5G communication cable insulation layer material with anti-printing migration and flame retardant functions and preparation method thereof

Abstract

The invention discloses a 5G communication cable insulation layer material with anti-printing migration and flame retardant functions. The material comprises the following components: 100 phr polypropylene pellets, 0.2-0.5 phr antioxidant, 0.2-1.0 phr lubricant, 4.0-20.0 phr layered nano material modified bio-based carbon-forming agent and 6.5-24.0 phr ammonium polyphosphate; a preparation method of the material comprises the following steps: 100 phr polypropylene pellets, 0.2-0.5 phr antioxidant, 0.2-1.0 phr lubricant, 4.0-20.0 phr layered nano material modified bio-based carbon-forming agent and 6.5-24.0 phr ammonium polyphosphate are uniformly mixed in a high-speed mixer, and then added into a twin-screw extruder for melt blending; the material has excellent flame retardant properties, and printing ink can be stably attached to the surface of the material, which effectively solves the problems of the current communication cable insulation layer material being unable to be printed and printing migration.

Description

Technical Field

[0001] The present invention relates to a 5G communication cable insulation layer material with anti-printing migration and flame retardant functions, belonging to the technical field of wire and cable insulation layer materials. The present invention also relates to a preparation method of the above material. Background Art

[0002] With the rapid development of science and technology, application scenarios such as high-definition video, Internet of Things (Internet of Vehicles), VR / AR, etc. have gradually emerged, bringing with them a strong demand for enhanced mobile broadband, massive connections, low latency, and high-reliability communication technologies. 5G is a breakthrough mobile communication technology, and communication cables are the most basic part of 5G communication networks. Polypropylene is widely used to prepare the insulation layer of 5G communication cables due to its advantages such as good electrical insulation, chemical corrosion resistance and low price. However, polypropylene has weak polarity and low surface energy, and it is difficult for printing ink to adhere. During the production and use process, communication cables often have problems such as inability to print and printing migration, which not only affects the appearance of the product, but also causes some cable products to be unable to identify their model specifications and uses, and ultimately need to be returned. In addition, polypropylene has the defect of being flammable. In the face of common electrical faults such as overload and short circuit, there is a risk of fire and combustion causing damage to 5G communication base stations or even paralysis of the entire communication network. Therefore, the insulation material of 5G communication cables is required to have good flame retardant properties.

[0003] As halogen flame retardants are gradually banned, most of the communication cable materials on the market currently use inorganic flame retardants such as aluminum hydroxide or small molecule phosphorus flame retardants, intumescent flame retardants, etc. as flame retardant additives for cable insulation materials. Although these flame retardants are cheap, their flame retardant efficiency is low, and because of their small molecular weight, they are easy to migrate to the surface of the cable, which not only causes frosting on the cable surface, but also further affects printing and causes printing migration. Therefore, how to improve the flame retardant properties of the cable insulation layer and solve the problems of flame retardant precipitation and printing migration at the same time is a major challenge currently facing the 5G communication cable field.

[0004] Layered nanomaterials are widely used in the field of flame retardancy due to their sheet barrier effect, nanocatalytic effect and nanosize effect. Most current flame retardant systems exert their flame retardant effect by forming a physical barrier layer on the surface of the material, while the sheet barrier effect of layered nanomaterials can effectively improve the strength and air tightness of the physical barrier layer; at the same time, its nanocatalytic effect has a catalytic carbonization effect, which can effectively improve the formation speed and quality of the barrier carbon layer (CN101214947A; Catalyzing Carbonization of Organophilic Alpha-Zirconium Phosphate / Acrylonitrile-Butadiene-Styrene Copolymer Nanocomposites [J]. Journal of Applied Polymer Science, 2013, 130 (5): 3038-2042); in addition, its nanosize effect makes it have the characteristics of low amount and high efficiency, and only a very small amount (generally 0.1-5.0 phr) needs to be added to exert a significant effect. However, current nanomaterials are often simply blended with other traditional flame retardants to exert a synergistic flame retardant effect. Although the flame retardant efficiency of these flame retardant systems has been improved to a certain extent, problems such as flame retardant precipitation and printing migration cannot be solved. Summary of the invention

[0005] The purpose of the present invention is to provide a 5G communication cable insulation layer material with anti-printing migration and flame retardant functions in view of the shortcomings of existing 5G communication cable insulation layer materials. The material has excellent flame retardant properties, and the printing ink can be firmly attached to its surface, effectively solving the problems of the current communication cable insulation layer material being unable to be printed and printing migration. The present invention also provides a method for preparing the above material.

[0006] To solve the above technical problems, the 5G communication cable insulation layer material with anti-printing migration and flame retardant functions of the present invention comprises the following components: 100 phr (phr is parts by weight, the same below) polypropylene pellets, 0.2-0.5 phr antioxidant, 0.2-1.0 phr lubricant, 4.0-20.0 phr layered nanomaterial modified bio-based carbon-forming agent and 6.5-24.0 phr ammonium polyphosphate.

[0007] Specifically, the antioxidant is one or more of 168, 616, 618, 626, 1010 and 1076. The lubricant is one or more of polypropylene wax, paraffin, stearic acid alcohol, stearic acid amide, butyl stearate and stearic acid monoglyceride.

[0008] Specifically, the layered nanomaterial-modified bio-based carbon-forming agent is synthesized by the following steps:

[0009] (1) Synthesis of organically modified layered nanomaterials:

[0010] Solvent A and layered nanomaterials are added into a reaction kettle, and the layered nanomaterials are fully dispersed through the synergistic effect of mechanical stirring and ultrasonic treatment for 20-180 minutes; the layered nanomaterials are preferably one or more of boron nitride, montmorillonite, zirconium phosphate, graphene, graphene oxide and double metal hydroxide.

[0011] The temperature of the reaction kettle is controlled at 60-100° C., and the silane coupling agent is dissolved in solvent B and added dropwise into the reaction kettle within 0.5-3 hours. After the addition is completed, the reaction is continued for 4-24 hours; the silane coupling agent is preferably one or more of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidyloxypropylmethyldimethoxysilane.

[0012] After the reaction is completed, the mixed solution is centrifuged, and the precipitate is washed with solvent B and dried to obtain an organic modified layered nanomaterial;

[0013] The mass ratio of the silane coupling agent to the layered nanomaterial is 0.25:1-4:1;

[0014] (2) Synthesis of bio-based carbon-forming agents modified by layered nanomaterials:

[0015] Solvent C, bio-based polymer and the organic modified layered nanomaterial prepared in step (1) are added to a reaction kettle, and they are uniformly dispersed through the synergistic effect of mechanical stirring and ultrasonic treatment for 20-60 minutes; the bio-based polymer is preferably one or more of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, carboxymethyl chitosan, hydroxypropyl chitosan and sodium alginate.

[0016] The temperature of the reaction kettle is controlled at 60-110°C, the pH is controlled at 2-12 by a pH regulator, and the cross-linking agent is dissolved in solvent D and added dropwise into the reaction kettle within 0.5-2h. After the addition is completed, the reaction is continued for 6-24h; the cross-linking agent is preferably one or more of glyoxal, glutaraldehyde and adipaldehyde; the pH regulator is preferably one or more of hydrochloric acid, phosphoric acid, sodium hydroxide and potassium hydroxide.

[0017] After the reaction is completed, the mixed solution is centrifuged, and the precipitate is washed with solvent D and deionized water, and dried to obtain a layered nanomaterial-modified bio-based carbon-forming agent;

[0018] The mass ratio of the organic modified layered nanomaterial to the bio-based polymer is 0.1:1-1:1, and the mass ratio of the cross-linking agent to the bio-based polymer is 0.03:1-0.1:1.

[0019] The solvent A, solvent B, solvent C and solvent D are preferably one or more of deionized water, ethanol, n-butanol, acetone and toluene.

[0020] The preparation method of the above-mentioned 5G communication cable insulation layer material with anti-printing migration and flame retardant functions comprises the following steps: 100phr polypropylene pellets, 0.2-0.5phr antioxidant, 0.2-1.0phr lubricant, 4.0-20.0phr layered nanomaterial modified bio-based carbon-forming agent and 6.5-24.0phr ammonium polyphosphate are mixed evenly in a high-speed mixer, and then added into a twin-screw extruder for melt blending.

[0021] Parameter settings of the twin-screw extruder: zone 1 150-180℃, zones 2-5 170-200℃, zones 6-9 160-190℃, die head 180-200℃, screw speed 300-450r / min, feeding rate 15-50kg / h.

[0022] The present invention modifies the layered nanomaterial onto the bio-based polymer through covalent cross-linking, synthesizes the layered nanomaterial modified bio-based carbon-forming agent, and adds it together with ammonium polyphosphate, antioxidant and lubricant, etc., by controlling the processing technology, and uniformly adding it to polypropylene using a twin-screw extruder, to prepare a 5G communication cable insulation layer material with anti-printing migration and flame retardant functions. The carbon content of the bio-based polymer is rich, and it contains a large number of active groups such as hydroxyl, amino and carboxyl groups, so that it exhibits excellent carbonization. It can be efficiently carbonized in situ on the surface of the layered nanomaterial under the dual effects of nano-catalysis of the layered nanomaterial and acid catalysis of ammonium polyphosphate, and expand under the action of the cracked gas of ammonium polyphosphate to form a porous carbon layer with a layered nanomaterial as the skeleton and a dense surface, which plays an efficient heat insulation and oxygen isolation role, and gives the polypropylene substrate excellent flame retardant properties. In addition, the lamellar structure of the layered nanomaterial makes it difficult to move after being embedded in the polypropylene material, and it is even more difficult to precipitate. Both bio-based polymers and ammonium polyphosphate are macromolecular materials, and bio-based polymers are fixed to layered nanomaterials through covalent bonds, and abundant hydrogen bonds can be formed between ammonium polyphosphate and bio-based polymers, thereby effectively solving the problem of flame retardant precipitation. At the same time, since the layered nanomaterials modified bio-based carbon-forming agents and ammonium polyphosphate both have a certain polarity, the surface energy of polypropylene and the interaction force with printing ink can be effectively improved, so that the printing ink can be firmly attached to polypropylene, solving the problems of the inability to print the cable insulation layer material and printing migration. Therefore, the polypropylene insulation layer material provided by the present invention has excellent anti-printing migration and flame retardant properties, which can effectively improve the yield rate of the printing process in the cable processing process and the fire safety during use, which is of great significance to the development of the communication cable industry.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0024] 1. In the polypropylene insulation layer material provided by the present invention, the layered nanomaterial modified bio-based carbon-forming agent has excellent carbon-forming properties. The bio-based carbon-forming agent can efficiently form carbon in situ on the surface of the layered nanomaterial under the dual effects of nano-catalysis of the layered nanomaterial and acid catalysis of ammonium polyphosphate, and expand under the action of the cracking gas of ammonium polyphosphate to form a porous carbon layer with the layered nanomaterial as the skeleton and a dense surface, which plays an efficient heat insulation and oxygen isolation role, and gives the polypropylene insulation layer material excellent flame retardant properties.

[0025] 2. In the polypropylene insulation layer material provided by the present invention, the sheet structure of the layered nanomaterial makes it difficult to move after being embedded in the polypropylene material, and it is even more difficult to precipitate. The bio-based polymer and ammonium polyphosphate are both macromolecular materials, and the bio-based polymer is fixed to the layered nanomaterial through covalent bonds, and abundant hydrogen bonds can be formed between ammonium polyphosphate and the bio-based polymer, thereby effectively solving the problem of flame retardant precipitation.

[0026] 3. In the polypropylene insulation layer material provided by the present invention, the layered nanomaterial modified bio-based carbon-forming agent and ammonium polyphosphate have a certain polarity, which can effectively improve the surface energy of polypropylene and the interaction force with printing ink, so that the printing ink can be firmly attached to the polypropylene, solving the problems of the cable insulation layer material being unable to be printed and printing migration.

[0027] 4. The preparation process of the present invention is simple, easy to control, has low requirements on production equipment, and has high yield. The prepared flame-retardant polypropylene material with anti-printing migration and flame-retardant functions can be widely used in the field of wires and cables. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0029] Figure 1 These are SEM photos of (A) montmorillonite and (B) layered nanomaterial-modified bio-based carbon-forming agent in Example 1. DETAILED DESCRIPTION

[0030] Example 1

[0031] 1. Synthesis of bio-based carbon-forming agents modified by layered nanomaterials:

[0032] 1) Synthesis of organic modified layered nanomaterials: 200 mL of toluene and 2 g of montmorillonite were added to a 500 mL four-necked flask, and the montmorillonite was fully dispersed by the synergistic effect of mechanical stirring and ultrasonic treatment for 180 min. After that, the reaction temperature was controlled to 90 ° C, and 2.0 g of 3-glycidyloxypropyltrimethoxysilane was dissolved in 50 mL of ethanol and added dropwise to the four-necked flask within 0.5 h. After the dropwise addition, the reaction was continued for 24 h. After the reaction was completed, the mixed solution was centrifuged, the precipitate was washed with ethanol, and the organic modified layered nanomaterial was obtained after drying.

[0033] 2) Synthesis of layered nanomaterial modified bio-based carbon-forming agent: 200 mL of deionized water, 10 g of carboxymethyl cellulose and 3 g of the organic modified layered nanomaterial prepared in step 1) were added to a 500 mL four-necked flask, and they were uniformly dispersed by the synergistic effect of mechanical stirring and ultrasonic treatment for 20 min. After that, the temperature of the reactor was controlled to 80 ° C, the pH was controlled to 3 by hydrochloric acid, and 0.5 g of adipaldehyde was dissolved in 50 mL of ethanol and added dropwise to the reactor within 1 hour. After the dripping was completed, the reaction was continued for 22 hours. After the reaction was completed, the mixed solution was centrifuged, the precipitate was washed with ethanol and deionized water, and the layered nanomaterial modified bio-based carbon-forming agent was obtained after drying.

[0034] Depend on Figure 1 From the SEM image of (A), we can see that montmorillonite has a smooth flaky structure. After surface modification by silane coupling agent and covalent crosslinking with bio-based polymer, the obtained layered nanomaterials modify the bio-based carbon-forming agent (such as Figure 1 (B) shows a rough-surfaced flake structure, indicating that the layered nanomaterial-modified bio-based carbon-forming agent has been successfully synthesized.

[0035] 2. Mix 100phr polypropylene pellets, 0.3phr 168 antioxidant, 0.5phr butyl stearate, 8.0phr layered nanomaterial modified bio-based carbon-forming agent and 16.0phr ammonium polyphosphate in a high-speed mixer, and then add them into a twin-screw extruder for melt blending. The parameters of the twin-screw extruder are as follows: the temperatures of zones 1-9 are 160℃, 180℃, 185℃, 185℃, 190℃, 180℃, 175℃, 175℃, 170℃, respectively, the die temperature is 180℃, the screw speed is 300r / min, and the feeding rate is 15kg / h.

[0036] 3. Various standard samples were prepared by injection molding and tested for anti-printing migration and flame retardancy. The results are shown in Tables 1 and 2.

[0037] Example 2

[0038] The difference between this embodiment and embodiment 1 is that: in step 1, 200 mL of toluene is replaced by 200 mL of acetone, montmorillonite is replaced by boron nitride, and the reaction temperature is reduced to 60° C.; the hydrochloric acid in step 2 is replaced by sodium hydroxide, and the pH value is increased to 10; in step 2, 0.5 phr of butyl stearate is replaced by 1.0 phr of polypropylene wax.

[0039] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0040] Example 3

[0041] The difference between this embodiment and embodiment 1 is that: in step 1, 200 mL of toluene is replaced by 200 mL of deionized water, montmorillonite is replaced by zirconium phosphate, and the reaction time after the addition of the silane coupling agent is shortened to 8 h; the synergistic effect time of mechanical stirring and ultrasonic treatment in step 2 is extended to 60 min, hydrochloric acid is replaced by phosphoric acid, and the pH value is reduced to 2; in step 2, butyl stearate is replaced by stearic acid amide, the amount of layered nanomaterial modified bio-based carbon-forming agent is increased to 13 phr, and the amount of ammonium polyphosphate is reduced to 7 phr.

[0042] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0043] Example 4

[0044] The difference between this embodiment and embodiment 1 is that: the montmorillonite in step 1 is replaced by graphene, the reaction temperature is reduced to 80°C, and the amount of 3-glycidyloxypropyltrimethoxysilane is reduced to 0.5g; in step 2, 200mL of deionized water is replaced by 200mL of toluene, carboxymethyl cellulose is replaced by methyl cellulose, the reaction temperature is increased to 110°C, and the dropwise addition time of the ethanol solution of adipaldehyde is shortened to 0.5h; in step 2, 168 antioxidant is replaced by 626 antioxidant, butyl stearate is replaced by paraffin, and the feeding speed of the twin-screw extruder is increased to 30kg / h.

[0045] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0046] Example 5

[0047] The difference between this embodiment and Example 1 is that: in step 1, 200 mL of toluene is replaced by 200 mL of deionized water, and montmorillonite is replaced by graphene oxide; in step 2, 200 mL of deionized water is replaced by 200 mL of n-butanol, carboxymethyl cellulose is replaced by hydroxypropyl methylcellulose, the amount of adipaldehyde is reduced to 0.3 g, and the reaction time after the adipaldehyde is dripped is extended to 24 h; in step 2, butyl stearate is replaced by stearic acid monoglyceride, and the temperatures of zones 1-9 of the twin-screw extruder are changed to 170°C, 185°C, 190°C, 195°C, 200°C, 190°C, 185°C, 180°C, and 180°C, respectively, and the head temperature is changed to 190°C.

[0048] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0049] Example 6

[0050] The difference between this embodiment and embodiment 1 is that: in step 1, montmorillonite is replaced by double metal hydroxide, and the addition time of the ethanol solution of 3-glycidyloxypropyltrimethoxysilane is extended to 1.5h; in step 2, carboxymethyl cellulose is replaced by cellulose acetate, the amount of organically modified layered nanomaterial is increased to 8.0g, and the ethanol solution of adipaldehyde is replaced by a deionized aqueous solution of glyoxal; in step 2, 0.3phr 168 antioxidant is replaced by 0.5phr 626 antioxidant, the amount of layered nanomaterial modified bio-based carbon-forming agent is increased to 20phr, and the amount of ammonium polyphosphate is reduced to 10phr.

[0051] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0052] Example 7

[0053] The difference between this embodiment and embodiment 1 is that: in step 1, 200 mL of toluene is replaced by 200 mL of n-butanol, and the reaction time after the addition of the silane coupling agent is shortened to 16 h; in step 2, carboxymethyl cellulose is replaced by carboxymethyl chitosan, hydrochloric acid is replaced by potassium hydroxide, and the pH value is increased to 12; in step 2, butyl stearate is replaced by stearic acid alcohol, the screw speed of the twin-screw extruder is increased to 450 r / min, and the feeding rate is increased to 45 kg / h.

[0054] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0055] Example 8

[0056] The difference between this embodiment and embodiment 1 is that: in step 1, the ethanol solution of 3-glycidyloxypropyltrimethoxysilane is replaced by a deionized water solution of 3-aminopropyltriethoxysilane; in step 2, 200 mL of deionized water is replaced by 200 mL of ethanol, carboxymethyl cellulose is replaced by hydroxypropyl chitosan, the reaction temperature is reduced to 60°C, and the addition time of the ethanol solution of adipaldehyde is extended to 2 h; in step 2, 168 antioxidant is replaced by 616 antioxidant, the amount of layered nanomaterial-modified bio-based carbon-forming agent is reduced to 5 phr, and the amount of ammonium polyphosphate is increased to 20 phr.

[0057] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0058] Example 9

[0059] The difference between this embodiment and embodiment 1 is that: in step 1, 2.0 g of 3-glycidyloxypropyltrimethoxysilane is replaced by 8.0 g of 3-aminopropylmethyldiethoxysilane, and the dropping time is extended to 2.5 h; in step 2, carboxymethyl cellulose is replaced by sodium alginate, the amount of organically modified layered nanomaterial is reduced to 1.0 g, and the solvent of adipaldehyde is replaced by ethanol by n-butanol; in step 2, 168 antioxidant is replaced by 1010 antioxidant, and the temperatures of zones 1-9 of the twin-screw extruder are changed to 160°C, 170°C, 180°C, 185°C, 190°C, 175°C, 175°C, 170°C, and 170°C, respectively, and the head temperature is changed to 180°C.

[0060] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0061] Example 10

[0062] The difference between this embodiment and embodiment 1 is that: in step 1, the ethanol solution of 3-glycidyloxypropyltrimethoxysilane is replaced by an acetone solution of 3-glycidyloxypropylmethyldimethoxysilane; in step 2, 0.5 g of adipaldehyde is replaced by 1.0 g of glutaraldehyde, and the reaction time after the addition of glutaraldehyde is shortened to 6 h; in step 2, 168 antioxidant is replaced by 1076 antioxidant, and the amount of butyl stearate is reduced from 0.5 phr to 0.2 phr.

[0063] The test results of anti-printing migration and flame retardant properties are shown in Tables 1 and 2.

[0064] Comparative Example 1

[0065] In order to prove that the flame retardant system provided by the present invention can effectively improve the anti-printing migration and flame retardant properties of the polypropylene substrate, pure polypropylene without adding flame retardant is used as a comparison.

[0066] 100phr polypropylene pellets, 0.3phr 168 antioxidant and 0.5phr butyl stearate were mixed evenly in a high-speed mixer, and then added to a twin-screw extruder for melt blending. The parameters of the twin-screw extruder were set as follows: the temperatures of zones 1-9 were 160°C, 180°C, 185°C, 185°C, 190°C, 180°C, 175°C, 175°C, 170°C, the die temperature was 180°C, the screw speed was 300r / min, and the feed rate was 15kg / h.

[0067] Various standard samples were prepared by injection molding and tested for anti-printing migration and flame retardancy. The results are shown in Tables 1 and 2.

[0068] Comparative Example 2

[0069] In order to prove that the 5G communication cable insulation layer material provided by the present invention has better anti-printing migration and flame retardant properties than the currently commonly used cable insulation layer materials, the commonly used formulas in the current cable field are used as a comparison.

[0070] 100phr polypropylene pellets, 0.3phr 168 antioxidant, 0.5phr butyl stearate and 30phr aluminum hydroxide were mixed evenly in a high-speed mixer, and then added to a twin-screw extruder for melt blending. The parameters of the twin-screw extruder were set as follows: the temperatures of zones 1-9 were 160°C, 180°C, 185°C, 185°C, 190°C, 180°C, 175°C, 175°C, 170°C, the die temperature was 180°C, the screw speed was 300r / min, and the feeding rate was 15kg / h.

[0071] Various standard samples were prepared by injection molding and tested for anti-printing migration and flame retardancy. The results are shown in Tables 1 and 2.

[0072] Test method:

[0073] 1. Scanning electron microscopy (SEM): It was carried out on a thermal field emission scanning electron microscope (Carl Zeiss, Germany, model: Merlin). The sample was adhered to the sample stage with conductive glue and the surface was sprayed with gold. The electron beam with an acceleration voltage of 5 kV was used for scanning imaging to observe the surface morphology of the sample.

[0074] 2. Anti-printing migration performance test: Print the sample surface, wait for the ink to dry, place it in a high humidity and high temperature environment for 48 hours, then use polypropylene film to stick the printed symbols on the sample surface for 30 minutes and then separate them, and record the migration of the ink. According to the adhesion of the printing ink, the grades are divided into: difficult to print (blurred symbols), printable (basic recognizable symbols), easy to print (clear symbols); according to the symbol migration ratio, the migration grades are divided into: 0 (no migration), 1 (1-25% migration), 2 (25-50% migration), 3 (51-75% migration), 4 (76-100% migration).

[0075] 3. Limiting oxygen index (LOI) test: carried out in accordance with ASTM D2863 standard, the sample size is 120mm×6.5mm×3mm.

[0076] 4. Vertical burning (UL-94) test: carried out according to ASTM 635-2003 standard, sample size is 127mm×12.7mm×3.2mm.

[0077] Table 1

[0078]

[0079] Table 2

[0080]

[0081] It can be seen from the data of Examples 1-10 in Table 1 and Table 2 that by using different layered nanomaterials, silane coupling agents, bio-based polymers and cross-linking agents, layered nanomaterials synthesized by different processes to modify bio-based carbon-forming agents, and adding ammonium polyphosphate, antioxidants and lubricants to polypropylene in different proportions and process conditions, 5G communication cable insulation layer materials with excellent anti-printing migration and flame retardant properties can be prepared.

[0082] As can be seen from Table 1, the polypropylene insulation layer material provided by the present invention has excellent anti-printing migration performance. The surface of the polypropylene material provided in Example 1 is easy to print, and after being treated at 40°C and 100% relative humidity for 24 hours, there is still no printing migration phenomenon. The surface of the polypropylene material provided in Comparative Example 1 is difficult to print, and a level 1 printing migration phenomenon will occur even if it is placed in an ordinary environment. High temperature (40°C) and high humidity (100% relative humidity) environments will increase the printing migration level to level 2, and the combined effect of high temperature and high humidity will worsen the printing migration phenomenon to level 3. This is because polypropylene has weak polarity and low surface energy, and printing ink is difficult to adhere to, so it is difficult to print and easy to migrate, and high temperature and high humidity will promote ink migration. The layered nanomaterial-modified bio-based carbon-forming agent and ammonium polyphosphate of the present invention both have a certain polarity, which can effectively increase the surface energy of polypropylene and the interaction force with printing ink, so that printing ink can be firmly attached to polypropylene.

[0083] In addition, the data of comparative example 2 in Table 1 show that the surface of the currently commonly used cable material can be printed, but printing migration will occur under high temperature and high humidity. This is because flame retardants such as aluminum hydroxide have poor compatibility with polypropylene substrates, and will precipitate to the substrate surface under high temperature and high humidity, and the printing ink on the surface will migrate. The sheet structure of the layered nano material of the present invention makes it difficult to move after being embedded in the polypropylene material, and it is more difficult to precipitate. Bio-based polymers and ammonium polyphosphate are both macromolecular materials, and bio-based polymers are fixed to the layered nano material through covalent bonds, and abundant hydrogen bonding can be formed between ammonium polyphosphate and bio-based polymers, thereby effectively solving the precipitation problem of flame retardants.

[0084] As can be seen from Table 2, the polypropylene insulation layer material provided by the present invention has excellent flame retardant properties. For example, the polypropylene material provided in Example 6 has a limiting oxygen index (LOI) increased from 18% to 30.5% compared to Comparative Example 1, and the vertical combustion (UL-94) test result has increased from no grade (NR) to V-0. However, the LOI of the currently commonly used polypropylene insulation layer material (Comparative Example 2) is only 26.0%, and the UL-94 grade only reaches V-2. This is because the layered nanomaterial modified bio-based carbon-forming agent of the present invention has excellent carbon-forming properties, wherein the bio-based carbon-forming agent has a rich carbon content and contains a large number of active groups such as hydroxyl, amino and carboxyl groups, which can be efficiently carbonized in situ on the surface of the layered nanomaterial under the dual effects of nano-catalysis of the layered nanomaterial and acid catalysis of ammonium polyphosphate, and expand under the action of the cracking gas of ammonium polyphosphate to form a porous carbon layer with a layered nanomaterial as the skeleton and a dense surface, which plays an efficient heat insulation and oxygen insulation role, and gives the polypropylene insulation layer material excellent flame retardant properties.

[0085] In summary, the polypropylene insulation layer material provided by the present invention has excellent anti-printing migration and flame retardant properties, can effectively improve the yield rate of the printing process in the cable processing process and the fire safety during use, and is of great significance to the development of the communication cable industry.

[0086] The above embodiments do not limit the present invention in any way, and any technical solutions obtained by equivalent replacement or equivalent transformation fall within the protection scope of the present invention.

Claims

1. 5G communication cable insulation material with anti-printing migration and flame retardant functions, characterized in that The invention comprises the following components: 100 phr polypropylene pellets, 0.2-0.5 phr antioxidant, 0.2-1.0 phr lubricant, 4.0-20.0 phr layered nanomaterial modified bio-based carbon-forming agent and 6.5-24.0 phr ammonium polyphosphate; the layered nanomaterial modified bio-based carbon-forming agent is synthesized by the following steps: (1) Synthesis of organically modified layered nanomaterials: Adding solvent A and layered nanomaterials into a reaction kettle, and fully dispersing the layered nanomaterials through the synergistic effect of mechanical stirring and ultrasonic treatment for 20-180 minutes; Control the temperature of the reactor to 60-100°C, dissolve the silane coupling agent in solvent B, add it dropwise into the reactor within 0.5-3h, and continue the reaction for 4-24h after the addition is complete; After the reaction is completed, the mixed solution is centrifuged, and the precipitate is washed with solvent B and dried to obtain an organic modified layered nanomaterial; The mass ratio of the silane coupling agent to the layered nanomaterial is 0.25:1-4:1; (2) Synthesis of bio-based carbon-forming agents modified by layered nanomaterials: Adding solvent C, bio-based polymer and the organic modified layered nanomaterial prepared in step (1) into a reaction kettle, and uniformly dispersing them by the synergistic effect of mechanical stirring and ultrasonic treatment for 20-60 minutes; The temperature of the reaction kettle is controlled at 60-110°C, the pH is controlled at 2-12 by a pH adjuster, and the cross-linking agent is dissolved in solvent D, and added dropwise into the reaction kettle within 0.5-2h, and the reaction is continued for 6-24h after the addition is completed; After the reaction is completed, the mixed solution is centrifuged, and the precipitate is washed with solvent D and deionized water, and dried to obtain a layered nanomaterial-modified bio-based carbon-forming agent; The mass ratio of the organic modified layered nanomaterial to the bio-based polymer is 0.1:1-1:1, and the mass ratio of the cross-linking agent to the bio-based polymer is 0.03:1-0.1:

1.

2. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The antioxidant is one or more of 168, 616, 618, 626, 1010 and 1076.

3. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The lubricant is one or more of polypropylene wax, paraffin wax, stearic acid alcohol, stearic acid amide, butyl stearate and stearic acid monoglyceride.

4. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The layered nanomaterial is one or more of boron nitride, montmorillonite, zirconium phosphate, graphene, graphene oxide and double metal hydroxide.

5. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The silane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropylmethyldimethoxysilane.

6. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The bio-based polymer is one or more of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, carboxymethyl chitosan, hydroxypropyl chitosan and sodium alginate.

7. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The cross-linking agent is one or more of glyoxal, glutaraldehyde and adipaldehyde.

8. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The pH adjuster is one or more of hydrochloric acid, phosphoric acid, sodium hydroxide and potassium hydroxide.

9. The 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 1 is characterized in that: The solvent A, solvent B, solvent C and solvent D are one or more of deionized water, ethanol, n-butanol, acetone and toluene.

10. The method for preparing a 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to any one of claims 1 to 9, characterized in that The method comprises the following steps: uniformly mixing 100phr polypropylene pellets, 0.2-0.5phr antioxidant, 0.2-1.0phr lubricant, 4.0-20.0phr layered nanomaterial modified bio-based carbon-forming agent and 6.5-24.0phr ammonium polyphosphate in a high-speed mixer, and then adding the mixture into a twin-screw extruder for melt blending.

11. The method for preparing the 5G communication cable insulation layer material with anti-printing migration and flame retardant functions according to claim 10, characterized in that: Parameter settings of the twin-screw extruder: zone 1 150-180℃, zones 2-5 170-200℃, zones 6-9 160-190℃, die head 180-200℃, screw speed 300-450r / min, feeding rate 15-50kg / h.

Images