Halogen-containing flame-retardant v-0 polyolefin masterbatch for silane self-crosslinking material and preparation method thereof

Abstract

This invention provides a halogenated flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials and its preparation method. It comprises the following raw material components in parts by weight: 20-23 parts LDPE; 53-56 parts brominated flame retardant; 17-19 parts antimony flame retardant; 0.8-1.2 parts coupling agent; 2-3 parts UV stabilizer; 1.4-1.6 parts lubricant; and 0.4-0.5 parts antioxidant. The LDPE has a melt flow index of 1.5-2.5 g / 10 min. The combined use of these components produces a synergistic effect: even with relatively low addition levels, the resulting silane self-crosslinking material achieves a UL 94V-0 flame retardant rating, effectively reducing costs.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials and relates to a polyolefin masterbatch, specifically to a silane self-crosslinking material for use in sunlight-resistant, corrosion-resistant, low-addition halogen-containing flame-retardant V-0 polyolefin masterbatch and its preparation method. Background Technology

[0002] With the continuous development of the international plastics industry, power industry, and construction industry, as well as people's close attention to electrical safety, the application of wire and cable materials is becoming more and more widespread, and the use of silane self-crosslinking materials in the wire and cable industry is also constantly increasing.

[0003] Silane self-crosslinking materials have the following characteristics: (1) Silane self-crosslinking materials are pure resin materials. Such materials have excellent basic properties, such as mechanical and physical properties, electrical properties, etc.; (2) Silane self-crosslinking materials are self-crosslinking materials. After the finished wire and cable products are made, they only need to be steamed at high temperature to form their own crosslinking properties. Compared with the irradiated crosslinking materials on the market, the irradiation step is eliminated, saving cable processing costs and reducing the time required for finished products.

[0004] However, silane self-crosslinking materials have some problems in terms of flame retardancy: (1) When silane self-crosslinking materials are made, flame retardants are added directly. Since the self-crosslinking rate of silane self-crosslinking materials is not high when they are made into finished products, the temperature resistance of the material will be worse and the basic performance of the material will be worse; (2) Silane crosslinking materials are pure resin materials. Ordinary flame retardant masterbatches need to add more than 25% to achieve the flame retardant UL 94V-0 level, which increases the cost. Ordinary flame retardant masterbatches have poor dispersion in silane self-crosslinking materials, which affects the performance of the material. In addition, ordinary flame retardant masterbatches cannot meet the special performance requirements of the material. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a halogenated flame-retardant V-O polyolefin masterbatch for silane self-crosslinking materials.

[0006] The first objective of this invention is to provide a halogenated flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials, comprising the following raw material components in parts by weight:

[0007]

[0008] The melt index of the LDPE is 1.5 to 2.5 g / 10 min.

[0009] Optimally, the LDPE is a mixture of one or more components selected from Yangba 2220H, Shenhua 2426H and Iran Petrochemical 2102.

[0010] Ideally, the lubricant is a high molecular weight and high viscosity silicone oil, preferably Dow Corning PMX-200-10000.

[0011] Optimally, the bromine-based flame retardant is decabromodiphenyl ethane, and the antimony-based flame retardant is antimony trioxide with a content of 99.8%.

[0012] Optimally, the coupling agent is a titanate coupling agent, preferably Sky SK505.

[0013] Optimally, the UV stabilizer is a mixture of light stabilizer 783 and light stabilizer 5411 in a mass ratio of 1:1, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0014] Another objective of this invention is to provide a method for preparing the above-mentioned silane self-crosslinking halogen-containing flame-retardant V-0 polyolefin masterbatch, comprising the following steps: mixing each raw material in proportion, adding it to a closed internal mixer for heating and internal mixing, double-stage cone feeding, twin-screw shearing discharge, single-screw mixing extrusion, pelletizing with a pelletizer, collecting with a fan and silo, cooling the material with a vibrating screen, collecting the material in a large silo, and vacuum packaging to obtain the silane self-crosslinking halogen-containing flame-retardant V-0 polyolefin masterbatch.

[0015] In an optimized manner, the following steps are repeated: heating and mixing in a closed internal mixer, feeding with a double-stage cone, shearing and discharging with a twin-screw extruder, mixing and extruding with a single screw, pelletizing with a pelletizer, collecting with a fan and silo, cooling the material with a vibrating screen, and collecting the material in a large silo.

[0016] Ideally, the mixing temperature is 155-160℃, and the double-cone feeder is preheated to 105-115℃; the twin-screw shearing discharge temperature is set at 110-120℃, the single-screw mixing extrusion temperature is set at 120-130℃, the die head temperature is 145-155℃, and the baffle filter screen uses a 100-150 mesh screen.

[0017] Furthermore, the twin-screw shear discharge port is also equipped with an L-shaped elbow, and the pellet size cut by the pelletizer is 3×3mm.

[0018] This invention relates to a halogenated flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials. While ensuring the flame retardancy, sunlight resistance, and corrosion resistance of the finished cables, the use of LDPE with a melt index of 1.5-2.5 g / min improves the compatibility between the silane crosslinking material and the masterbatch. The mixed use of decabromodiphenyl ethane and 99.8% antimony trioxide further enhances the flame retardant properties of the material. The use of UV stabilizers effectively improves the sunlight resistance of the material. The addition of lubricants improves the dispersibility of the material during addition and also improves the surface smoothness after cabling. Coupling... The addition of additives improves the corrosion resistance of the material and also improves the dispersibility of the masterbatch in the silane crosslinking material; the addition of antioxidants prevents the material from decomposing at high temperatures during the two processing steps; through the compounding of various components, a synergistic effect is also produced: the compounding of specific types and contents of resin materials (such as LDPE) and flame retardants can make the effective flame retardant of the masterbatch well integrated into the silane self-crosslinking material, and the introduction of coupling additives can effectively promote the dispersion of flame retardants in the silane self-crosslinking material. With a low addition content, the obtained silane self-crosslinking material can achieve the flame retardant UL 94V-0 rating, effectively reducing costs. Detailed Implementation

[0019] This invention relates to a halogenated flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials, comprising the following raw material components in parts by weight: 20-23 parts LDPE; 53-56 parts bromine-based flame retardant; 17-19 parts antimony-based flame retardant; 0.8-1.2 parts coupling agent; 2-3 parts UV stabilizer; 1.4-1.6 parts lubricant; and 0.4-0.5 parts antioxidant; wherein the melt index of the LDPE is 1.5-2.5 g / 10 min (190℃ × 2.16 kg). Selecting LDPE with a melt index of 1.5-2.5 g / min can improve the compatibility between silane crosslinking materials and masterbatches; the mixed use of decabromodiphenyl ethane and 99.8% antimony trioxide can further improve the flame retardant properties of the material; the use of UV stabilizers can effectively improve the material's resistance to sunlight; the addition of lubricants improves the dispersibility of the material during addition and also improves the surface smoothness after cabling; the coupling agent improves the corrosion resistance of the material and also improves the dispersibility of the masterbatch in the silane crosslinking material; the addition of antioxidants prevents the material from decomposing at high temperatures during the two processing steps; through the compounding of various components, a synergistic effect is also produced: the compounding of resin materials and flame retardant materials can allow the effective flame retardant of the masterbatch to be well integrated into the silane self-crosslinking material, and the introduction of coupling agents can effectively promote the dispersion of flame retardant materials in the silane self-crosslinking material. With a low content of additives, the resulting silane self-crosslinking material can achieve a flame retardant UL 94V-0 rating, effectively reducing costs.

[0020] The above-mentioned LDPE is a mixture of one or more of Yangba 2220H, Shenhua 2426H and Iranian Petrochemical 2102. The lubricant is a high molecular weight and high viscosity silicone oil, preferably Dow Corning PMX-200-10000; such silicone oil has the following characteristics: (1) good lubrication effect, and easier dispersion in the formulation, without coagulation and aggregation, which well ensures the dispersibility of the material when added as a masterbatch; (2) high molecular weight and high viscosity improve the temperature resistance of silicone oil to a certain extent, which well solves the problem of silicone oil precipitation in the finished material. The bromine flame retardant is decabromodiphenyl ethane, which has a high halogen content, good flame retardant effect, and environmental performance: compliant with RoSH Reach; the antimony flame retardant is antimony trioxide with a content of 99.8%, which has a high antimony content, good flame retardant effect, and environmental performance: compliant with RoSH Reach. The coupling agent is a titanate coupling agent, preferably Sky SK505. The UV stabilizer is a mixture of light stabilizer 783 and light stabilizer 5411 in a mass ratio of 1:1, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0021] The preparation method of the above-mentioned silane self-crosslinking halogenated flame-retardant V-0 polyolefin masterbatch is characterized by the following steps: mixing each raw material in proportion, adding it to a closed internal mixer for heating and internal mixing, double-stage cone feeding, twin-screw shearing discharge, single-screw mixing extrusion, pelletizing by a pelletizer, collecting by a fan and silo, cooling the material by a vibrating screen, collecting the material in a large silo, and vacuum packaging to obtain the silane self-crosslinking halogenated flame-retardant V-0 polyolefin masterbatch.

[0022] It is also preferable to repeat the following steps: heating and mixing in a closed internal mixer, feeding with a double-stage cone, shearing and discharging with a twin-screw extruder, mixing and extruding with a single screw, pelletizing with a pelletizer, collecting with a fan and silo, cooling the material with a vibrating screen, and collecting the material in a large silo.

[0023] The mixing temperature is 155-160℃, and the double-cone feeder undergoes preheating treatment at a temperature of 105-115℃. The twin-screw shear discharge temperature is set at 110-120℃, and the single-screw mixing extrusion temperature is set at 120-130℃, with a die head temperature of 145-155℃ and a 100-150 mesh filter screen used for the baffle. An L-shaped elbow is added to the twin-screw shear discharge port, and the pelletizer cuts pellets with a diameter of 3×3mm.

[0024] The present invention will be further described below with reference to the embodiments shown.

[0025] Examples 1-3, Comparative Examples 1-10

[0026] Examples 1-3 and Comparative Examples 1-9 each provide a halogenated flame-retardant polyolefin masterbatch for silane self-crosslinking materials, the specific composition of which is shown in Table 1.

[0027] Table 1. Composition of halogenated flame retardant masterbatches in Examples 1-3 and Comparative Examples 1-9

[0028]

[0029]

[0030] Note: The melt index of LDPE is 1.5-2.5 g / min (190℃×2.16 kg), using Yangba 2220H. The melt index of LDPE in Comparative Example 1 is 3.5 g / min (190℃×2.16 kg), and the grade is 7042. The UV stabilizer is a mixture of light stabilizers 783 and 5411 in a 1:1 mass ratio, from Shanghai Dirui. The titanate coupling agent is Nanjing Sky SK505. The antioxidants are 1010 and 168 in a 1:1 mass ratio, from Shanghai Dirui. The silicone oil is Dow Corning PMX-200-10000 (Wacker AK-3100 was used in Comparative Example 9, which has low viscosity and low molecular weight).

[0031] The preparation method of the above-mentioned silane self-crosslinking halogenated flame-retardant V-0 polyolefin masterbatch includes the following steps (the following temperature range has little impact on the final performance of the product):

[0032] After mixing the raw materials in the specified proportions, the mixture is added to a closed internal mixer for heated mixing (temperature 155-160℃, within which the product performance is not significantly affected). The mixture then undergoes a double-cone feeding process (preheating is performed before feeding at 105-115℃; in this embodiment, it is 110℃), twin-screw shearing discharge (temperature set at 110-120℃, with an L-shaped elbow added to the discharge port), and single-screw mixing extrusion (temperature set at 120-130℃, die head temperature 145-155℃; in this embodiment, it is 145-155℃). The process involves: 25℃, die head temperature 150℃, using a 120-mesh baffle filter, pelletizing (particle size 3×3mm), collecting with a fan and silo, cooling the material with a vibrating screen, and collecting the material in a large silo (repeated steps of adding to a closed mixer for heating and mixing, double-stage cone feeding, twin-screw shearing and discharging, single-screw mixing and extrusion, pelletizing with a pelletizer, collecting with a fan and silo, cooling the material with a vibrating screen, and collecting the material in a large silo, i.e., operating twice), and vacuum packaging to obtain the silane self-crosslinking halogenated flame-retardant V-0 polyolefin masterbatch.

[0033] The flame-retardant polyolefin masterbatches produced in Examples 1-3 and Comparative Examples 1-9 were added to silane self-crosslinking materials for performance testing, and the results are shown in Table 2.

[0034] Table 2 Performance Application Table of Products from Examples 1-3 and Comparative Examples 1-9

[0035]

[0036]

[0037] From the data of Examples 1-3, it can be seen that: (1) The amount of auxiliary materials (silicone oil and titanate coupling agent) added during the production of the material will have a certain impact on the surface smoothness and production speed of the material particles: the more auxiliary materials added, the better the surface smoothness and the faster the production speed, but it needs to be controlled within a certain amount. Excessive addition will cause screw slippage and precipitation on the material surface, while insufficient addition will result in the inability to guarantee the processing performance of the product. (2) The mixed use of antioxidants and UV stabilizers will further produce a synergistic effect: while fixing the amount of UV stabilizer added, increasing the amount of antioxidant can increase the sunlight resistance of the material and also improve the thermal stability of the material, but it is necessary to control the amount added. Excessive addition will result in white crystal precipitation on the material surface, while insufficient addition will result in the inability to guarantee the sunlight resistance and thermal stability of the product. (3) The amount and selection of LDPE are mainly to ensure the performance of the material when it is mixed with silane self-crosslinking material in the later stage. Specific grades of LDPE can improve the compatibility between the masterbatch and the self-crosslinking material. The amount is mainly to ensure the addition of effective flame retardants in the material, so as to ensure the flame retardant effect after the mixed use to form the cable. The larger the amount of LDPE, the less material and effective flame retardant, and the worse the flame retardant performance of the product. If the amount is too small, the process requirements are too high when making the masterbatch, and the masterbatch cannot be produced normally. (4) The selection of flame retardants decabromodiphenyl ethane and antimony trioxide is mainly based on the environmental friendliness and high flame retardant performance of the materials. The selected ratio (mass ratio) is approximately 3:1 for decabromodiphenyl ethane and antimony trioxide. The 3:1 ratio obtained through ratio test is the best effect of the two materials in synergistic flame retardancy. In addition, the amount of the two materials also has a great influence on the flame retardancy and processing performance of the product. Adding too much masterbatch makes the production difficult, and adding too little masterbatch will not meet the V-0 test in the UL94 standard in subsequent use (such as adding 20% ​​masterbatch to silane self-crosslinking material to make 2mm sheets for flame retardant test).

[0038] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials, characterized in that it comprises It comprises the following raw material components by weight: LDPE 20-23 parts; Bromine-based flame retardant 53-56 parts; Antimony-based flame retardant 17-19 parts; Coupling aid 0.8-1.2 parts; Anti-UV agent 2-3 parts; Lubricant 1.4-1.6 parts; Antioxidant 0.4-0.5 parts; The LDPE has a melt index of 1.5-2.5 g / 10 min at 190℃ under a load of 2.16 kg.

2. Halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 1, characterized in that: The LDPE is a mixture composed of one or more selected from Yangba 2220H, Shenhua 2426H and Iran Petrochemical 2102.

3. Halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 1, characterized in that: The lubricant is Dow Corning PMX-200-10000.

4. The halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 1, characterized in that: The bromine-based flame retardant is decabromodiphenyl ethane, and the antimony-based flame retardant is diantimony trioxide with a content of 99.8%.

5. The halogen-containing flame-retarded V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 1, characterized in that: The coupling aid is a titanate coupling agent.

6. Halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 5, characterized in that: The coupling aid is Think SK505.

7. The halogen-containing flame-retarded V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 1, characterized in that: The anti-UV agent is a mixture of light stabilizer 783 and light stabilizer 5411 in a mass ratio of 1:1, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:

1.

8. Process for the preparation of halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to any one of claims 1 to 7, characterized in that, The following steps are included: After mixing the raw materials in proportion, heating and kneading in a closed mixer, double-stage cone feeding, double-screw shearing discharge, single-screw mixing extrusion, granulator granulation, fan and bin collection, vibrating screen cooling material, large bin collection, vacuum packaging, the silane self-crosslinking halogen-containing flame-retardant V-0 polyolefin masterbatch is obtained.

9. Process for the preparation of halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 8, characterized in that, The following steps are also repeated: heating and kneading in a closed mixer, double-stage cone feeding, double-screw shearing discharge, single-screw mixing extrusion, granulator granulation, fan and bin collection, vibrating screen cooling material, and large bin collection.

10. Process for the preparation of halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 8, characterized by the fact that: The temperature of the kneading is 155-160℃, and the preheating temperature before double-stage cone feeding is 105-115℃; the set temperature of the double-screw shearing discharge is 110-120℃, and the set temperature of the single-screw mixing extrusion is 120-130℃, the head temperature is 145-155℃, and the baffle screen uses a filter screen with a mesh size of 100-150 mesh.

11. Process for the preparation of halogen-containing flame-retardant V-0 polyolefin masterbatch for silane self-crosslinking materials according to claim 10, characterized in that: The double-screw shearing discharge port is additionally provided with an L-shaped elbow, and the granulator granulation has a particle size of 3×3 mm.

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