Composite particle and preparation method thereof, PVC leather and vehicle

Abstract

The invention provides a composite particle and a preparation method thereof, PVC leather and a vehicle, in the application, the composite particle comprises an inner core and a polymer layer, and the inner core comprises inorganic particles with conductivity; the polymer layer coats the inner core, and a molecular chain of the polymer layer has an amino group. When the composite particles are applied to preparation of the PVC leather, on one hand, the inorganic particles can improve the conductivity of the PVC leather; on the other hand, preparation raw materials of the PVC leather generally comprise polyvinyl chloride, a polyvinyl chloride molecular chain contains chlorine atoms with relatively strong electronegativity, and amino groups on the molecular chain of the polymer layer can be subjected to nucleophilic substitution reaction with the chlorine atoms to form C-N covalent bonds, so that the composite particles can be combined onto the polyvinyl chloride through chemical bonds; furthermore, the compatibility of the composite particles and the polyvinyl chloride and the distribution uniformity of the inorganic particles in the PVC leather can be improved, so that the PVC leather is ensured to have relatively good conductivity.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of PVC leather, and particularly relates to a composite particle and a preparation method thereof, PVC leather and a vehicle. BACKGROUND

[0002] PVC (polyvinyl chloride) leather is widely used in automotive interior parts such as automotive seats, instrument panels, door trim panels and the like due to its excellent physical properties, low cost and good processing performance. With the development of intelligentization of the automotive industry, new performance requirements such as flame retardance and electrical conductivity are put forward for the PVC leather used in vehicles.

[0003] In the related art, inorganic particles with electrical conductivity are generally added to a PVC composite during preparation of the PVC leather to improve the electrical conductivity of the PVC leather. However, the inorganic particles have poor compatibility with the PVC composite, and the inorganic particles cannot be uniformly dispersed in the PVC leather, which reduces the electrical conductivity of the PVC leather and needs to be further improved. SUMMARY

[0004] Embodiments of the application provide a composite particle and a preparation method thereof, PVC leather and a vehicle, and aim to solve the foregoing technical problems.

[0005] In a first aspect, embodiments of the application provide a composite particle, comprising:

[0006] a core, the core comprising inorganic particles with electrical conductivity;

[0007] a polymer layer, the polymer layer constituting a coating for the core, and the polymer layer having amino groups on molecular chains thereof.

[0008] In an embodiment, the polymer layer has at least one of sulfur atoms, phosphorus atoms and nitrogen atoms on the molecular chains thereof; and / or

[0009] the inorganic particles comprise at least one of graphene and carbon nanotubes.

[0010] In a second aspect, embodiments of the application provide a preparation method of the composite particle as described above, comprising the following steps:

[0011] providing a multi-amino compound, a multi-aldehyde compound and inorganic particles;

[0012] causing the multi-amino compound and the multi-aldehyde compound to undergo a polymerization reaction to form a polymer layer on a surface of the inorganic particles, to obtain the composite particle.

[0013] In an embodiment, the preparation method specifically comprises:

[0014] A mixed solution is provided, which includes the polyamino compound, the polyaldehyde compound and the inorganic particles;

[0015] The polyamino compound and the polyaldehyde compound in the mixed solution are subjected to a polymerization reaction to form the polymer layer on the surface of the inorganic particles, and dried to obtain the composite particles.

[0016] In an embodiment, the method for preparing the mixed solution specifically includes:

[0017] A first solution is provided, which includes a first solvent and the inorganic particles dispersed in the first solvent;

[0018] A second solution and a third solution are sequentially added to the first solution to obtain the mixed solution, the second solution including the polyamino compound and a second solvent, and the third solution including the polyaldehyde compound and a third solvent.

[0019] In an embodiment, the temperature of the polymerization reaction is 20-30°C.

[0020] In an embodiment, the first solvent includes at least one of methanol and ethanol; and / or

[0021] The second solvent includes at least one of methanol and ethanol; and / or

[0022] The third solvent includes at least one of methanol and ethanol; and / or

[0023] The concentration of the inorganic particles in the first solution is 0.5-20 mg / mL; and / or

[0024] The concentration of the polyamino compound in the second solution is 0.1-1 mg / mL; and / or

[0025] The concentration of the polyaldehyde compound in the third solution is 0.1-1 mg / mL.

[0026] In an embodiment, the molar ratio of the polyamino compound to the polyaldehyde compound is 1:(1-3); and / or

[0027] The mass ratio of the polyamino compound, the polyaldehyde compound and the inorganic particles is (1-10):(1-15):30.

[0028] In an embodiment, the polyamino compound includes at least one of the following compounds:

[0029]

[0030] In an embodiment, the polyaldehyde-based compound comprises at least one of the following compounds:

[0031]

[0032] In a third aspect, embodiments of the present application provide a PVC leather, raw materials for preparing the PVC leather comprising a PVC compound and a composite particle.

[0033] The composite particle is the composite particle described above or obtained by the preparation method described above.

[0034] The PVC compound comprises polyvinyl chloride.

[0035] In a fourth aspect, embodiments of the present application provide a preparation method of a PVC leather, comprising the following steps:

[0036] Mixing the PVC compound and the composite particle to obtain a mixture.

[0037] Hot-pressing the mixture onto a base cloth to obtain the PVC leather.

[0038] The composite particle is the composite particle described above or obtained by the preparation method described above.

[0039] The PVC compound comprises polyvinyl chloride.

[0040] In an embodiment, the mass percentage of the composite particle in the mixture is 2%-15%.

[0041] In an embodiment, the temperature of the mixing is 170°C-190°C; and / or

[0042] The temperature of the hot-pressing is 150°C-180°C.

[0043] In a fifth aspect, embodiments of the present application provide a vehicle comprising the PVC leather described above or prepared by the preparation method described above.

[0044] The beneficial effects of embodiments of the present application are as follows:

[0045] In the embodiment of the present application, the composite particle comprises a core and a polymer layer, the core comprises inorganic particles with conductive properties; the polymer layer covers the core, and the polymer layer has amino groups on the molecular chain. When the composite particle is applied to the preparation of PVC leather, on the one hand, the inorganic particles can improve the conductive properties of the PVC leather; on the other hand, the raw materials for preparing the PVC leather generally comprise polyvinyl chloride, the molecular chain of the polyvinyl chloride contains chlorine atoms with strong electronegativity, the amino groups on the molecular chain of the polymer layer can undergo nucleophilic substitution reaction with the chlorine atoms to form C-N covalent bonds, so that the composite particle can be combined with the polyvinyl chloride through chemical bonds, thereby improving the compatibility of the composite particle with the polyvinyl chloride and the uniformity of the distribution of the inorganic particles in the PVC leather, thereby ensuring that the PVC leather has good conductive properties. BRIEF DESCRIPTION OF DRAWINGS

[0046] In order to more clearly illustrate the scheme in the present application or prior art, the drawings required to be used in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings;

[0047] Figure 1 XRD curve of the composite particle in the embodiment 1 of the present application;

[0048] Figure 2 TEM image of the graphene in the embodiment 1 of the present application;

[0049] Figure 3 TEM image of the composite particle in the embodiment 1 of the present application;

[0050] Figure 4 Nitrogen element distribution map of the composite particle in the embodiment 1 of the present application;

[0051] Figure 5 Oxygen element distribution map of the composite particle in the embodiment 1 of the present application;

[0052] Figure 6 Boron element distribution map of the composite particle in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0053] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the scope of protection of the present application. In addition, it should be understood that the specific implementation described herein is only used to illustrate and explain the present application, and is not used to limit the present application. In the present application, the orientation words such as “upper” and “lower” generally refer to the upper and lower in the actual use or working state of the device, and specifically refer to the direction of the drawing surface in the drawings; and “inner” and “outer” refer to the contour of the device.

[0054] In the related art, when the PVC leather is prepared, the compatibility of the inorganic particles and the PVC compound is poor, the inorganic particles cannot be uniformly dispersed in the PVC leather, and the conductivity of the PVC leather is reduced, which needs to be further improved.

[0055] The present application provides a composite particle, which comprises a core and a polymer layer. The core comprises inorganic particles with conductivity. The polymer layer covers the core, and the molecular chain of the polymer layer has an amino group. When the composite particle is applied to the preparation of the PVC leather, on the one hand, the inorganic particles can improve the conductivity of the PVC leather; on the other hand, the raw material for preparing the PVC leather generally comprises polyvinyl chloride, and the molecular chain of the polyvinyl chloride contains chlorine atoms with strong electronegativity. The amino group on the molecular chain of the polymer layer can undergo a nucleophilic substitution reaction with the chlorine atoms to form a C-N covalent bond, so that the composite particle can be combined with the polyvinyl chloride through a chemical bond, thereby improving the compatibility of the composite particle and the polyvinyl chloride and the uniformity of the distribution of the inorganic particles in the PVC leather, and thereby ensuring that the PVC leather has good conductivity.

[0056] In an embodiment, the polymer layer has at least one of a sulfur atom, a phosphorus atom, and a nitrogen atom on the molecular chain. In this embodiment, the polymer layer has a nitrogen atom on the molecular chain, and the polymer layer can decompose at high temperature and release a large amount of inert gas (such as NH3, H2O, and N2) to dilute the concentration of oxygen and combustible volatiles, so that the concentration of oxygen and volatiles is lower than the critical value of combustion, thereby inhibiting the combustion of high molecules in the PVC leather and improving the flame retardant performance of the PVC leather. The polymer layer has a phosphorus atom on the molecular chain, and the polymer layer can generate phosphorus-containing radicals (such as PO·, HPO·, and HPO2·) that can capture high-energy radicals (such as HO· and H·) in the gas phase under the condition of combustion or high temperature, thereby inhibiting the combustion of high molecules in the PVC leather and improving the flame retardant performance of the PVC leather. In addition, the polymer layer has a phosphorus atom or a sulfur atom on the molecular chain, and the polymer layer can generate a large amount of phosphoric acid and sulfonic acid at high temperature, thereby promoting the carbonization of the high molecular matrix of the PVC leather and forming a higher-quality protective carbon layer. The formation of the protective carbon layer releases a large amount of water vapor, thereby reducing the concentration of combustible volatiles. In addition, the presence of the protective carbon layer can act as a barrier to reduce the heat and mass transfer of the material during the decomposition process and inhibit the combustion of high molecular materials in the PVC leather.

[0057] In an embodiment, the inorganic particles include at least one of graphene and carbon nanotubes. The carbon nanotubes can include single-walled carbon nanotubes or multi-walled carbon nanotubes. The above inorganic particles all have good electrical conductivity.

[0058] The application also provides a preparation method of the composite particles as described above, including the following steps:

[0059] S1, providing a polyamino compound, a polyaldehyde compound, and inorganic particles;

[0060] S2, causing the polyamino compound and the polyaldehyde compound to undergo a polymerization reaction to form a polymer layer on the surface of the inorganic particles, thereby obtaining the composite particles.

[0061] In this embodiment, the polyamino compound is a compound having at least two amino groups, and the polyaldehyde compound is a compound having at least two aldehyde groups. The polyamino compound can first be combined with the surface of the inorganic particles through hydrogen bonding, and then undergo a polymerization reaction with the aldehyde groups of the polyaldehyde compound, thereby forming a polymer layer on the surface of the inorganic particles. The polymerization reaction between the polyamino compound and the polyaldehyde compound is a reversible reaction, and after the reaction is completed, part of the amino groups will remain in the polymer layer, so that the polymer layer has amino groups on the molecular chain.

[0062] In an embodiment, the preparation method of the composite particles specifically includes:

[0063] S11, providing a mixed solution, the mixed solution comprising the polyamino compound, the polyaldehyde compound and the inorganic particles;

[0064] S12, causing the polyamino compound and the polyaldehyde compound in the mixed solution to undergo a polymerization reaction to form a polymer layer on the surface of the inorganic particles, and drying to obtain the composite particles.

[0065] In an embodiment, the method for preparing the mixed solution specifically comprises:

[0066] S111, providing a first solution, the first solution comprising a first solvent and inorganic particles dispersed in the first solvent;

[0067] S112, sequentially adding a second solution and a third solution to the first solution to obtain the mixed solution, the second solution comprising a polyamino compound and a second solvent, and the third solution comprising a polyaldehyde compound and a third solvent.

[0068] In the present embodiment, the second solution is added to the first solution first, and the amino groups of the polyamino compound in the second solution can be combined on the surface of the inorganic particles through hydrogen bonds, and then the third solution is added, and the polyaldehyde compound in the third solution and the polyamino compound on the surface of the inorganic particles undergo a polymerization reaction to form a polymer layer on the surface of the inorganic particles.

[0069] In an embodiment, the temperature of the polymerization reaction is 20-30°C. In the present embodiment, the polyamino compound and the polyaldehyde compound are reacted at 20-30°C, the reaction condition is mild and easy to control, the particle size of the obtained composite particles is single and stable, the morphology is regular, and at the same time, heating equipment and inert gas protection are not required, which can simplify the production equipment and production steps.

[0070] In an embodiment, the first solvent comprises at least one of methanol and ethanol.

[0071] In an embodiment, the second solvent comprises at least one of methanol and ethanol.

[0072] In an embodiment, the third solvent comprises at least one of methanol and ethanol.

[0073] In an embodiment, the concentration of the inorganic particles in the first solution is 0.5-20 mg / mL. Alternatively, the concentration of the inorganic particles in the first solution can be any one of 0.5 mg / mL, 1 mg / mL, 5 mg / mL, 15 mg / mL, 20 mg / mL or a range between any two of them, which is not limited herein.

[0074] In an embodiment, the concentration of the polyamino compound in the second solution is 0.1 mg / mL-1 mg / mL. Alternatively, the concentration of the polyamino compound in the second solution can be any one of 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 1 mg / mL, or a range between any two of them, without limitation.

[0075] In an embodiment, the concentration of the polyaldehyde compound in the third solution is 0.1 mg / mL-1 mg / mL. Alternatively, the concentration of the polyaldehyde compound in the second solution can be any one of 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 1 mg / mL, or a range between any two of them, without limitation.

[0076] In an embodiment, the molar ratio of the polyamino compound and the polyaldehyde compound is 1:(1-3). Alternatively, the molar ratio of the polyamino compound and the polyaldehyde compound can be any one of 1:1, 1:1.5, 1:2, 1:2.5, 1:3, or a range between any two of them, without limitation. In this embodiment, by setting the molar ratio of the polyamino compound and the polyaldehyde compound to 1:(1-3), the reaction of the polyamino compound and the polyaldehyde compound can be ensured to be more sufficient.

[0077] In an embodiment, the mass ratio of the polyamino compound, the polyaldehyde compound, and the inorganic particles is (1-10):(1-15):30. Alternatively, the mass ratio of the polyamino compound, the polyaldehyde compound, and the inorganic particles can be any one of 1:15:30, 1:1:30, 5:1:30, 8:1:30, 10:1:30, or a range between any two of them, without limitation. In this embodiment, by setting the mass ratio of the polyamino compound, the polyaldehyde compound, and the inorganic particles to (1-10):(1-15):30, the coating effect of the generated polymer on the core can be ensured, the separation between the core and the polymer layer can be reduced, at the same time, the content of the core in the composite particles can be prevented from being too small, and the conductivity of the composite particles can be ensured.

[0078] In an embodiment, the polyamino compound includes at least one of the following compounds:

[0079]

[0080] In this embodiment, by using the above polyamino compound as a reactant, nitrogen atoms and sulfur atoms can be introduced into the polymer layer, and when the composite particles are applied to the preparation of PVC leather, the flame retardant effect of the PVC leather can be improved.

[0081] In the present embodiment, the CAS number of the compound represented by formula (1-1) is 1824592-95-1, the CAS number of the compound represented by formula (1-2) is 104617-80-3, the compound CID number of the compound represented by formula (1-3) is 45077087, and the CAS number of the compound represented by formula (1-4) is 4651-82-5.

[0082] In an embodiment, the polyaldehyde-based compound includes at least one of the following compounds:

[0083]

[0084] In the present embodiment, the polyaldehyde-based compound described above is used as a reactant to introduce phosphorus atoms into the polymer layer, and the use of the composite particles in the preparation of PVC leather can improve the flame retardant effect of the PVC leather.

[0085] In the present embodiment, the compound CID number of the compound represented by formula (2-1) is 14935713, the compound CID number of the compound represented by formula (2-2) is 23414693, and the compound CID number of the compound represented by formula (2-3) is 14944320.

[0086] The present application also provides a PVC leather, and the raw materials for preparing the PVC leather include a PVC composite and composite particles; wherein the composite particles are the composite particles described above or obtained by the preparation method described above; and the PVC composite includes polyvinyl chloride.

[0087] In the present embodiment, the PVC composite is a conventional PVC composite in the art. For example, the PVC composite can only include polyvinyl chloride. For another example, the PVC composite can include polyvinyl chloride, dioctyl phthalate plasticizer, calcium zinc stearate stabilizer, and calcium carbonate filler.

[0088] In the present embodiment, the composite particles include a core and a polymer layer, the core includes inorganic particles having conductive properties; the polymer layer coats the core, and the polymer layer has amino groups on the molecular chain. When the composite particles are applied to the preparation of PVC leather, on the one hand, the inorganic particles can improve the conductive properties of the PVC leather; on the other hand, the raw materials for preparing the PVC leather generally include polyvinyl chloride, the molecular chain of polyvinyl chloride contains chlorine atoms with strong electronegativity, and the amino groups on the molecular chain of the polymer layer can undergo nucleophilic substitution reaction with the chlorine atoms to form C-N covalent bonds, so that the composite particles can be chemically bonded to polyvinyl chloride, thereby improving the compatibility of the composite particles with polyvinyl chloride and the uniformity of the distribution of the inorganic particles in the PVC leather, thereby ensuring that the PVC leather has good conductive properties.

[0089] The application also provides a preparation method of the PVC leather, comprising the following steps:

[0090] S21, mixing the PVC compound and the composite particles to obtain a mixture;

[0091] S22, hot-pressing the mixture onto the base cloth to obtain the PVC leather;

[0092] The composite particles are the composite particles described above or obtained by the preparation method described above; the PVC compound comprises polyvinyl chloride.

[0093] In this embodiment, the composite particles comprise a core and a polymer layer, the core comprises inorganic particles with conductive properties; the polymer layer coats the core, and the polymer layer has amino groups on the molecular chain. When the composite particles are applied to the preparation of the PVC leather, on the one hand, the inorganic particles can improve the conductive properties of the PVC leather; on the other hand, the PVC compound comprises polyvinyl chloride, the molecular chain of the polyvinyl chloride contains chlorine atoms with strong electronegativity, and the amino groups on the molecular chain of the polymer layer can undergo nucleophilic substitution reaction with the chlorine atoms to form C-N covalent bonds, so that the composite particles can be combined with the polyvinyl chloride through chemical bonds, thereby improving the compatibility of the composite particles with the polyvinyl chloride and the uniformity of the distribution of the inorganic particles in the PVC compound, thereby ensuring that the PVC compound has good conductive properties.

[0094] In this embodiment, by integrating the multifunctional composite particles into the PVC leather in one step, the multi-step addition of multiple single-function additives is avoided, which not only improves the functionality of the PVC leather. At the same time, the method has simple process steps and is suitable for large-scale production.

[0095] In an embodiment, the mass percentage of the composite particles in the mixture is 2%-15%; alternatively, the mass percentage of the composite particles in the mixture can be any one of 2%, 5%, 8%, 12%, 15%, or a range between any two of them, which is not limited herein. In this embodiment, when the mass percentage of the composite particles in the mixture is less than 2%, the conductive effect of the PVC leather is not ideal; when the mass percentage of the composite particles in the mixture is greater than 15%, the mechanical properties of the PVC leather are easily reduced, and the material cost is increased.

[0096] In an embodiment, the temperature of the mixing of the PVC compound and the composite particles is 170-190℃. Alternatively, the temperature of the mixing of the PVC compound and the composite particles can be any one of 170℃, 175℃, 180℃, 185℃, 190℃, or a range between any two of them, without limitation. In this embodiment, the temperature of the mixing of the PVC compound and the composite particles is 170-190℃, which can ensure that the PVC compound is in a molten state, the fluidity is increased, the mixing effect of the PVC compound and the composite particles can be improved, the composite particles are less likely to agglomerate, and the dispersion uniformity of the composite particles in the mixture is improved.

[0097] In an embodiment, the temperature of the hot pressing is 150-180℃. Alternatively, the temperature of the hot pressing can be any one of 150℃, 160℃, 170℃, 180℃, or a range between any two of them, without limitation. During the hot pressing, part of the molten mixture can penetrate into the weaving structure of the base fabric, and is deposited on the surface of the fabric and combined with the base fabric after cooling.

[0098] In the prior art, when the PVC compound further includes a plasticizer, the plasticizer is prone to overflow from the PVC leather at high temperature, which affects the air quality in the vehicle and may also pose a threat to the health of the driver and passengers. In this embodiment, the composite particles include a core and a polymer layer, the core includes inorganic particles having electrical conductivity, and the polymer layer coats the core and has amino groups on the molecular chain. When the composite particles are applied to the preparation of the PVC leather, on the one hand, the amino groups on the molecular chain of the polymer layer can undergo a nucleophilic substitution reaction with chlorine atoms to form C-N covalent bonds, so that the composite particles can be combined with the polyvinyl chloride through chemical bonds, thereby improving the compatibility of the composite particles with the polyvinyl chloride and the uniformity of the distribution of the inorganic particles in the PVC leather; on the other hand, when the inorganic particles are graphene, the special sheet structure of the graphene itself forms a three-dimensional spatial network at the micro level of the PVC leather, and the “labyrinth effect” formed by these uniformly dispersed sheet-shaped graphenes increases the complexity of the migration path of the plasticizer molecules when the plasticizer migrates out, making it more difficult for the plasticizer to overflow, thereby improving the low-fogging performance of the PVC leather.

[0099] The application also provides a vehicle including the PVC leather described above or including the PVC leather prepared by the preparation method described above. In this embodiment, the vehicle can be a fuel automobile, a plug-in hybrid electric vehicle, or a new energy vehicle, without specific limitation in the disclosure.

[0100] The application will be further described below through specific embodiments.

[0101] Embodiment 1

[0102] A preparation method of PVC leather, comprising the following steps:

[0103] (1) uniformly dispersing 30 mg of graphene in 50 ml of methanol to obtain a first solution;

[0104] (2) dispersing a multi-amino compound shown in formula (1-1) in methanol to obtain a second solution, and the concentration of the second solution is 0.5 mg / ml;

[0105] (3) dispersing a multi-aldehyde compound shown in formula (2-1) in methanol to obtain a third solution; the concentration of the third solution is 0.5 mg / ml;

[0106] (4) sequentially adding 10 ml of the second solution and 10 ml of the third solution into the first solution dropwise, reacting at room temperature after the dropwise addition is completed, removing unreacted raw materials after the reaction is completed, washing the solid filter with anhydrous methanol twice, and drying to obtain a composite particle;

[0107] (5) placing 100 parts of polyvinyl chloride, 60 parts of dioctyl phthalate plasticizer, 5 parts of calcium zinc stearate stabilizer and 20 parts of calcium carbonate filler by weight in a banbury mixer, and uniformly stirring and mixing to obtain a PVC compound;

[0108] (6) uniformly mixing 95 parts of the PVC compound and 5 parts of the composite particle by weight at 180 DEG C by means of a double screw to obtain a mixture;

[0109] (7) hot pressing the mixture on a base fabric (the base fabric is polyester weft-knitted double-sided fabric) with a thickness of 0.4 mm at a temperature of 160 DEG C, slowly cooling to room temperature, and obtaining PVC leather.

[0110] The preparation method of the PVC leather in examples 2-15 is the same as that in example 1, except that the types and contents of the multi-amino compound and the multi-aldehyde compound are different, and the mass percentage of the composite particle in the mixture is different, and the specific conditions are shown in table 1.

[0111] Comparative example 1

[0112] (1) placing 100 parts of polyvinyl chloride, 60 parts of dioctyl phthalate plasticizer, 5 parts of calcium zinc stearate stabilizer and 20 parts of calcium carbonate filler by weight in a banbury mixer, and uniformly stirring and mixing to obtain a PVC compound;

[0113] (2) uniformly mixing 100 parts of the PVC compound by weight at 180 DEG C by means of a double screw to obtain a mixture;

[0114] (3) hot pressing the mixture on a base fabric (the base fabric is polyester weft-knitted double-sided fabric) with a thickness of 0.4 mm at a temperature of 160 DEG C, slowly cooling to room temperature, and obtaining PVC leather.

[0115] Comparative Example 2

[0116] (1) 100 parts by weight of polyvinyl chloride, 60 parts by weight of dioctyl phthalate plasticizer, 5 parts by weight of calcium zinc stearate stabilizer, and 20 parts by weight of calcium carbonate filler were weighed and placed in a mixer to mix and stir uniformly, to obtain a PVC composite;

[0117] (2) 95 parts by weight of the above-mentioned PVC composite and 5 parts by weight of graphene were mixed uniformly at 180°C by a double screw, to obtain a mixture;

[0118] (3) The mixture was hot-pressed onto a base fabric (base fabric: polyester blended knitted fabric) with a thickness of 0.4 mm at a temperature of 160°C, and slowly cooled to room temperature, to obtain a PVC leather.

[0119] Table 1

[0120]

[0121]

[0122] Test method:

[0123] (I) Vertical burning (UL-94) test

[0124] According to the ASTM-D 3801 standard, the PVC leather obtained from Examples 1-15 and Comparative Examples 1-2 was subjected to vertical burning (UL-94) test, and the test results are shown in Table 2 below; wherein V0 represents the highest flame retardant grade, V1 represents the medium flame retardant grade, and NR represents that the material fails to pass the test.

[0125] (II) Limiting oxygen index (LOI) test

[0126] According to the ASTM-D 2863 standard, the PVC leather obtained from Examples 1-15 and Comparative Examples 1-2 was subjected to limiting oxygen index (LOI) test, and the test results are shown in Table 2 below.

[0127] (III) Fogging performance test

[0128] According to the GB / T 40726-2021 standard, the PVC leather obtained from Examples 1-15 and Comparative Examples 1-2 was subjected to fogging performance test, and the test results are shown in Table 2 below.

[0129] (IV) Conductive performance test

[0130] According to the GB / T 3048.2 standard, the PVC leather obtained from Examples 1-15 and Comparative Examples 1-2 was subjected to conductive performance test, and the test results are shown in Table 2 below.

[0131] (V) X-ray diffraction test

[0132] X-ray diffraction tests were performed on the composite particles of Example 1 using a Bruker D8-A25X X-ray diffractometer. The samples were scanned at a scan rate of 0.1° / s under conditions of 40mA and 40kV. The test results are as follows: Figure 1 As shown.

[0133] exist Figure 1 The rGO@FR curve is the XRD curve of the composite particles in Example 1, the FR curve is the XRD curve of graphene, and the rGO curve is the XRD curve of the polymer layer. Compared with the rGO curve and the FR curve, the rGO@FR curve shows a diffraction peak of the GO(002) crystal plane similar to that of the rGO curve at 25.3°. At the same time, the rGO@FR curve shows diffraction peaks generated by the ordered aromatic structure and the intermolecular π-π stacking interaction at 12.5° and 22.7°

[100] , indicating that the surface of graphene is covered with a polymer layer.

[0134] (vi) Transmission Electron Microscopy (TEM) Testing

[0135] The morphology and elemental distribution of the composite particles in Example 1 were characterized using a TALOS F200 transmission electron microscope at an accelerating voltage of 200 kV. The test results are referenced. Figures 2 to 6 .

[0136] in, Figure 2 This is a TEM image of graphene. Figure 3 The image shows a TEM image of the composite particles. Figure 4 This is a nitrogen distribution diagram of the composite particles. Figure 5 This is a distribution diagram of oxygen in the composite particles. Figure 6 This is a distribution diagram of phosphorus in the composite particles. Figures 4 to 6 This indicates that nitrogen, oxygen, and phosphorus elements are evenly distributed in the composite particles.

[0137] Table 2

[0138]

[0139]

[0140] From the test results of the above examples 1 to 15 and comparative examples 1 and 2, it can be seen that the PVC leather prepared in examples 1 to 15 has better conductivity, which may be due to the fact that the composite particles include a core and a polymer layer, the core includes inorganic particles having conductivity, the polymer layer has amino groups on the molecular chain, the PVC composite has chlorine atoms with strong electronegativity on the molecular chain of polyvinyl chloride, and the amino groups of the polymer layer can undergo nucleophilic substitution reaction with chlorine atoms to form C-N covalent bonds, so that the composite particles can be chemically bonded to polyvinyl chloride, thereby improving the compatibility of the composite particles with polyvinyl chloride and the uniformity of the distribution of inorganic particles in the PVC leather, thereby ensuring that the PVC leather has better conductivity.

[0141] From the comparison of examples 1 to 15 and comparative examples 1 to 2, it can be seen that the PVC leather prepared in examples 1 to 15 has better flame retardant performance. The reason may be that the molecular chain of the polymer layer includes sulfur atoms, nitrogen atoms and boron atoms, which can improve the flame retardant performance of the PVC leather.

[0142] From the comparison of examples 1 to 3 and examples 6, examples 4 to 5 and examples 7 to 8, it can be seen that when preparing the PVC leather, controlling the mass ratio of the polyamino compound, the polyaldehyde compound and the graphene within an appropriate range can make the PVC leather have better conductivity, low fogging performance and flame retardant performance at the same time, thereby improving the comprehensive performance of the PVC leather.

[0143] From the comparison of examples 1, examples 12 to 14, it can be seen that controlling the mass percentage of the composite particles in the mixture within an appropriate range can make the PVC leather have better flame retardant performance, low fogging performance and conductivity at the same time, thereby improving the comprehensive performance of the PVC leather.

[0144] The above describes the embodiments of the present application in detail, and the specific examples are applied to explain the principles and implementation modes of the present application. The above examples are only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, the specific implementation mode and application range can be changed, and the above description should not be understood as limiting the present application.

Claims

1. A composite particle, characterized in that, include: The core comprises inorganic particles with conductive properties; A polymer layer that encapsulates the core, wherein the polymer layer has amino groups on its molecular chains.

2. The composite particles according to claim 1, characterized in that, The polymer layer has at least one of sulfur atoms, phosphorus atoms, and nitrogen atoms on its molecular chain; and / or The inorganic particles include at least one of graphene and carbon nanotubes.

3. A method for preparing composite particles as described in claim 1 or 2, characterized in that, Includes the following steps: It provides polyamino compounds, polyaldehyde compounds, and inorganic particles; The polyamino compound and the polyaldehyde compound are polymerized to form a polymer layer on the surface of the inorganic particles, thereby obtaining the composite particles.

4. The method for preparing composite particles according to claim 3, characterized in that, The preparation method specifically includes: A mixed solution is provided, the mixed solution comprising the polyamino compound, the polyaldehyde compound, and the inorganic particles; The polyamino compounds and polyaldehyde compounds in the mixed solution are subjected to a polymerization reaction to form the polymer layer on the surface of the inorganic particles, and then dried to obtain the composite particles.

5. The method for preparing composite particles according to claim 4, characterized in that: The specific method for preparing the mixed solution includes: A first solution is provided, the first solution comprising a first solvent and the inorganic particles dispersed in the first solvent; A second solution and a third solution are added sequentially to the first solution to obtain the mixed solution. The second solution includes the polyamino compound and a second solvent, and the third solution includes the polyaldehyde compound and a third solvent.

6. The method for preparing composite particles according to any one of claims 3-5, characterized in that: The polymerization reaction is carried out at a temperature of 20℃-30℃.

7. The method for preparing composite particles according to claim 5, characterized in that, The first solvent includes at least one of methanol and ethanol; and / or The second solvent includes at least one of methanol and ethanol; and / or The third solvent includes at least one of methanol and ethanol; and / or The concentration of the inorganic particles in the first solution is 0.5 mg / mL to 20 mg / mL; and / or The concentration of the polyamino compound in the second solution is 0.1 mg / mL to 1 mg / mL; and / or The concentration of the polyaldehyde compound in the third solution is 0.1 mg / mL to 1 mg / mL.

8. The method for preparing composite particles according to any one of claims 3-5, characterized in that, The molar ratio of the polyamino compound to the polyaldehyde compound is 1:(1-3); and / or The mass ratio of the polyamino compound, the polyaldehyde compound, and the inorganic particles is (1-10):(1-15):

30.

9. The method for preparing composite particles according to any one of claims 3-5, characterized in that, The polyamino compounds include at least one of the following compounds:

10. The method for preparing composite particles according to any one of claims 3-5, characterized in that, The polyaldehyde compounds include at least one of the following compounds:

11. A type of PVC leather, characterized in that, The raw materials for preparing the PVC leather include PVC composites and composite particles; The composite particles are those described in claim 1 or 2, or those prepared by any one of claims 3-10. The PVC compound includes polyvinyl chloride.

12. A method for preparing PVC leather, characterized in that, Includes the following steps: The PVC composite and composite granules are mixed to obtain a mixture; The mixture is hot-pressed onto a base fabric to obtain the PVC leather; The composite particles are those described in claim 1 or 2, or those prepared by any one of claims 3-10. The PVC compound includes polyvinyl chloride.

13. The method for preparing PVC leather according to claim 12, characterized in that, The composite particles constitute 2%-15% of the mass of the mixture.

14. The method for preparing PVC leather according to claim 12 or 13, characterized in that, The mixing temperature is 170℃-190℃; and / or The hot pressing temperature is 150℃-180℃.

15. A vehicle, characterized in that, Includes the PVC leather as described in claim 11, or includes PVC leather prepared by the preparation method described in any one of claims 12-14.

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