CN108164798B - Low-smoke-amount thermoplastic low-smoke halogen-free flame-retardant polyolefin material and preparation method thereof - Google Patents
Low-smoke-amount thermoplastic low-smoke halogen-free flame-retardant polyolefin material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the field of cable materials, and particularly discloses a thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke quantity and a preparation method thereof. The thermoplastic low-smoke halogen-free flame-retardant polyolefin material comprises the following components in parts by weight: 40-60 parts of EVA resin, 10-30 parts of LLDPE resin, 10-30 parts of graft, 60-80 parts of aluminum hydroxide, 60-80 parts of magnesium hydroxide, 10-15 parts of smoke suppressant, 1-2 parts of lubricant and 1-2 parts of antioxidant. The thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke quantity prepared by the invention has the advantages of environmental protection, heat resistance, cold resistance, cracking resistance and flame retardance, overcomes the defects of the existing material, and can meet the harsh condition that the light transmittance of a large-size control cable is more than or equal to 60%.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke quantity and a preparation method thereof.
Background
The wire and cable industry is the second industry in China next to the automobile industry, and both the product variety satisfaction rate and the domestic market share rate exceed 90%. The total output value of the electric wire and the electric cable in China exceeds the United states worldwide, and the electric wire and the electric cable become the first country for producing the electric wire and the electric cable in the world.
The control cable is a wire cable suitable for industrial and mining enterprises, energy traffic departments, control and protection circuits with the AC rated voltage of below 450/750 volts, and the like. With the continuous enlargement of the scales of industries such as the Chinese power industry, the data communication industry, the urban rail transit industry, the automobile industry, the shipbuilding industry and the like, the demand on control cables is rapidly increased, and the wire and cable industry has huge development potential in the future.
The cable is used in places with high requirements on the flame retardant property of the cable, such as subways, high-rise buildings, markets, theaters, power stations, chemical plants, urban squares and other utilities. The cable has the characteristics of no halogen, low smoke, low halogen, low spreading speed, low smoke concentration, high visibility, small release amount of harmful gas and convenience for people to evacuate when a fire disaster happens. The combustion gas has low corrosiveness, and the damage to instrument and equipment is avoided. Therefore, in recent years, the development of low smoke zero halogen control cables is on the rise.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low-smoke thermoplastic low-smoke halogen-free flame-retardant polyolefin material and a preparation method thereof, the prepared low-smoke thermoplastic low-smoke halogen-free flame-retardant polyolefin material has the advantages of environmental protection, heat resistance, cold resistance, cracking resistance and flame retardance, overcomes the defects of the prior material, and can meet the harsh condition that the light transmittance of a large-size control cable is more than or equal to 60%.
In order to achieve the above objects and other related objects, the present invention provides a low smoke thermoplastic low smoke zero halogen flame retardant polyolefin material, which comprises the following components in parts by weight:
preferably, the LLDPE resin is 10-25 parts.
Preferably, the graft is 10-25 parts.
Preferably, the aluminum hydroxide is 65-75 parts.
Preferably, the magnesium hydroxide is 60 to 75 parts.
The EVA resin is selected from EVA resins with the VA content of more than 26%.
More preferably, the EVA resin is selected from EVA resins with a VA content of more than 38%.
Preferably, the LLDPE has a melt index of (2-8) g/10min at 190 ℃ and 2.16 kg.
Preferably, the graft is selected from one or more combinations of maleic anhydride grafted EVA resins and acrylate grafted EVA resins.
Preferably, in the maleic anhydride grafted EVA resin, the grafting rate of maleic anhydride is 3-8%.
Preferably, the melt index of the maleic anhydride grafted EVA resin at 190 ℃ and 2.16kg is (5-15) g/10 min.
Preferably, in the acrylate grafted EVA resin, the grafting rate of acrylate is 5-8%.
Preferably, the melt index of the acrylate grafted EVA resin at 190 ℃ and 2.16kg is (8-15) g/10 min.
Preferably, the aluminum hydroxide is selected from one or more of aluminum hydroxide with fineness of 2500 meshes or more.
More preferably, the aluminum hydroxide is selected from one or more of aluminum hydroxide with the fineness of more than 3000 meshes.
The aluminum hydroxide, the magnesium hydroxide and the smoke suppressant can be purchased from the market.
Preferably, the lubricant is selected from one or more of magnesium stearate, stearic acid and polyethylene wax. Preferably, the lubricant is a mixture of polyethylene wax, magnesium stearate and stearic acid.
Preferably, the antioxidant is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (referred to as antioxidant 1010 for short), dilauryl thiodipropionate (referred to as antioxidant DLTP for short) and tris (2, 4-di-tert-butylphenyl) phosphite (referred to as antioxidant 168 for short).
The invention further provides a preparation method of the thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke quantity, which comprises the following steps:
1) weighing EVA resin, LLDPE resin, graft, antioxidant and lubricant according to a ratio, placing the materials in a kneading pot, mixing at low speed at normal temperature, weighing magnesium hydroxide and aluminum hydroxide according to a ratio, adding the magnesium hydroxide and the aluminum hydroxide, and starting high-speed mixing;
2) after the powder and the granules are uniformly dispersed, starting low-speed mixing again, adding the smoke suppressant weighed according to the proportion, and after uniform mixing, continuing low-speed mixing to obtain a mixture;
3) extruding the mixture obtained in the step 2) by a double-screw extruder for material forming, and drying to obtain the material.
Preferably, in step 1), the temperature of the kneading pot is normal temperature.
Preferably, in the step 1), the magnesium hydroxide and the aluminum hydroxide are added in a plurality of times. More preferably, the number of divided additions is 2 to 3.
Preferably, in the step 1) and the step 2), the rotation speed of the low-speed mixing is 500-1000 rpm.
Preferably, in the step 1) and the step 2), the rotation speed of the high-speed mixing is 1500-3000 rpm.
Preferably, in step 2), the time for continuing the low-speed mixing is 30 to 60 seconds.
Preferably, in the step 3), the extrusion temperature of the twin-screw extruder is 130-150 ℃.
More preferably, the temperature of the twin-screw extruder is set as follows: the first zone of the cylinder is 140-.
Preferably, in the step 3), the drying temperature is 60-70 ℃.
Preferably, in the step 3), the drying time is 20 to 30 minutes.
The invention also discloses the thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke generation amount used as large-specification control electricity
Use in a cable.
The invention is improved on the basis of low smoke halogen-free materials commonly used in cable materials, so that the cable material can meet various requirements of large-specification control cables, and a good effect is achieved. The thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke quantity prepared by the invention has the advantages of environmental protection, heat resistance, cold resistance, cracking resistance and flame retardance, overcomes the defects of the existing material, and can meet the harsh condition that the light transmittance of a large-size control cable is more than or equal to 60%.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
Examples 1 to 4
1. Experimental Material
EVA resins (VA content 26) from Ningbo Tai plastics, EVA resins (VA content 28%) from DuPont, USA; LLDPE resins (middlings), grafts; aluminum hydroxide of over 2500 mesh was purchased from Zibopenfeng aluminum industries, Inc.; magnesium hydroxide over 2500 mesh was purchased from yabao, usa; the smoke suppressant is purchased from American Yabao; antioxidant 1010, antioxidant DLTP, antioxidant 168 were purchased from Pasteur, American jaba.
2. Experimental methods
The EVA resin, the LLDPE resin, the graft, the antioxidant and the lubricant are weighed according to the proportion and placed in a kneading pot, low-speed mixing is carried out at normal temperature, the rotating speed is 500rpm, then the magnesium hydroxide and the aluminum hydroxide are weighed according to the proportion and added in several times, then high-speed mixing is started, the aluminum hydroxide and the magnesium hydroxide are added in three times, and the mixing rotating speed is told to be 1500 rpm.
Mixing at high speed until the powder and the granules are uniformly dispersed, starting low-speed mixing again, adding the smoke suppressant weighed according to the proportion under the condition of low-speed operation, mixing uniformly, continuing to mix at low speed and 800rpm for a period of time, and obtaining a mixture after a certain time
The mixture is directly fed into a double-screw material making machine for extrusion material making, and the heating temperature of each section of the double-screw material making machine is 130-150 ℃ according to the number of the heating sections. (the specific temperature is set as 140 ℃ C. in the first barrel region, 150 ℃ C. in the second barrel region, 140 ℃ C., 130 ℃ C. in the third barrel region, 140 ℃ C. in the fourth barrel region, 130 ℃ C. in the fifth barrel region, 120 ℃ C. in the fourth barrel region, 130 ℃ C. in the fourth barrel region, and 130 ℃ C. in the head and the mold).
And drying the extruded and granulated finished product at 60-70 ℃ for 20-30 minutes to obtain the finished product.
The compositions and weight proportions of the raw material components in examples 1 to 4 are shown in Table 1.
Table 1 cable compound tables for examples 1-4
3. Results of the experiment
The performance tests (JB/T10707-.
TABLE 2 detection Properties of thermoplastic low-smoke halogen-free flame-retardant polyolefin materials with low smoke generation
As shown in the table 2, the light transmittance of the products obtained in the examples 1 and 2 is low, the thermoplastic low-smoke halogen-free flame retardant polyolefin materials with low smoke amount prepared in the examples 3 and 4 have excellent mechanical properties, and have good aging resistance, cold resistance and low temperature impact at-25 ℃ and excellent smoke density performance. The light transmittance test result after the cable is manufactured is better.
Examples 5 to 8
1. Experimental Material
EVA resins are available from DuPont, USA; LLDPE resins (middlings), grafts; aluminum hydroxide of over 2500 mesh was purchased from Zibopenfeng aluminum industries, Inc.; magnesium hydroxide over 2500 mesh was purchased from yabao, usa; the smoke suppressant is purchased from American Yabao; antioxidant 1010, antioxidant DLTP, antioxidant 168 were purchased from Pasteur, American jaba.
11. Experimental methods
The EVA resin, the LLDPE resin, the graft, the antioxidant and the lubricant are weighed according to the proportion and placed in a kneading pot, low-speed mixing is carried out at normal temperature, the rotating speed is 500rpm, then the magnesium hydroxide and the aluminum hydroxide are weighed according to the proportion and added in several times, then high-speed mixing is started, the aluminum hydroxide and the magnesium hydroxide are added in three times, and the mixing rotating speed is told to be 1500 rpm.
Mixing at high speed until the powder and the granules are uniformly dispersed, starting low-speed mixing again, adding the smoke suppressant weighed according to the proportion under the condition of low-speed operation, mixing uniformly, continuing to mix at low speed and 800rpm for a period of time, and obtaining a mixture after a certain time
The mixture is directly fed into a double-screw material making machine for extrusion material making, and the heating temperature of each section of the double-screw material making machine is 130-150 ℃ according to the number of the heating sections. (the specific temperature is set as 140 ℃ C. in the first barrel region, 150 ℃ C. in the second barrel region, 140 ℃ C., 130 ℃ C. in the third barrel region, 140 ℃ C. in the fourth barrel region, 130 ℃ C. in the fifth barrel region, 120 ℃ C. in the fourth barrel region, 130 ℃ C. in the fourth barrel region, and 130 ℃ C. in the head and the mold).
And drying the extruded and granulated finished product at 60-70 ℃ for 20-30 minutes to obtain the finished product.
The compositions and the weight proportions of the raw material components in examples 5 to 8 are shown in Table 3.
Table 3 formulation of cable materials of examples 5-8
3. Results of the experiment
The results of the low smoke thermoplastic low smoke zero halogen flame retardant polyolefin materials prepared according to the formulation of the embodiment 5-the embodiment 8 are shown in the table 4.
TABLE 4
As can be seen from Table 4, the low smoke thermoplastic low smoke zero halogen flame retardant polyolefin materials prepared in the above examples 5-8 have reduced tensile strength and elongation at break after increasing the smoke suppressant ratio. The light transmittance and the smoke density performance are further improved, but after the light transmittance and the smoke density performance are improved to a certain degree, the improvement effect on the light transmittance and the smoke density performance is not obvious.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (7)
1. The thermoplastic low-smoke halogen-free flame-retardant polyolefin material with low smoke generation amount is characterized by comprising the following components in parts by weight:
the EVA resin is one or a combination of more than 26% of EVA resin with VA content;
the melt index of the LLDPE resin at 190 ℃ under the condition of 2.16kg is (2-8) g/10 min;
the graft is prepared by grafting EVA resin with maleic anhydride, and the melt index is (5-15) g/10min at 190 ℃ under the condition of 2.16 kg;
the aluminum hydroxide is 2500 meshes or more;
the magnesium hydroxide is over 2500 meshes of magnesium hydroxide;
the smoke suppressant is one or more of silicon series/molybdenum series combined smoke suppressants;
the lubricant is obtained by mixing polyethylene wax, magnesium stearate and stearic acid according to the mass ratio of 2:1: 1;
the antioxidant is prepared by mixing tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, dilauryl thiodipropionate and tris (2, 4-di-tert-butylphenyl) phosphite according to a mass ratio of 1:6: 6.
2. A method for preparing the thermoplastic low-smoke zero-halogen flame-retardant polyolefin material with low smoke emission according to any one of claim 1, which comprises the following steps:
1) weighing EVA resin, LLDPE resin, graft, antioxidant and lubricant according to a ratio, placing the materials in a kneading pot, mixing at low speed at normal temperature, weighing magnesium hydroxide and aluminum hydroxide according to a ratio, adding the magnesium hydroxide and the aluminum hydroxide in batches, and starting high-speed mixing;
2) after the powder and the granules are uniformly dispersed, starting low-speed mixing again, adding the smoke suppressant weighed according to the proportion, after uniform mixing, continuing low-speed mixing for a period of time, and obtaining a mixture after a certain period of time;
3) extruding and granulating the mixture obtained in the step 2) by a double-screw extruder, and drying to obtain the product.
3. The preparation method of the thermoplastic low-smoke zero-halogen flame-retardant polyolefin material with low smoke generation according to claim 2, characterized in that in the step 1), the magnesium hydroxide and the aluminum hydroxide are added for 2 to 3 times.
4. The method for preparing the thermoplastic low-smoke zero-halogen flame-retardant polyolefin material with low smoke generation according to claim 2, wherein in the step 1) and the step 2), the rotation speed of the low-speed mixing is 500-1000 rpm; the rotation speed of the high-speed mixing is 1500-3000 rpm.
5. The method for preparing the low-smoke thermoplastic low-smoke zero-halogen flame-retardant polyolefin material according to claim 2, wherein the extrusion temperature of the twin-screw extruder in the step 3) is 130-150 ℃.
6. The preparation method of the thermoplastic low-smoke zero-halogen flame-retardant polyolefin material with low smoke emission according to claim 2, characterized in that in the step 3), the drying temperature is 60-70 ℃.
7. Use of the low smoke thermoplastic low smoke zero halogen flame retardant polyolefin material according to claim 1 as large gauge control cable.
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| CN113429667A (en) * | 2021-08-03 | 2021-09-24 | 安徽滁州德威新材料有限公司 | Low-smoke halogen-free high-flame-retardant B1/B2 material and preparation method thereof |
| CN116102817A (en) * | 2023-03-15 | 2023-05-12 | 上海凯波电缆特材股份有限公司 | High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
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| CN101100537A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院上海应用物理研究所 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
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| JP2003183451A (en) * | 2001-12-17 | 2003-07-03 | Sumitomo Wiring Syst Ltd | Wear-resistant and flame-retardant resin composition and electric wire coated therewith |
| US8263674B2 (en) * | 2011-07-25 | 2012-09-11 | King Abdulaziz City for Science and Technology “KACST” | Eco friendly crosslinked flame retardant composition for wire and cable |
| CN103172918B (en) * | 2011-12-22 | 2016-12-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of fireproofing cable material without halide and preparation method thereof |
| CN103030917B (en) * | 2012-12-28 | 2015-04-22 | 浙江万马高分子材料有限公司 | Cracking-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material |
| CN103524869B (en) * | 2013-10-11 | 2015-09-30 | 常熟市中联光电新材料有限责任公司 | The heat-resisting thermoplastic halogen-free and low-smoke flame-retardant polyolefin plastics of electric wire |
| CN105367886B (en) * | 2015-11-30 | 2018-02-06 | 无锡杰科塑业有限公司 | Heat-resistant halogen-free flame-retardant polyolefin material and preparation method thereof |
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Address after: 201802 Shanghai City, Jiading District Nanxiang Town Yongle Village No. 271 Applicant after: Shanghai Kaibo cable special material Co., Ltd Address before: 201802 Shanghai City, Jiading District Nanxiang Town Yongle Village No. 271 Applicant before: SHANGHAI KAIBO SPECIAL CABLE FACTORY Co.,Ltd. |
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