Ceramic polyolefin composite material, ceramic polyolefin coiled material and application

Abstract

The invention discloses a ceramic polyolefin composite material, a ceramic polyolefin coiled material and application, and relates to the technical field of ceramic polyolefin, the ceramic polyolefin composite material comprises the following components by weight: 25-35% of EVA resin, 5-15% of PP resin, 15-30% of low melting point glass powder, 10-35% of zinc borate coated inorganic phosphate, 10-15% of silicate, and the balance of an auxiliary agent; the ceramic polyolefin composite material provided by the invention has excellent processability at normal temperature, can be used for preparing a coiled material with the thickness of 0.5-10mm and the width of 300-1300mm, has excellent mechanical properties, fire resistance and heat insulation performance, and is wide in application range.

Description

Technical Field

[0001] The present invention relates to the field of ceramic forming and protection technology, in particular to a ceramic polyolefin composite material, a ceramic polyolefin coil and applications thereof. Background Art

[0002] With the development of social science and technology and the improvement of living standards, organic polymer composite filled flame retardant materials have been rapidly developed, and their output has increased year by year. Composite polymer materials have been widely used in building materials, decorative materials, wires and cables, electronic appliances, information and transportation.

[0003] In the field of lithium batteries, thermal runaway is the most important research subject in terms of battery safety. Overheating, impact, overcharging and internal short circuit of the battery may all trigger thermal runaway of the lithium battery, causing the lithium battery to emit a large amount of heat and toxic and harmful gases in a short period of time. In severe cases, it may even cause the battery to catch fire and explode, which in turn causes the aluminum top cover of the battery cell to fail thermally and be punctured, which may expand the scope of the fire or explosion and bring troubles to the application of lithium batteries. In order to avoid the expansion of the impact of thermal runaway of lithium batteries, a fireproof and explosion-proof barrier can be set between the lithium battery cell and the cell top cover. In the existing technology, thermal insulation felt and aerogel insulation are generally used as thermal pads.

[0004] Ceramic polyolefin materials possess the excellent properties of ordinary polymers at room temperature and can form a self-supporting ceramic structure at high temperatures. While they can provide fire and heat insulation, their thermal shock resistance is poor. In the event of a battery explosion, they cannot effectively block the impact of a cell explosion and can still cause the cell cover to pierce. To improve the impact resistance of thermal insulation pads, reinforcing fibers are generally added to the polyolefin material. However, this also makes it difficult to evenly disperse the reinforcing fibers in the polyolefin material, resulting in poor processing performance of the polyolefin material. The resulting extruded coils are unlikely to meet actual needs.

[0005] In addition, existing ceramic polyolefin materials are difficult to shape. The thickness of the prepared polyolefin coils is generally greater than 10 mm, and the width of the coils is no more than 300 mm. It is impossible to prepare coils with a thickness less than 5 mm and a width greater than 500 mm, which limits the application of polyolefin coils. Summary of the Invention

[0006] In order to overcome the problems of existing ceramic polyolefin coils such as large thickness, small width and poor thermal shock resistance, the present invention provides a ceramic polyolefin composite material. The ceramic polyolefin coil prepared from the ceramic polyolefin composite material has small thickness, large width and good flame retardancy and thermal shock resistance.

[0007] The technical problem to be solved by the present invention is achieved by adopting the following technical solutions:

[0008] One of the objects of the present invention is to provide a ceramic polyolefin composite material comprising the following components in percentage by weight:

[0009]

[0010] The rest are additives;

[0011] The MFR of the EVA resin at a temperature of 190° C. and a load of 5 kg is 5 to 7 g / 10 min;

[0012] The MFR of the PP resin at a temperature of 190° C. and a load of 5 kg is 30 to 35 g / 10 min;

[0013] The ceramic polyolefin composite material has an MFR of 5 to 10 g / 10 min at a temperature of 190° C. and a load of 5 kg.

[0014] Ethylene vinyl acetate resin, referred to as EVA resin. Polypropylene resin, referred to as PP resin.

[0015] A second object of the present invention is to provide a ceramic polyolefin coil comprising a first reinforcing fiber cloth, a second reinforcing fiber cloth and a ceramic polyolefin layer disposed between the first reinforcing fiber cloth and the second reinforcing fiber cloth, wherein the ceramic polyolefin layer is processed from the ceramic polyolefin composite material.

[0016] A third object of the present invention is to provide applications of the ceramic polyolefin coil in the fields of automotive parts and / or building fire protection.

[0017] The beneficial effects of the present invention are:

[0018] (1) The ceramic polyolefin composite material provided by the present invention has excellent processing performance at room temperature and can be used to prepare coils with a thickness of 0.5 to 10 mm and a width of 300 to 1300 mm, and has a wide range of applications.

[0019] (2) The ceramic polyolefin coil prepared by the present invention has excellent mechanical properties, fire resistance and thermal insulation properties. When the thickness of the ceramic polyolefin layer is 1 mm, the tensile strength of the ceramic polyolefin coil can reach 40 MPa; it can be kept at 1200°C for more than 30 minutes without being melted through by the flame; and it also has good thermal insulation properties. When the front temperature is 1000°C, the back temperature is about 400-500°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Schematic diagram of the structure of the ceramic polyolefin coil of the present invention;

[0021] Among them, 1-first reinforcing fiber cloth; 2-ceramic polyolefin layer; 3-second reinforcing fiber cloth;

[0022] Figure 2 Schematic diagram of the fire-resistant sandblasting test of the ceramic polyolefin coil of the present invention;

[0023] Figure 3 This is a picture of the ceramic polyolefin coil prepared in Example 11;

[0024] Figure 4 Graphs showing heat release of ceramic polyolefin coils prepared in Example 1 and Comparative Example 19;

[0025] Figure 5 This is a picture of the ceramic polyolefin coil prepared in Comparative Example 1;

[0026] Figure 6 This is a picture of the ceramic polyolefin coil prepared in Comparative Example 6. DETAILED DESCRIPTION

[0027] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is further described below with reference to specific embodiments and illustrations.

[0028] The present invention provides a ceramic polyolefin composite material comprising the following components in percentage by weight:

[0029]

[0030] The rest are additives;

[0031] The MFR of the EVA resin at a temperature of 190° C. and a load of 5 kg is 5 to 7 g / 10 min;

[0032] The MFR of the PP resin at a temperature of 190° C. and a load of 5 kg is 30 to 35 g / 10 min;

[0033] The ceramic polyolefin composite material has an MFR of 5 to 10 g / 10 min at a temperature of 190° C. and a load of 5 kg.

[0034] By adjusting the amounts of EVA and PP resins and combining them with specific melt flow rates, the present invention achieves a ceramicized polyolefin composite material that meets processing performance requirements. This composite material can be used to produce ceramicized polyolefin coils with a width of at least 900 mm. Under optimal conditions, the EVA resin has an MFR of 5 to 7 g / 10 min at a temperature of 190°C and a load of 5 kg; the PP resin has an MFR of 30 to 35 g / 10 min at a temperature of 190°C and a load of 5 kg.

[0035] The ceramic polyolefin composite material provided by the present invention is formed by combining a specific proportion of zinc borate-coated inorganic phosphate with low-melting-point glass powder and silicate materials to form a synergistic effect. When the ceramic polyolefin is heated, it can form a ceramic body, achieving ideal fire-resistant heat-insulating effects and fire-resistant impact performance.

[0036] The present invention utilizes the good surface compatibility of supporting material and polyolefin material, and the grid-like supporting material is embedded into the layered polyolefin sheet surface by the hot pressing process of calender.When heated, the polyolefin surface and the grid-like supporting layer form a ceramic body, and the grid-like supporting layer provides a skeleton reinforcement structure for the surface layer, and the surface polyolefin layer is constantly ceramicized, which continuously increases hardness.In the continuous heating process, the polyolefin material is thermally decomposed to produce flammable small molecule hydrocarbon gas (methane, ethylene, etc.) and incombustible gas (carbon dioxide and carbon monoxide, etc.), forming a loose and porous gap, and the gap periphery forms a ceramic layer of stable structure, and then forms a confined air inside the material, and high temperature prompts the polyolefin material overall structure to produce a certain degree of expansion.Because air is a poor conductor of heat, this characteristic can significantly reduce heat conduction efficiency, so that a larger temperature difference is formed between the fire-facing surface and the back-fire surface of the material.

[0037] In the present invention, the melting temperature range of the low-melting glass powder is preferably 550-650°C. Precise control of this temperature range is of great significance. If the melting temperature of the low-melting glass powder is too low, it may cause the gas generated during the combustion of the composite material to be difficult to discharge, thereby forming a large number of pores or bubbles inside the ceramic body; at the same time, it will also inhibit the full reaction of the silicate material and the glass phase, which may cause a reduction in the amount of crystal phase generated or fine grain development, ultimately affecting the strength and structural stability of the ceramic body. If the melting temperature of the low-melting glass powder is too high: on the one hand, insufficient liquid phase formation at high temperature will lead to insufficient densification of the ceramic body, and a large number of unfilled pores will remain inside. At the same time, the bonding force between the particles is weak due to the lack of liquid phase bonding, which significantly reduces the strength of the ceramic body; on the other hand, high temperature may cause the zinc borate coating or inorganic phosphate to decompose prematurely (such as phosphate decomposition to produce P2O5), or cause the low-melting point components (such as B2O3, ZnO) to be lost due to volatilization, destroying the balance of the formula ratio, and ultimately affecting the flame retardant properties, molding properties and impact resistance of the ceramic body.

[0038] In the present invention, the silicate includes but is not limited to one or more of wollastonite, mica, asbestos, feldspar, talc, and diatomaceous earth. These silicates can improve the fire resistance of polyolefin materials.

[0039] In the present invention, the inorganic phosphate in the zinc borate-coated inorganic phosphate includes, but is not limited to, one or more of aluminum dihydrogen phosphate, aluminum phosphate, calcium hydroxyphosphate, calcium hydrogen phosphate, amorphous calcium phosphate, magnesium phosphate, magnesium phosphate, magnesium phosphate hydrate, and magnesium ammonium phosphate hydrate. Preferably, the inorganic phosphate has a particle size of micrometers, preferably 1 to 100 μm.

[0040] In the present invention, the auxiliary agent includes but is not limited to one or more of an antioxidant, a lubricant, a release agent, a plasticizer, an anti-ultraviolet agent, and a pigment. The amount of these auxiliary agents can be adjusted according to actual needs. The antioxidant includes but is not limited to one or more of phenolic antioxidants, amine antioxidants, phosphite antioxidants, and thioacrylate antioxidants. The lubricant includes but is not limited to one or more of polyethylene wax, silicone masterbatch, stearic acid, ethylene bisstearamide, and paraffin wax.

[0041] In this application, under preferred conditions, the ceramic polyolefin composite material also includes an organic flame retardant. The organic flame retardant is composed of an organic phosphate and a triazine compound in a mass ratio of 1 to 4:1. Compared to inorganic phosphates, the zinc borate-coated inorganic phosphate used in this application has the following advantages: it promotes low-temperature sintering, provides uniform dispersion, improves mechanical strength, and enhances chemical stability.

[0042] The organic phosphate includes but is not limited to one or more of phosphites, aminotrimethylene phosphate (ATMP), ethylenediaminetetramethylene phosphate (EDTMP), and hydroxyethylenediphosphonate; the triazine compound includes but is not limited to one or more of benzotriazine, tribromotriazine, tribromoisocyanurate, and hexachlorotriazine.

[0043] The inventors have found that the ceramic polyolefin composite material has an MFR of 5 to 10 g / 10 min at a temperature of 190° C. and a load of 5 kg. Under these conditions, a coil with a width of 1000 to 1350 mm can be produced.

[0044] The present invention also provides a ceramic polyolefin coil, comprising a first reinforcing fiber cloth 1, a second reinforcing fiber cloth 3 and a ceramic polyolefin layer 2 arranged between the first reinforcing fiber cloth and the second reinforcing fiber cloth, wherein the ceramic polyolefin layer is processed from the ceramic polyolefin composite material.

[0045] The width of the ceramicized polyolefin coil is not less than 300 mm, preferably not less than 500 mm, and more preferably not less than 900 mm.

[0046] The thickness of the ceramic polyolefin coil is 0.5 to 10 mm, preferably 0.5 to 5 mm, and more preferably 0.5 to 3 mm.

[0047] The thickness of the ceramic polyolefin layer is 0.5-2 mm.

[0048] The thickness of the first reinforcing fiber cloth 1 and / or the second reinforcing fiber cloth 3 is 0.05-0.5 mm.

[0049] The first reinforcing fiber cloth and the second reinforcing fiber cloth are each independently selected from one of glass fiber cloth, basalt fiber cloth and high silica fiber cloth.

[0050] The present invention also provides applications of the ceramic polyolefin composite material and the ceramic polyolefin coil in the fields of automobile parts and / or building fire protection.

[0051] Performance testing method in the present invention:

[0052] MFR is tested in accordance with GB / T 3682.1-2018 “Plastics Thermoplastics Melt Mass-Flow Rate (MFR) and Melt Volume-Flow Rate (MVR) Part 1: Standard Method” at a temperature of 190°C and a load of 5 kg.

[0053] The test methods for tensile strength and elongation at break are in accordance with GB / T 1040.3.

[0054] Fire resistance impact performance test method: according to Figure 2 The schematic diagram in the figure shows the settings of a sandblasting gun and a flame spraying gun. The parameter settings are: the angle between the spray direction and the plane of the sheet sample is 45°, the spraying conditions are: the inner diameter of the sandblasting gun nozzle is 6 mm, the distance from the sample is 20 cm, the gas-driven spraying object is 80-mesh quartz sand, and the center temperature of the sample surface is maintained at 120°C. The test is carried out according to the following method: (1) the coil is burned at 1200°C for 10 seconds; then, it is sandblasted for 5 seconds at an outlet pressure of 0.8 MPa, and then burned for 5 seconds. (2) Step (1) is repeated 3 times; then the coil is observed to see if it is penetrated (if penetrated, it is unqualified). If the coil is not penetrated (if not penetrated, it is qualified), the back temperature of the coil is measured.

[0055] The transverse / longitudinal shrinkage rate is tested according to GB / T 12027-2004 "Test method for dimensional change of plastic film and sheeting caused by heating".

[0056] Calculation method of maximum thickness tolerance: According to the national standard GB / T 6672-1986 "Plastic film and sheeting - Determination of thickness - Mechanical measurement method", test the thickness of 20 random points on the coil and record the maximum thickness value X max And the minimum thickness value X min , and calculate the average thickness X of 20 points 平均 , the maximum thickness tolerance is calculated by the following formula. Maximum thickness tolerance = |(X max / min -X 平均 / )X平均 |×100%.

[0057] Fire-resistant insulation withstand voltage and leakage current performance test method: At a DC voltage of 1000V, the sample is burned with a butane torch for 3 minutes. The insulation resistance before and after burning is measured. If the resistance is greater than 200MΩ, the test is passed; if the resistance is less than 200MΩ, the test is failed.

[0058] The flame retardant rating test is carried out according to the UL-94 method of vertical burning test (V-0 / V-1 / V-2).

[0059] The heat release rate test was conducted according to the plastic cone calorimeter test standard ISO 5660, with a sample thickness of 3 mm.

[0060] Preparation example:

[0061] Preparation of zinc borate-coated aluminum phosphate (weight ratio of zinc borate to aluminum phosphate is 10:100)

[0062] Step S1: Weigh 2.43 g of borax, add 150 mL of deionized water, and stir at 300 r / min for 15 min to obtain borax solution A.

[0063] Step S2: 5.21 g of zinc chloride was weighed, 150 mL of deionized water was added, and the mixture was stirred at 300 r / min for 15 min. Then, 40 g of aluminum phosphate was added, and stirring was continued for 30 min. Borax solution A was added to form a mixed system B.

[0064] Step S3: Slowly add a 0.5 mol / L sodium hydroxide aqueous solution dropwise to the mixed system B, while strictly controlling the addition rate to maintain the pH value of the system at 7.5 to 8.0. After the addition is complete, stir and react at a speed of 300 r / min and a temperature of 90° C. for 6 hours. After the reaction is completed, the mixed system is filtered, and the filter cake is washed and dried to obtain zinc borate-coated aluminum phosphate.

[0065] Example 1

[0066] The formula of the ceramic polyolefin composite material is shown in Table 1.

[0067] Table 1

[0068] raw material Weight percentage EVA resin (MFR 5g / 10min) 35％ PP resin (MFR 35g / 10min) 10％ Low melting point glass powder (melting point is 550℃) 23％ Zinc borate coated aluminum phosphate 15％ Wollastonite 15％ Antioxidant 1010 0.5％ Polyethylene wax 0.5％ Silicone masterbatch PA445200 1％

[0069] According to Table 1, the ceramic polyolefin composite material was fed into an extruder. The extrusion port passed through a die, and then, using upper and lower rollers, glass fiber cloth was hot-pressed and laminated to the upper and lower sides of the extruded polyolefin layer to produce a ceramic polyolefin coil with a width of 900 mm and a thickness of 1.4 mm. The ceramic polyolefin coil obtained in this example comprised, from top to bottom, a first reinforcing fiber cloth 1, a ceramic polyolefin layer 2, and a second reinforcing fiber cloth 3. The thickness of both the first reinforcing fiber cloth 1 and the second reinforcing fiber cloth 3 was 0.2 mm.

[0070] Examples 2 to 3 and Comparative Examples 1 to 4

[0071] The method of Example 1 was followed, except that EVA resin and PP resin with different MFRs were used, as shown in Table 2.

[0072] The performance tests were conducted on the ceramic polyolefin composite materials and ceramic polyolefin coils prepared in Examples 1 to 3 and Comparative Examples 1 to 4. The results are shown in Table 2.

[0073] Table 2

[0074]

[0075] As can be seen from Table 2, as the MFR of EVA and PP increases, the MFR of the masterbatch also increases. When the MFR of EVA is 3 g / 10 min or the MFR of PP is 25 g / 10 min, a 900 mm wide coil cannot be produced. When the MFR of the masterbatch reaches 10 g / min or more, the fluidity of the material in the molten state is too high. Excessive fluidity will cause the flow rate of the material in the extrusion die to be unstable, resulting in an increase in the coil thickness tolerance (required to be less than 10%) and even the appearance of periodic stripes. At the same time, it causes the longitudinal or transverse shrinkage rate of the coil to exceed (required to be less than 3%) and poor dimensional stability.

[0076] Example 4 and Comparative Examples 5-6

[0077] The method of Example 1 was followed, except that the amounts of EVA and PP were adjusted, as shown in Table 3.

[0078] The performance tests were conducted on the ceramic polyolefin composite materials and ceramic polyolefin coils prepared in Example 4 and Comparative Examples 5-6. The results are shown in Table 3.

[0079] Table 3

[0080]

[0081] As can be seen from Table 3: as the amount of PP increases, the MFR of the masterbatch increases, the mechanical properties of the coil decrease, and the transverse / longitudinal shrinkage and maximum thickness tolerance increase significantly. This shows that an excessively large MFR of the masterbatch will increase the difficulty of process control during the actual extrusion process to form the coil, which is not conducive to the production of products that meet the quality control range; when the amount of EVA is too large, the MFR of the masterbatch is small, and it is impossible to prepare a 900mm wide coil.

[0082] Examples 5 to 7 and Comparative Examples 7 to 10

[0083] The method of Example 1 was followed, except that the initial melting temperature of the low-melting-point glass powder and the amount of the low-melting-point glass powder were changed, as shown in Table 4.

[0084] The performance of the ceramicized polyolefin coils prepared in Examples 5 to 7 and Comparative Examples 7 to 10 was tested. The results are shown in Table 4.

[0085] Table 4

[0086]

[0087]

[0088] From Table 4 we can see that:

[0089] When the melting point of the low-melting-point glass powder is too low or too high, the material cannot be porcelainized in a short period of time, and the material does not have fire-resistant impact properties. During the test, the sandblasting pressure causes it to be burned through.

[0090] The reason why the fire-resistant impact performance of comparative examples 7 / 8 failed the test is that if the melting temperature of the low-melting-point glass powder is too low, the glass powder may flow excessively due to a long residence time in a high-temperature environment, making it difficult for the gas trapped in the combustion process to be discharged, and then forming a large number of pores or bubbles inside the ceramic body. At the same time, low temperature conditions will inhibit the full reaction of the silicate material and the glass phase, which may result in a reduction in the amount of crystal phase generated or fine grain development, ultimately affecting the strength and structural stability of the ceramic body. If the melting temperature of the low-melting-point glass powder is too high, insufficient liquid phase formation at high temperature will lead to insufficient densification of the ceramic body, and a large number of unfilled pores will remain inside. At the same time, the bonding force between the particles is weak due to the lack of liquid phase adhesion, which significantly reduces the strength of the ceramic body. When the amount of low-melting-point glass powder is too high, it will also cause the material to be over-softened and unable to withstand the impact of quartz sand.

[0091] The reasons why Examples 6 / 7 and Comparative Examples 9 / 10 failed the fire-resistant impact performance test are: when the initial melting temperature is the same, the usage of low-melting-point glass powder is too high, which will cause excessive softening of the material during the porcelain-forming process, which is not conducive to improving the strength of the porcelain; the usage of low-melting-point glass powder is too low, the liquid phase is insufficiently formed, the voids cannot be completely filled, and the density is insufficient.

[0092] Examples 8 to 9 and Comparative Examples 11 to 17

[0093] The method of Example 1 was followed, except that the total amount of low-melting-point glass powder, wollastonite and zinc borate-coated aluminum phosphate was kept unchanged (53%), and the amount ratio of low-melting-point glass powder, zinc borate, wollastonite and aluminum phosphate was adjusted, as shown in Table 5.

[0094] The performance of the ceramic polyolefin coils prepared in Examples 8 to 9 and Comparative Examples 11 to 17 was tested. The results are shown in Table 5.

[0095] Table 5

[0096]

[0097]

[0098] Table 5 shows that low-melting-point glass powder melts at high temperatures to form a liquid phase, which facilitates the vitrification of the ceramic filler. Consequently, in Comparative Examples 11-13, as the low-melting-point glass powder content decreases, insufficient liquid phase forms, resulting in inadequate vitrification of the ceramic filler, impacting vitrification and shell shielding, ultimately affecting refractory impact resistance. In Comparative Examples 14-16, due to an unsuitable proportion of vitrifiable materials, the resulting coils are also prone to burn-through.

[0099] Examples 10-11 and Comparative Examples 17-18

[0100] The method of Example 1 is followed, except that flame retardant powder is added to the formula, and the flame retardant powder is composed of divinyl aluminum hypophosphite and tribromotriazine in a mass ratio of 4:1.

[0101] Among them, the total amount of porcelain-forming powder (low-melting point glass powder, zinc borate-coated aluminum phosphate, wollastonite) and flame-retardant powder (divinyl aluminum hypophosphite, tribromotriazine) is kept unchanged (53%), and the amount ratio of each component in the porcelain-forming powder is kept unchanged (the amount ratio of low-melting point glass powder, wollastonite, and zinc borate-coated aluminum phosphate is 23:15:15), and the amount ratio of powder combination 1 and powder combination 2 is adjusted, as shown in Table 6.

[0102] Comparative Example 19

[0103] The method of Example 11 was followed, except that the zinc borate-coated aluminum phosphate was replaced with a physical mixture of zinc borate and aluminum phosphate, and the weight ratio of zinc borate to aluminum phosphate was 1.5:13.5. The experimental results are shown in Table 6.

[0104] The performance of the ceramicized polyolefin coils prepared in Examples 10-11 and Comparative Examples 18-19 was tested. The results are shown in Table 6.

[0105] Table 6

[0106] Porcelain powder (%) Flame retardant powder (%) Fire impact resistance Flame retardant grade Example 1 53 0 qualified V-2 Example 10 38 15 qualified V-0 Example 11 33 20 qualified V-0 Comparative Example 17 28 25 Unqualified V-0 Comparative Example 18 23 30 Unqualified V-0 Comparative Example 19 53 0 Unqualified HB

[0107] It can be seen from Table 6 that when the content of the ceramic powder is within the range of 33% to 53%, coils that meet both flame retardancy and fire impact resistance properties can be prepared.

[0108] Figure 3 The ceramic polyolefin coil is obtained by extrusion according to the formula of Example 11. Figure 3 It can be seen from the figure that the embodiment of the present invention can extrude a ceramic polyolefin coil having a smooth surface and a width greater than 900 mm.

[0109] from Figure 4 It can be seen that the comparative example 19 using uncoated ceramic powder has a higher peak heat release than the example 1 using zinc borate coated aluminum phosphate.

[0110] Table 7 shows the heat release, heat production rate per unit mass, mass loss rate and specific extinction area performance of the coils prepared in Example 1 and Comparative Example 19 after burning for 3 minutes.

[0111] Table 7

[0112] Test items Example 1 Comparative Example 19 <![CDATA[Heat release (kW / m 2 )]]> 157.77 164.63 Heat production per unit mass (MJ / kg) 27.45 29.43 <![CDATA[Mass loss rate (g / s·m 2 )]]> 5.09 5.59 <![CDATA[Specific extinction area (m 2 / kg)]]> 249.33 290.82

[0113] It can be seen from Table 7 that after 3 minutes of combustion, the heat release, heat production rate per unit mass, mass loss rate, and specific extinction area generated by Example 1 are all better than those of Comparative Example 19. This shows that the use of zinc borate to coat inorganic phosphate can be better dispersed in low-melting-point glass powder and silicate materials. On the one hand, the coating layer can prevent the agglomeration of inorganic phosphate particles; on the other hand, zinc borate helps the entire system to reach a more uniform mixing state before the high-temperature reaction, so that the reaction proceeds evenly, and the uniform and consistent ceramic structure finally formed has more stable performance. During the test process, a layer of ceramic with a protective effect can be formed on the surface, thereby making the heat release, heat production rate per unit mass, mass loss rate, and specific extinction area performance better.

[0114] Examples 12-13 and Comparative Examples 19-20

[0115] The method of Example 10 was followed, except that the ratio of divinyl aluminum phosphite to tribromotriazine was adjusted, and the total amount of flame retardant powder (organic phosphate, tribromotriazine) was kept unchanged (15%), as shown in Table 8.

[0116] The performance of the ceramic polyolefin coils prepared in Examples 12 to 13 and Comparative Examples 20 to 21 was tested. The results are shown in Table 8.

[0117] Table 8

[0118]

[0119] It can be seen from Table 6 that when only organic phosphate is added, the flame retardant grade of the coil is V-2; by adjusting the ratio of diethylene aluminum hypophosphite and tribromotriazine to a mass ratio of 4:1, the overall flame retardant performance of the material can be further improved to V-0 without increasing the content of flame retardant.

[0120] Comparative Example 21

[0121] According to the method of CN 114230903A, only a coil with a width of 300 mm can be prepared, and a coil with a width of 900 mm cannot be prepared.

[0122] The ceramic polyolefin composite material and ceramic polyolefin coil prepared in Comparative Example 21 were subjected to performance tests. The results are shown in Table 9.

[0123] Table 9

[0124] Coil width Flame retardant grade Fire impact resistance Comparative Example 20 300mm HB Burn through

[0125] It can be seen from Table 8 that the ceramic polyolefin coil prepared according to the method of CN 114230903A not only cannot reach a width of 900 mm, but also its fire retardant performance and fire impact resistance are worse than those of Example 11.

[0126] Comparative Example 22

[0127] According to the method of CN 117264304A, the resin cannot be evenly dispersed in the extruder, resulting in a wavy texture on the surface. As a result, a coil with a stable and uniform smooth surface cannot be formed, and a coil with a width of 300 mm or more cannot be prepared.

[0128] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. A ceramic polyolefin composite material, characterized in that: The ceramic polyolefin composite material comprises the following components in percentage by weight: The rest are additives; The MFR of the EVA resin at a temperature of 190° C. and a load of 5 kg is 5 to 7 g / 10 min; The MFR of the PP resin at a temperature of 190° C. and a load of 5 kg is 30 to 35 g / 10 min; The ceramic polyolefin composite material has an MFR of 5 to 10 g / 10 min at a temperature of 190° C. and a load of 5 kg.

2. The ceramic polyolefin composite material according to claim 1, characterized in that: The melting temperature of the low-melting-point glass powder is in the range of 550 to 650°C.

3. The ceramic polyolefin composite material according to claim 1, characterized in that: The silicate is selected from one or more of wollastonite, mica, asbestos, feldspar, talc, and diatomaceous earth.

4. The ceramic polyolefin composite material according to claim 1, characterized in that: The weight ratio of zinc borate to inorganic phosphate in the zinc borate-coated inorganic phosphate is (10-20):100; Preferably, the inorganic phosphate is selected from one or more of aluminum dihydrogen phosphate, aluminum phosphate, calcium hydroxyphosphate, calcium hydrogen phosphate, amorphous calcium phosphate, magnesium phosphate, magnesium phosphate stone, magnesium phosphate hydrate, magnesium ammonium phosphate hydrate, and calcium silicate minerals.

5. The ceramic polyolefin composite material according to claim 1, characterized in that: The auxiliary agent includes one or more of an antioxidant, a lubricant, a release agent, a plasticizer, an anti-ultraviolet agent, and a pigment.

6. The ceramic polyolefin composite material according to claim 1, characterized in that: The ceramic polyolefin composite material further comprises an organic flame retardant, wherein the organic flame retardant is composed of an organic phosphate and a triazine compound in a mass ratio of (1 to 4):1; Preferably, the organic phosphate is selected from one or more of phosphites, amino trimethylene phosphates, ethylenediamine tetramethylene phosphates, and hydroxyethylene diphosphonates; Preferably, the triazine compound is one or more of benzotriazine, tribromotriazine, tribromoisocyanurate, and hexachlorotriazine.

7. A ceramic polyolefin coil, characterized in that: The ceramic polyolefin coil comprises a first reinforcing fiber cloth (1), a second reinforcing fiber cloth (3) and a ceramic polyolefin layer (2) arranged between the first reinforcing fiber cloth and the second reinforcing fiber cloth, and the ceramic polyolefin layer is processed from the ceramic polyolefin composite material according to any one of claims 1 to 6.

8. The ceramic polyolefin coil according to claim 7, characterized in that: The width of the ceramicized polyolefin coil is not less than 300 mm, preferably not less than 500 mm, more preferably not less than 900 mm; Preferably, the thickness of the ceramicized polyolefin coil is 0.5 to 10 mm, preferably 0.5 to 5 mm, more preferably 0.5 to 3 mm; Preferably, the thickness of the first reinforcing fiber cloth (1) and / or the second reinforcing fiber cloth (3) is 0.05 to 0.5 mm; Preferably, the thickness of the ceramicized polyolefin layer (2) is 0.5 to 2 mm.

9. The ceramic polyolefin coil according to claim 7, characterized in that: The first reinforcing fiber cloth (1) and the second reinforcing fiber cloth (3) are each independently selected from one of glass fiber cloth, basalt fiber cloth, and high silica fiber cloth.

10. Use of the ceramic polyolefin coil according to any one of claims 7 to 9 in the fields of automobile parts and / or building fire protection.

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