CN114133657A - Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material - Google Patents
Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material Download PDFInfo
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- CN114133657A CN114133657A CN202111656495.XA CN202111656495A CN114133657A CN 114133657 A CN114133657 A CN 114133657A CN 202111656495 A CN202111656495 A CN 202111656495A CN 114133657 A CN114133657 A CN 114133657A
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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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- 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
- C08L2201/22—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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
A preparation method of a high-performance flame-retardant low-smoke halogen-free polyolefin cable material is characterized by comprising the following steps: the preparation method comprises the following steps of preparing the master batch A, preparing the master batch B and preparing the polyolefin cable material. The filling amount of the first flame retardant aluminum hydroxide is reduced by adding the phosphorus-nitrogen compound flame retardant, the flame retardant property of the low-smoke halogen-free material is ensured, and meanwhile, the overall mechanical property of the material is improved by introducing the polyurethane elastomer and blending. The technical scheme prepares the master batch A and the master batch B step by step, strictly controls the proportion of each component, and finally obtains the material which meets the requirements of the low-smoke halogen-free flame-retardant polyolefin sheath material for GB/T32129-: the tensile strength is more than or equal to 10MPa, the elongation at break is more than or equal to 160 percent, the retention rate of physical properties after aging for 168 hours at 100 ℃ is less than or equal to 25 percent, and the oxygen index is more than or equal to 30 percent.
Description
Technical Field
The invention belongs to the field of polyolefin cable materials, and particularly relates to a preparation method of a high-performance flame-retardant low-smoke halogen-free polyolefin cable material.
Background
Along with the development of science and technology, people's consciousness to environmental protection is gradually improved, and the application of low smoke zero halogen flame retardant cable material on wire and cable is increasing day by day.
At present, hydroxide is mostly used as a flame retardant for the low-smoke halogen-free flame-retardant polyolefin cable material, and the addition amount of the hydroxide is usually more than 150 wt% of the base material, so that the material performance is greatly deteriorated and the extrusion is difficult due to the large amount of filling. Therefore, phosphorus-nitrogen flame retardants are added in a compounding way at present, so that firstly, the addition of powder fillers is reduced, and the mechanical property of the material is improved; and secondly, the flame retardant property can be continuously kept good, and the flame retardant can be applied to the production and the use of various flame retardant low-smoke halogen-free materials at present.
Nevertheless, the phosphorus-nitrogen-based flame retardant cannot solve the problem of tensile properties. The high flame retardancy of the material means that the amount of filler is indispensable, and the tensile properties of the material become a problem, and the tensile properties may be greatly attenuated with time and difficult to meet the requirements of the aging test. Therefore, the flame retardant property of the material is kept good, and the mechanical property of the material is good, which becomes a difficult problem.
In view of the above, the present invention provides a flame retardant and high performance polyolefin cable material.
Disclosure of Invention
The invention provides a preparation method of a high-performance flame-retardant low-smoke halogen-free polyolefin cable material, and aims to solve the problem that the mechanical performance and the flame-retardant performance of the polyolefin cable material cannot be simultaneously considered.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-performance flame-retardant low-smoke halogen-free polyolefin cable material is characterized by comprising the following steps: the method comprises the following steps:
first step, preparation of masterbatch a:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader for uniform mixing at the speed of 200-400 r/min, then 50-80 parts by mass of polyurethane elastomer, 1-5 parts by mass of antioxidant, 0.1-10 parts by mass of lubricant and 1-10 parts by mass of surface treating agent are added, the mixture is continuously and uniformly mixed at the speed of 500-800 r/min, the extrusion temperature is set to be 150-190 ℃, and the mixture is extruded and granulated by a single-screw extruder and fully dried to obtain the master batch A of the formula;
step two, preparing master batch B:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader at the temperature of 170-;
step three, preparing a polyolefin cable material:
uniformly mixing the master batch A and the master batch B according to the weight ratio of 1: 4, extruding and granulating by a double-screw extruder, and fully drying to obtain the high-performance flame-retardant low-smoke halogen-free polyolefin cable material;
the polyolefin resin is a mixture of EVA resin, PE resin and POE resin, and the mass ratio of the EVA resin to the PE resin to the POE resin is 70-90:2-8: 10-20;
the flame retardant is a mixture of aluminum hydroxide and phosphorus-nitrogen flame retardant, the mass ratio of the aluminum hydroxide to the phosphorus-nitrogen flame retardant is 200-250:60-80, and the nitrogen-phosphorus flame retardant is a mixture of melamine cyanurate) and diethyl aluminum hypophosphite in a mass ratio of 1: 2;
the surface treating agent is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane, titanate and sepiolite.
Preferably, the vinyl acetate content of the EVA resin is greater than or equal to 25%.
Preferably, the shore hardness of the POE resin is greater than 80A.
Preferably, the PE resin is a metallocene linear low density polyethylene.
Preferably, the antioxidant is a mixture of at least two of antioxidant 1010, antioxidant 1035 and antioxidant DLTP.
Preferably, the lubricant is one or a mixture of more of calcium stearate, barium stearate, magnesium stearate, stearic acid, polyethylene wax and polysiloxane. .
The design principle and the effect of the invention are as follows:
1. the first flame retardant is aluminum hydroxide, the second flame retardant is compounded by phosphorus-nitrogen flame retardants, and melamine cyanurate (C) with the proportion of 2:1 is selected6H9N9O3) And diethyl aluminum hypophosphite, which forms a flame-retardant system with good flame retardance and low smoke generation and has excellent char forming effect. The phosphorus flame retardant has the advantages of good flame retardant effect, high thermal stability, lower toxicity and the like, can greatly reduce the dosage of the flame retardant, avoids the performance reduction of an insulating material added in a system, and is compounded with the nitrogen flame retardant to form an intumescent flame retardant system, so that the flame retardant effect can be improved, and the water resistance can also be improved. The thermoplastic polyurethane elastomer can form blending crosslinking when being added in a small amount during preparation, and further improves the mechanical properties of the material. In conclusion, the formula can simultaneously improve the flame retardant property and the mechanical property of the material, and can be applied to the field of low-smoke halogen-free cable materials.
2. The filling amount of the first flame retardant aluminum hydroxide is reduced by adding the phosphorus-nitrogen compound flame retardant, the flame retardant property of the low-smoke halogen-free material is ensured, and meanwhile, the overall mechanical property of the material is improved by introducing the polyurethane elastomer and blending. The technical scheme prepares the master batch A and the master batch B step by step, strictly controls the proportion of each component, and finally obtains the material which meets the requirements of the low-smoke halogen-free flame-retardant polyolefin sheath material for GB/T32129-: the tensile strength is more than or equal to 10MPa, the elongation at break is more than or equal to 160 percent, the retention rate of physical properties after aging for 168 hours at 100 ℃ is less than or equal to 25 percent, and the oxygen index is more than or equal to 30 percent.
Detailed Description
The invention is further described below with reference to the following examples and comparative examples:
first step, preparation of masterbatch a:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader for uniform mixing at the speed of 200-400 r/min, then 50-80 parts by mass of polyurethane elastomer, 1-5 parts by mass of antioxidant, 0.1-10 parts by mass of lubricant and 1-10 parts by mass of surface treating agent are added, the mixture is continuously and uniformly mixed at the speed of 500-800 r/min, the extrusion temperature is set to be 150-190 ℃, and the mixture is extruded and granulated by a single-screw extruder and fully dried to obtain the master batch A of the formula;
step two, preparing master batch B:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader at the temperature of 170-;
step three, preparing a polyolefin cable material:
and uniformly mixing the master batch A and the master batch B according to the weight ratio of 1: 4, extruding and granulating by a double-screw extruder, and fully drying to obtain the high-performance flame-retardant low-smoke halogen-free polyolefin cable material.
Table 1 below shows the amounts of the components added in examples, comparative examples 1 and 2, and table 2 shows the results of the performance tests.
Table 1:
the cable materials prepared according to the example and comparative example ratios were subjected to performance tests, and the results are shown in table 2.
Table 2:
the above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of a high-performance flame-retardant low-smoke halogen-free polyolefin cable material is characterized by comprising the following steps: the method comprises the following steps:
first step, preparation of masterbatch a:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader for uniform mixing at the speed of 200-400 r/min, then 50-80 parts by mass of polyurethane elastomer, 1-5 parts by mass of antioxidant, 0.1-10 parts by mass of lubricant and 1-10 parts by mass of surface treating agent are added, the mixture is continuously and uniformly mixed at the speed of 500-800 r/min, the extrusion temperature is set to be 150-190 ℃, and the mixture is extruded and granulated by a single-screw extruder and fully dried to obtain the master batch A of the formula;
step two, preparing master batch B:
100 parts by mass of polyolefin resin and 20-30 parts by mass of ethylene acrylate maleic anhydride copolymer are placed in a 190 ℃ high-speed kneader at the temperature of 170-;
step three, preparing a polyolefin cable material:
uniformly mixing the master batch A and the master batch B according to the weight ratio of 1: 4, extruding and granulating by a double-screw extruder, and fully drying to obtain the high-performance flame-retardant low-smoke halogen-free polyolefin cable material;
the polyolefin resin is a mixture of EVA resin, PE resin and POE resin, and the mass ratio of the EVA resin to the PE resin to the POE resin is 70-90:2-8: 10-20;
the flame retardant is a mixture of aluminum hydroxide and phosphorus-nitrogen flame retardant, the mass ratio of the aluminum hydroxide to the phosphorus-nitrogen flame retardant is 200-250:60-80, and the nitrogen-phosphorus flame retardant is a mixture of melamine cyanurate) and diethyl aluminum hypophosphite in a mass ratio of 1: 2;
the surface treating agent is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane, titanate and sepiolite.
2. The method of claim 1, wherein: the EVA resin has a vinyl acetate content of 25% or more.
3. The method of claim 1, wherein: the Shore hardness of the POE resin is greater than 80A.
4. The method of claim 1, wherein: the PE resin is metallocene linear low density polyethylene.
5. The method of claim 1, wherein: the antioxidant is a mixture of at least two of antioxidant 1010, antioxidant 1035 and antioxidant DLTP.
6. The method of claim 1, wherein: the lubricant is one or a mixture of more of calcium stearate, barium stearate, magnesium stearate, stearic acid, polyethylene wax and polysiloxane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111656495.XA CN114133657A (en) | 2021-12-31 | 2021-12-31 | Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material |
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| CN202111656495.XA CN114133657A (en) | 2021-12-31 | 2021-12-31 | Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773826A (en) * | 2022-03-30 | 2022-07-22 | 中广核高新核材科技（苏州）有限公司 | Halogen-free flame-retardant water-mist-resistant polyurethane elastomer cable material and preparation method thereof |
| CN115558280A (en) * | 2022-11-10 | 2023-01-03 | 苏州亨利通信材料有限公司 | B1-level silane cross-linked flame-retardant polyolefin cable material for wire distribution and preparation method thereof |
| CN115806707A (en) * | 2022-12-28 | 2023-03-17 | 中广核高新核材科技（苏州）有限公司 | Low-smoke halogen-free polyolefin cable material with good processability and preparation method thereof |
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2021
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| JPH07216144A (en) * | 1994-02-03 | 1995-08-15 | Showa Electric Wire & Cable Co Ltd | Flame-retardant resin composition |
| JP2002302602A (en) * | 2001-04-05 | 2002-10-18 | Fujikura Ltd | Flame-retardant resin composition |
| US20120238689A1 (en) * | 2009-12-11 | 2012-09-20 | Yabin Sun | Thermoplastic Polymer Blends Comprising Dynamically Crosslinked Polyurethane in an Olefin Polymer Matrix |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773826A (en) * | 2022-03-30 | 2022-07-22 | 中广核高新核材科技（苏州）有限公司 | Halogen-free flame-retardant water-mist-resistant polyurethane elastomer cable material and preparation method thereof |
| CN115558280A (en) * | 2022-11-10 | 2023-01-03 | 苏州亨利通信材料有限公司 | B1-level silane cross-linked flame-retardant polyolefin cable material for wire distribution and preparation method thereof |
| CN115806707A (en) * | 2022-12-28 | 2023-03-17 | 中广核高新核材科技（苏州）有限公司 | Low-smoke halogen-free polyolefin cable material with good processability and preparation method thereof |
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