwise after the addition was completed, while mixing. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a copper-coated graphite-graphene powder. 100 g of the copper-coated graphite-graphene powder was ground in 1000 g of a deep eutectic solvent (choline chloride and urea were mixed in a molar ratio of 1:2), ultrasonically dispersed, and dried to obtain a copper-coated graphite-graphene material.

[0031] 2. 1000g of polyether polyol, 60g of copper-plated graphite-graphene material, 100g of sodium bicarbonate, 11g of dibutyltin dilaurate, and 70g of silicone oil were mixed evenly, and 130g of isophorone diisocyanate was added. After mixing evenly, the mixture was poured into a mold and foamed in a megasonic environment (a megasonic oscillator was installed outside the mold, and the megasonic frequency was 1.27MHz). After foaming, the mixture was sent to an oven for aging at 103±1°C for 3h. After aging, the polyurethane foam polymer material was obtained.

[0032] Example 3

[0033] 1. Stir 85 mol of ethanol, 1.6 mol of graphene, 1.6 mol of graphite and 0.5 mol of copper nitrate in a beaker to obtain a suspension; add a glucose solution prepared by 11.7 mol of glucose to the suspension, and then add a sodium hydroxide solution prepared by 20.8 mol of sodium hydroxide, adding and mixing while dropping. After the reaction is completed, filter, wash and dry to obtain copper-plated graphite-graphene powder. Take 100g of copper-plated graphite-graphene powder and grind it in 800g of low eutectic solvent (choline chloride and urea are mixed in a molar ratio of 1:2), ultrasonically disperse and dry to obtain copper-plated graphite-graphene material, the microscopic picture of which is shown in FIG. Figure 3 .

[0034] 2. 1000g of polyether polyol, 53g of copper-plated graphite-graphene material, 91g of sodium bicarbonate, 10g of dibutyltin dilaurate, and 66g of silicone oil were mixed evenly, and 120g of isophorone diisocyanate was added. After mixing evenly, the mixture was poured into a mold and foamed in a megasonic environment (a megasonic oscillator was installed outside the mold, and the megasonic frequency was 1.27MHz). After foaming, the mixture was sent to an oven for aging at 103±1°C for 3h. After aging, the polyurethane foam polymer material was obtained.

[0035] Comparative Example 1

[0036] Compared with Example 3, this example uses copper-plated graphene instead of copper-plated graphite-graphene material, and the rest remains unchanged; the preparation method of copper-plated graphene is as follows:

[0037] 85 mol of ethanol, 3.2 mol of graphene and 0.5 mol of copper nitrate were mixed and dispersed to obtain a suspension; a glucose solution prepared by 11.7 mol of glucose was added dropwise to the suspension, and a sodium hydroxide solution prepared by 20.8 mol of sodium hydroxide was added dropwise after the addition was completed, and the mixture was mixed while adding dropwise. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a copper-coated graphite-graphene powder. 100 g of the copper-coated graphite-graphene powder was ground in 800 g of a deep eutectic solvent (choline chloride and urea were mixed in a molar ratio of 1:2), ultrasonically dispersed, and dried to obtain copper-coated graphene.

[0038] Comparative Example 2

[0039] Compared with Example 3, this example uses copper-plated graphite instead of copper-plated graphite-graphene material, and the rest remains unchanged; the preparation method of copper-plated graphite is as follows:

[0040] 85 mol of ethanol, 3.2 mol of graphite and 0.5 mol of copper nitrate were mixed and dispersed to obtain a suspension; a glucose solution prepared by 11.7 mol of glucose was added dropwise to the suspension, and a sodium hydroxide solution prepared by 20.8 mol of sodium hydroxide was added dropwise after the addition was completed, and the mixture was mixed while adding dropwise. After the reaction was completed, the mixture was filtered, washed and dried to obtain a copper-coated graphite-graphene powder. 100 g of the copper-coated graphite-graphene powder was ground in 800 g of a deep eutectic solvent (choline chloride and urea were mixed in a molar ratio of 1:2), ultrasonically dispersed and dried to obtain copper-coated graphite.

[0041] Comparative Example 3

[0042] Compared with Example 3, this example uses graphene to replace the copper-plated graphite-graphene material, and the rest remains unchanged.

[0043] Comparative Example 4

[0044] Compared with Example 3, this example uses graphite instead of the copper-plated graphite-graphene material, and the rest remains unchanged.

[0045] Comparative Example 5

[0046] Compared with Example 3, this example uses graphene-graphite sintered powder instead of copper-plated graphite-graphene material, and the rest remains unchanged. The preparation method of graphene-graphite sintered powder is as follows:

[0047] Graphene and graphite were mixed in a molar ratio of 1:1, sintered at 1100° C. in a nitrogen atmosphere for 30 min, cooled, and ground to obtain graphene-graphite sintered powder.

[0048] Comparative Example 6

[0049] Compared with Example 3, this example does not dope the copper-plated graphite-graphene material into the polyurethane foam polymer material. Specifically:

[0050] 1000g of polyether polyol, 91g of sodium bicarbonate, 10g of dibutyltin dilaurate, and 66g of silicone oil were mixed evenly, and then 120g of isophorone diisocyanate was added. After mixing evenly, the mixture was poured into a mold and foamed in a megasonic environment (a megasonic oscillator was installed outside the mold, and the megasonic frequency was 1.27MHz). After the foaming was completed, the mixture was sent to an oven for curing at 103±1°C for 3h. After the curing was completed, the foamed material was obtained.

[0051] Comparative Example 7

[0052] Compared with Example 3, this example uses copper-plated graphite-graphene primary powder instead of copper-plated graphite-graphene material, and the rest remains unchanged.

[0053] Comparative Example 8

[0054] Compared with Example 3, the deep eutectic solvent used in this example is prepared by mixing choline chloride and ethylene glycol in a molar ratio of 1:2, and the rest are the same.

[0055] Comparative Example 9

[0056] Compared with Example 3, the deep eutectic solvent used in this example is prepared by mixing choline chloride and tetrabutylammonium bromide in a molar ratio of 1:2, and the rest are the same.

[0057] Comparative Example 10

[0058] Compared with Example 3, in this example, the mold is foamed in a non-megasonic environment (the megasonic vibrator is not activated), and the rest are the same.

[0059] The test results of Examples 1 to 3 and Comparative Examples 1 to 10 are shown in Table 1 and Table 2:

[0060] Table 1

[0061]

[0062] Table 2

[0063]

[0064] In Table 1, "1000 times of extrusion and rebound" refers to the process of the polyurethane foam polymer material undergoing 300 times of "extrusion-rebound recovery". During a single "extrusion-rebound recovery" process, the compression rate of the polyurethane foam polymer material is 50%, and then it is left to stand and wait for natural recovery.

[0065] Drying after soaking means soaking the polyurethane foam polymer material in deionized water for 1 hour and then drying it in a 60℃ oven.

[0066] As shown in Table 1, the corresponding polyurethane foam polymer materials in Examples 1-3 show a decrease in thermal conductivity of no more than 10% after undergoing "1000 squeeze-and-rebound cycles"; and after immersion in water followed by drying, the decrease in thermal conductivity is no more than 15%. Comparative Examples 1-5 show that only by combining graphene and graphite with a copper-plated layer as a medium can the copper-plated graphite-graphene material be firmly bonded to the polyurethane foam material. Even after undergoing "1000 squeeze-and-rebound cycles" and "immersion in water followed by drying," the thermal conductivity does not drop significantly.

[0067] It can be seen from Comparative Example 6 that if the copper-plated graphite-graphene material is not added and only megasonic treatment is used during foaming, the defect of thermal conductivity decreasing after long-term extrusion and water absorption cannot be improved.

[0068] It can be seen from Comparative Examples 7 to 9 that only by using a low eutectic solvent such as choline chloride and urea can trace amounts of choline chloride and urea be combined with the copper-plated graphite-graphene material through hydrogen bonds. The hydrogen bonds play a role of physical cross-linking between the polyurethane molecular chains, ultimately improving the stability of the bonding between the copper-plated graphite-graphene material and the polyurethane, mainly affecting the thermal conductivity of the polyurethane foam polymer material after "1000 times of extrusion rebound", and has little effect on the thermal conductivity of the "immersion and drying" treatment.

[0069] It can be seen from Comparative Example 10 that, under the premise of incorporating copper-plated graphite-graphene material, by adopting megasonic treatment during the foaming process, the internal distribution structure of the foaming cells can be significantly improved, thereby significantly improving the sound absorption performance; but there is little improvement on the thermal conductivity.

[0070] As shown in Table 2, the addition of copper-coated graphite-graphene material significantly improves the sound absorption performance compared to copper-coated graphite and copper-coated graphene. However, the addition of only graphite, graphene, and graphene-graphite sintered powder does not improve the sound absorption performance.

[0071] Comparative Example 11

[0072] In Example 3, if the megasonic foaming environment is replaced with an ultrasonic environment (20kHz to 100kHz), the mean value change curve of the sound absorption coefficient is shown in FIG. Figure 1 ;Depend on Figure 1 It can be seen that in the foaming system of the present invention, the average sound absorption coefficient is less than 0.26, and ultrasonic foaming is not suitable.

[0073] Comparative Example 12

[0074] In Example 3, the megasonic frequency in the megasonic foaming environment varies from 1.2 MHz to 1.3 MHz, and the mean value of the sound absorption coefficient is shown in FIG. Figure 2 ;Depend on Figure 2 It can be seen that in the foaming system of the present invention, the optimal megasonic frequency in the megasonic foaming environment is 1.27 MHz.

[0075] Comparative Example 13

[0076] In Example 3, the aging time was extended from 3 hours to 20 hours, with samples taken every hour to measure the material's sound absorption performance. The sound absorption coefficient for low-frequency sound waves (less than 500 Hz) remained below 0.198. However, when the aging time was extended to 21 hours, the sound absorption coefficient of the resulting polyurethane foam polymer material reached 0.881 for low-frequency sound waves (less than 500 Hz), but decreased to 0.157 for high-frequency sound waves (greater than 1500 Hz). In other words, extending the aging time to 21 hours resulted in the resulting polyurethane foam polymer material exhibiting excellent sound absorption for low-frequency sound waves, making it particularly suitable for reducing low-frequency noise in automobiles (such as engine exhaust noise, tire noise, and road noise, which are often high in energy, difficult to control, and have certain impacts on human health).

[0077] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A process for preparing a polyurethane foam polymer material, characterized in that: The following steps are involved: The polyether polyol, copper-plated graphite-graphene material, foaming agent, dibutyltin dilaurate, and silicone oil are evenly mixed, and isophorone diisocyanate is added. After mixing evenly, the mixture is poured into a mold for foaming under a megasonic environment. After the foaming is completed, the mixture is placed in an oven for aging to obtain the polyurethane foam polymer material.

2. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: The polyether polyol, copper-plated graphite-graphene material, foaming agent, dibutyltin dilaurate, silicone oil, and isophorone diisocyanate are prepared in a mass ratio of 100:(5-6):(8-10):(0.9-1.1):(6-7):(11-13).

3. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: The foaming agent is a carbonate or a bicarbonate.

4. The process for preparing a polyurethane foam polymer material according to claim 3, wherein: The foaming agent is sodium bicarbonate or potassium bicarbonate.

5. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: The preparation method of the copper-plated graphite-graphene material comprises the following steps: Step 1, mixing and dispersing an alcohol organic solvent, graphene, graphite and copper nitrate to obtain a suspension; adding a glucose solution dropwise to the suspension, and then adding an alkali solution dropwise after the addition is completed, while mixing while adding dropwise; after the reaction is completed, filtering, washing and drying to obtain a copper-plated graphite-graphene primary powder; Step 2: Grinding the copper-plated graphite-graphene powder in a low eutectic solvent, ultrasonically dispersing it, and drying it to obtain a copper-plated graphite-graphene material.

6. The process for preparing a polyurethane foam polymer material according to claim 5, wherein: The alcohol organic solvent is ethanol, the alkali solution is sodium hydroxide or potassium hydroxide solution, and the molar ratio of the alcohol organic solvent, graphene, graphite, copper nitrate, glucose, and hydroxide ions in the alkali solution is 85: 1.6:1.6:0.5:11.7:20.8。 7. The process for preparing a polyurethane foam polymer material according to claim 5, wherein: The mass ratio of the copper-plated graphite-graphene primary powder to the low eutectic solvent is 1:(7-10), and the low eutectic solvent is a mixture of choline chloride and urea in a molar ratio of 1:

2.

8. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: Foaming in a megasonic environment means foaming at a megasonic frequency of 1.27 MHz using a megasonic vibrator.

9. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: The temperature in the oven is 103±1°C.

10. The process for preparing a polyurethane foam polymer material according to claim 1, wherein: The curing time is 2 to 21 hours.

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