Heat-resistant and flame-retardant new energy automobile cable material and preparation method thereof

Abstract

The invention provides a heat-resistant and flame-retardant new energy automobile cable material and a preparation method thereof. Specifically, the new energy cable material comprises the following components in parts by weight: 100 parts of modified PVC resin; the flame retardant comprises the following components in parts by weight: 80-50 parts of styrene-ethylene-butylene-styrene, 5-15 parts of a bio-based modified MgOH flame retardant, 5-15 parts of color masterbatch and 5-10 parts of an auxiliary agent. According to the invention, the flame retardant is modified, and the bio-based phosphorus-containing compound is grafted with the Mo / GO doped MgOH material, so that the flame-retardant and smoke-suppression efficiency of MgOH is improved, cable resin is effectively toughened, and the service life is prolonged; by carrying out alcohol group modification on PVC, the hydrogen bond relation between the modified PVC resin and the bio-based modified MgOH flame retardant is improved, and the heat resistance and aging resistance of the PVC material cable are synergistically improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material preparation, and in particular to a heat-resistant and flame-retardant new energy vehicle cable material and a preparation method thereof. Background Art

[0002] As a key technology for scientific and technological development, green development, and sustainable development, new energy vehicles are undergoing gradual industrialization and scale-up, and the corresponding supporting equipment also needs to be gradually improved and enhanced. For cables used in new energy vehicle charging piles, polyurethane sheathing materials, rubber sheathing materials and insulation materials, and TPE sheathing materials and insulation materials are currently the most commonly used. Among these materials, polyurethane materials have poor processing performance and are relatively high in price, while rubber materials have significant limitations in processing technology and equipment. TPE materials have better overall performance and a high cost-effectiveness, but they also have performance flaws such as weather resistance, oil resistance, heat aging resistance, and thermal stress cracking, which require further improvement and resolution. PVC materials, as the most widely used, largest-volume, and longest-standing general-purpose plastic, are undergoing continuous technological development. Previous issues such as environmentally unfriendly additives, poor thermal performance, and combustion smoke generation are being addressed through new processes and technologies. PVC products are now widely used in the pharmaceutical, food, cable material, and automotive interior wiring fields, and are gaining wider adoption due to their high performance, reasonable price, and excellent cost-effectiveness.

[0003] PVC products also have a large market for cable materials, especially low-halogen (or halogen-free) cable materials. However, after reviewing and testing the charging pile cable materials on the market, we found that low-halogen or halogen-free materials have obvious defects in terms of softness, small bend radius, high and low temperature resistance, oil resistance, low smoke, and thermal stability (long-term and short-term thermal stability), and cannot meet the application requirements. This shows that such products still have high technical difficulty and research value, and the products are also difficult to be recognized and promoted in use. Summary of the Invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a heat-resistant and flame-retardant new energy vehicle cable material and a preparation method thereof, so as to improve the heat resistance, aging resistance and flame retardancy of existing PVC material cables and increase the service life of the cables.

[0005] The technical solution of the present invention:

[0006] In a first aspect, the present application provides a heat-resistant and flame-retardant new energy vehicle cable material, which comprises the following components in parts by weight: 100 parts of modified PVC resin; 80-50 parts of styrene-ethylene-butylene-styrene (SEBS), 5-15 parts of bio-based modified MgOH flame retardant, 5-15 parts of color masterbatch, and 5-10 parts of auxiliary agent.

[0007] In some embodiments, the modified PVC resin is obtained by polymerization of vinyl chloride and 3-buten-1-ol.

[0008] In some embodiments, the molar ratio of vinyl chloride and 3-buten-1-ol is 20-10:1.

[0009] In some embodiments, the number average molecular weight of the modified PVC resin is 40,000-80,000.

[0010] In some embodiments, the preparation method of the modified PVC resin comprises the following steps:

[0011] The 3-buten-1-ol is dissolved in a solvent, an initiator is added, and vinyl chloride gas is introduced under the protection of inert gas, and the reaction is carried out under pressure and heating. After the reaction is completed, an alcohol is added to precipitate the polymer, and the modified PVC resin is obtained after washing and drying.

[0012] In some embodiments, the bio-based modified MgOH flame retardant is a flame retardant with magnesium hydroxide as the inner layer, graphene oxide and nano-molybdenum oxide as the outer layer, and grafted with a phosphorus-containing bio-based material.

[0013] In some embodiments, the preparation method of the bio-based modified MgOH flame retardant comprises the following steps:

[0014] Step 1: weigh ammonium heptamolybdate and graphene oxide, add water and stir to obtain a mixed solution; add magnesium hydroxide to the above ammonium molybdate solution, transfer to a polytetrafluoroethylene lined reaction kettle, heat and stir to react, and obtain a suspension after the reaction is completed, and then filter and wash to obtain a doped material;

[0015] Step 2: add the doped material, boric acid, glycerophosphate and solvent to the reactor, then add urea and deionized water to the reactor, and then heat to react, and obtain the bio-based modified MgOH flame retardant after post-treatment.

[0016] In some embodiments, the molar ratio of ammonium heptamolybdate, graphene oxide and magnesium hydroxide is 0.2-0.8:0.5-1:1.

[0017] In some embodiments, the reaction temperature of step 1 is 80-160°C, and the reaction time is 4-6h.

[0018] In some embodiments, the addition ratio of the doping material, boric acid, glycerophosphate, and urea is 10 g: 1-4 mol: 1-2 mol: 1-2 mol.

[0019] In some embodiments, the reaction temperature of step 2 is 140-170° C., and the reaction time is 2-6 h.

[0020] In some embodiments, the auxiliary agent is selected from one or more combinations of light stabilizers, anti-aging agents, lubricants, antioxidants, compatibilizers, plasticizers, and ultraviolet absorbers.

[0021] By modifying the MgOH flame retardant to contain bio-based phosphorus and combining it with nano-molybdenum oxide, the smoke emission rate of MgOH is reduced, the flame retardant effect is improved, and the compatibility between the inorganic flame retardant particles and the resin is improved, thereby further improving the mechanical properties and service life of the cable material.

[0022] In a second aspect, the present invention provides a method for preparing the new energy vehicle cable material, which specifically comprises the following steps:

[0023] Step 1: Weigh each component according to the above raw material ratio;

[0024] Step 2: Mix the modified PVC resin, styrene-ethylene-butylene-styrene, bio-based modified MgOH flame retardant, masterbatch and additives at 100° C.-130° C. for 10-20 minutes and granulate.

[0025] Beneficial effects:

[0026] 1. The present invention improves the flame retardant and smoke suppression efficiency of MgOH by modifying the flame retardant and using bio-based phosphorus-containing compounds to graft Mo / GO doped MgOH materials, while effectively toughening the cable resin and improving its service life.

[0027] 2. By modifying PVC with alcohol groups, the hydrogen bond between the modified PVC resin and the bio-based modified MgOH flame retardant is improved, thereby synergistically improving the heat resistance and aging resistance of PVC material cables. DETAILED DESCRIPTION

[0028] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0029] Unless otherwise specified, the chemical reagents used in the present invention were all commercially available analytical grade. The SEBS used in the examples was selected from Baling Petrochemical YH-503T; the masterbatch was a white masterbatch purchased from Beijing Chemical High-Tech, brand PPB8259M; and the antioxidant was purchased from BASF, model 1010.

[0030] Preparation Example of Modified PVC Resin 1

[0031] 5 mmol of 3-butene-1-ol was dissolved in THF solvent, 0.03 g of AIBN was added, 95 mmol of vinyl chloride gas was introduced under inert gas protection, and the mixture was heated at 55°C at 3 atm for 6 h. After the reaction, excess methanol was added to precipitate the polymer, which was washed and dried to obtain the modified PVC resin.

[0032] The number average molecular weight of the polymer was determined by GPC gel permeation chromatography using THF as the solvent, and the Mn of the obtained polymer was ≈50,000.

[0033] Preparation Example 2 of Modified PVC Resin

[0034] The preparation method is basically the same as that of the modified PVC resin 1, except that the added molar amounts of 3-butene-1-ol and vinyl chloride are 5 mmol and 105 mmol, respectively.

[0035] Preparation Example of Bio-based Modified MgOH Flame Retardant 1

[0036] Step 1: Weigh 0.2 mol of ammonium heptamolybdate and 0.5 mol of graphene oxide, add 70 ml of water and stir evenly to obtain a mixed solution; add 1 mol of magnesium hydroxide to the above ammonium molybdate solution, transfer to a polytetrafluoroethylene-lined reactor, heat at 150°C and stir for 4 hours. After the reaction is completed, a suspension is obtained, which is filtered and washed to obtain a doping material;

[0037] Step 2: 10 g of doping material, 1 mol of boric acid, 1 mol of glycerophosphate and 100 ml of toluene solvent were added to the reactor, and then 1 mol of urea and 20 ml of deionized water were added to the reactor, and then heated to 150° C. for 4 h. After post-treatment, a bio-based modified MgOH flame retardant 1 was obtained, hereinafter referred to as modified flame retardant 1.

[0038] Preparation Example 2 of Bio-based Modified MgOH Flame Retardant

[0039] The preparation example is basically the same as that of the bio-based modified MgOH flame retardant 1, except that in step 1, the amount of graphene oxide added is 0 mol, and the bio-based modified MgOH flame retardant 2 is obtained, hereinafter referred to as modified flame retardant 2.

[0040] Preparation Example 3 of Bio-based Modified MgOH Flame Retardant

[0041] The preparation example of the bio-based modified MgOH flame retardant 1 is basically the same, except that in step 1, the addition amount of ammonium heptamolybdate is 0 mol, to obtain the bio-based modified MgOH flame retardant 3, hereinafter referred to as modified flame retardant 3.

[0042] Preparation example of bio-based modified MgOH flame retardant 4

[0043] The preparation example of the bio-based modified MgOH flame retardant 1 is basically the same, except that in step 2, the addition amount of boric acid is 0 mol, to obtain the bio-based modified MgOH flame retardant 4, hereinafter referred to as modified flame retardant 4.

[0044] Preparation example of bio-based modified MgOH flame retardant 5

[0045] The preparation example of the bio-based modified MgOH flame retardant 1 is basically the same, except that in step 2, the addition amount of glycerophosphate is 0 mol, to obtain the bio-based modified MgOH flame retardant 5, hereinafter referred to as modified flame retardant 5.

[0046] Example

[0047] Step 1: weigh each component according to the raw material ratio of Table 1;

[0048] Step 2: mix the modified PVC resin, styrene-ethylene-butylene-styrene, bio-based modified MgOH flame retardant, color masterbatch and auxiliary at 130°C for 12 min, granulate, and obtain new energy automobile cable materials, respectively.

[0049] Table 1

[0050] parts by weight Example 1 Example 2 Example 3 Modified PVC resin 100 100 100 SEBS 80 60 50 Modified flame retardant 1 15 10 5 White mother 7 7 7 antioxidants 5 5 5

[0051] Comparative example

[0052] Step 1: weigh each component according to the raw material ratio of Table 2;

[0053] Step 2: mix the modified PVC resin (PVC resin), styrene-ethylene-butylene-styrene, bio-based modified MgOH flame retardant, color masterbatch and auxiliary at 130°C for 12 min, granulate, and obtain new energy automobile cable materials, respectively.

[0054] Table 2

[0055]

[0056]

[0057] Performance test:

[0058] 1. Tensile property test: the cable material obtained above is subjected to tensile property test according to JIS K6251.

[0059] 2. Aging resistance test: The cable material obtained above was treated at 135° C. for 240 h, and then subjected to a tensile property test again according to JIS K6251.

[0060] 3. Flame retardant grade: The flame retardant properties of the cable material obtained above were tested according to UL94 standard.

[0061] 4. Oxygen index test: The oxygen index is tested in accordance with standard GB / T2406.2-2009.

[0062] 5. Smoke density test: Use building material smoke density tester to test in accordance with standard GB / T8627-2007.

[0063] The above test results are shown in Table 3.

[0064] Table 3 Test results

[0065]

[0066] It can be seen from Example 2 and Comparative Example 1 in the table that the addition of graphene oxide can significantly improve the various properties of the cable material. This is because the subsequent reactions are all carried out on the hydroxyl groups of graphene oxide, and graphene oxide itself can also improve the mechanical properties of the cable material.

[0067] It can be seen from Example 2 and Comparative Examples 2-4 in the table that the addition of boric acid, graphene oxide, molybdenum oxide, and glycerol phosphate can synergistically enhance the flame retardancy and smoke suppression of MgOH, which is more in line with environmental protection and smoke suppression requirements.

[0068] As shown in Example 2 and Comparative Example 5, grafting hydroxyl groups onto the modified PVC facilitates hydrogen bonding with the surface of the bio-based modified MgOH flame retardant, thereby enhancing the stability of the cable material. However, excessive grafting of hydroxyl groups can negatively impact the flame retardancy of the PVC due to its hydrophilicity and viscosity. However, omitting the grafting of hydroxyl groups, or failing to graft glycerol phosphate onto the modified bio-based surface, reduces the compatibility between the resin matrix and the flame retardant, thereby diminishing the flame retardancy and stability, and shortening the service life.

[0069] The present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A heat-resistant and flame-retardant new energy vehicle cable material, characterized in that: The cable material comprises the following components in parts by weight: 100 parts of modified PVC resin; 80-50 parts of styrene-ethylene-butylene-styrene, 5-15 parts of bio-based modified MgOH flame retardant, 5-15 parts of masterbatch and 5-10 parts of additives.

2. The new energy vehicle cable material according to claim 1, characterized in that: The modified PVC resin is obtained by polymerizing vinyl chloride and 3-butene-1-ol.

3. The new energy vehicle cable material according to claim 2, characterized in that: The molar ratio of vinyl chloride to 3-butene-1-ol is 20-10:

1.

4. The new energy vehicle cable material according to claim 1, characterized in that: The bio-based modified MgOH flame retardant is a flame retardant with magnesium hydroxide as an inner layer, graphene oxide and nano-molybdenum oxide as an outer layer, and grafted with phosphorus-containing bio-based materials.

5. The new energy vehicle cable material according to claim 1 or 4, characterized in that: The preparation method of the bio-based modified MgOH flame retardant comprises the following steps: Step 1: Weigh ammonium heptamolybdate and graphene oxide, add water and stir to obtain a mixed solution; add magnesium hydroxide to the above ammonium molybdate solution, transfer to a polytetrafluoroethylene-lined reactor, heat and stir to react, and obtain a suspension after the reaction is completed. The suspension is filtered and washed to obtain a doping material; Step 2: adding the doping material, boric acid, glycerophosphate and solvent into a reactor, then adding urea and deionized water into the reactor, and then heating the reactor for reaction, and obtaining the bio-based modified MgOH flame retardant through post-treatment.

6. The new energy vehicle cable material according to claim 5, characterized in that: The added molar ratio of the ammonium heptamolybdate, graphene oxide and magnesium hydroxide is 0.2-0.8:0.5-1:

1.

7. The new energy vehicle cable material according to claim 5, characterized in that: The addition ratio of the doping material, boric acid, glycerophosphate and urea is 10 g: 1-4 mol: 1-2 mol: 1-2 mol.

8. The new energy vehicle cable material according to claim 1, characterized in that: The auxiliary agent is selected from one or more combinations of light stabilizers, anti-aging agents, lubricants, antioxidants, compatibilizers, plasticizers, and ultraviolet absorbers.

9. The method for preparing the new energy vehicle cable material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Weigh each component according to the above raw material ratio; Step 2: Mix the modified PVC resin, styrene-ethylene-butylene-styrene, bio-based modified MgOH flame retardant, masterbatch and additives at 100° C.-130° C. for 10-20 minutes and granulate.

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