CN111961277A - Low-smoke halogen-free flame-retardant cable material with good char formation, preparation method thereof and cable - Google Patents
Low-smoke halogen-free flame-retardant cable material with good char formation, preparation method thereof and cable Download PDFInfo
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- CN111961277A CN111961277A CN202010864571.5A CN202010864571A CN111961277A CN 111961277 A CN111961277 A CN 111961277A CN 202010864571 A CN202010864571 A CN 202010864571A CN 111961277 A CN111961277 A CN 111961277A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a low-smoke halogen-free flame-retardant cable material with good char forming property, a preparation method thereof and a cable, wherein the low-smoke halogen-free cable material comprises the following components in parts by weight: 40 parts of matrix resin, 50-60 parts of flame retardant, 0.5-1.5 parts of antioxidant and 1-5 parts of lubricant; the base resin consists of EVA and a compatilizer, wherein the VA content in the EVA is 0.28; the flame retardant comprises the following components in parts by weight: 35-40 parts of II-type ammonium polyphosphate, 7-10 parts of cellulose nano-fiber, 1-5 parts of a dispersing agent, 5-10 parts of layered graphite and 35-50 parts of a solvent, wherein the crystallinity of the cellulose nano-fiber is more than or equal to 75%. The low-smoke halogen-free flame-retardant cable material disclosed by the invention has the advantages of good compatibility of the base material and the flame retardant, compact char formation, good char formation performance and excellent mechanical properties and flame retardance.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a low-smoke halogen-free flame-retardant cable material with good char formation, a preparation method thereof and a cable.
Background
Along with the environmental awareness of people and the requirement of environmental protection in the cable industry, the demand of the low-smoke halogen-free flame-retardant polyolefin cable material is gradually increased. EVA (ethylene-vinyl acetate copolymer) is a halogen-free polar polymer, which is considered one of the most promising base materials for sheathing, oxygen barrier and shielding materials due to its good electrical, physical and processing properties. However, the flame retardant property of EVA is not excellent, most of the current EVA flame retardant systems use inorganic flame retardants such as metal hydroxides and graphite as fillers, and also use relatively high-efficiency intumescent flame retardants such as phosphorus-nitrogen system for filling, which significantly improves the flame retardant property of EVA.
However, after the flame retardant filler is added, the flame retardant property of the EVA is improved, and at the same time, the defect is obvious and unavoidable. Because EVA itself has polar linear chain molecules, and general flame retardants are nonpolar or weakly polar, compatibility between the base material and the flame retardant is poor, and mechanical properties are reduced. In addition to the compatibility problem, the char formation effect of the cable material is also a difficult point, the inorganic metal hydroxide does not contain carbon, the amount of residual carbon is small, while the graphite has high carbon content but is used as a flame retardant alone, the flame retardant effect is not ideal, and the smaller the particle size is due to the existence of the size effect, the poorer the flame retardant effect is. As for the efficient phosphorus-nitrogen flame retardant, in addition to being easy to absorb moisture, the carbon forming effect is not ideal, and the continuity and compactness of the carbon layer cannot be ensured.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-smoke halogen-free flame-retardant cable material with good compatibility between a base material and a flame retardant and good char formation.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a low-smoke halogen-free flame-retardant cable material with good char forming property, which comprises the following components in parts by weight: 40 parts of matrix resin, 50-60 parts of flame retardant, 0.5-1.5 parts of antioxidant and 1-5 parts of lubricant;
the base resin consists of EVA and a compatilizer, wherein the VA content in the EVA is 0.28; the flame retardant comprises the following components in parts by weight: 35-40 parts of II-type ammonium polyphosphate, 7-10 parts of cellulose nano-fiber, 1-5 parts of a dispersing agent, 5-10 parts of layered graphite and 35-50 parts of a solvent, wherein the crystallinity of the cellulose nano-fiber is more than or equal to 75%.
Cellulose nano-fiber, also known as nano-cellulose, is a novel green nano-material. Besides the natural advantages of abundant reserves and reproducible circulation, the nanocellulose also has the advantages of nano-scale structure, good mechanical strength, lower thermal expansion coefficient and the like. Therefore, cellulose nanofibers are generally used in energy storage devices such as metal ion batteries and supercapacitors as separator and electrode materials.
In the invention, the inventor introduces cellulose nano-fiber into the field of cable materials, and mixes the cellulose nano-fiber with ammonium polyphosphate and layered graphite as a flame retardant, and aims to: on one hand, the polarity of the cellulose nanofiber is close to that of the EVA base material, and meanwhile, the fiber structure of the cellulose nanofiber can be better dispersed in the base material, so that the compatibility of the flame retardant and the EVA base material is improved, and the mechanical property of the cable material is favorably improved; on the other hand, the cellulose nano-fiber has high carbon content, high and stable carbon forming rate, and after being combined with ammonium polyphosphate and layered graphite through hydrogen bonds, the carbon forming performance of the flame retardant is improved, and a continuous and compact carbon layer can be formed. In addition, as the cellulose nano-fibers and the ammonium polyphosphate form hydrogen bonds, the moisture absorption degree of the ammonium polyphosphate can be reduced, and the flame retardant effect is further improved.
In the invention, the preferable scheme is that the compatilizer is at least one of POE-g-MAH, EVA-g-MAH and PE-g-MAH.
In the invention, the preferable scheme is that the weight ratio of the type II ammonium polyphosphate, the cellulose nano-fiber and the layered graphite in the flame retardant is 10:2: 1.
In the present invention, it is preferable that the antioxidant is at least one of antioxidant 1010, antioxidant 300 and antioxidant 168.
In the present invention, it is preferable that the dispersant is at least one of a fatty acid amide dispersant and a surfactant.
In the present invention, it is preferable that the lubricant is at least one of calcium stearate, silicone, and silica.
In the invention, the preferable scheme is that the solvent is a mixed solution of deionized water and absolute ethyl alcohol, and the mass ratio of the deionized water to the absolute ethyl alcohol is 3: 1.
The invention also provides a preparation method of the low-smoke halogen-free flame-retardant cable material with good char forming property, which comprises the following steps:
dispersing the layered graphite in a solvent, stirring, adding a dispersing agent, stirring for 5-10min, adding cellulose nanofiber, stirring for 10-20min, adding type II ammonium polyphosphate, and continuously stirring for 20-30 min; removing the solvent to obtain the flame retardant;
stirring EVA, compatilizer, antioxidant, lubricant and flame retardant for 3-5min, adding the obtained mixture into an internal mixer, extruding and granulating by a single screw at the temperature of 150-.
According to the invention, the cellulose nanofibers and the ammonium polyphosphate are firstly prepared into the master batch, so that hydrogen bonds formed between the cellulose nanofibers and the ammonium polyphosphate are more sufficient, the moisture absorption degree of the ammonium polyphosphate is reduced, and the flame retardant effect is ensured.
The invention also provides a cable prepared from the low-smoke halogen-free flame-retardant cable material with good char forming property.
Compared with the prior art, the invention has the beneficial effects that:
the flame retardant with good compatibility with the EVA substrate is prepared by pre-crosslinking the cellulose nano-fiber, ammonium polyphosphate and layered graphite, and has the advantages of high carbonization rate, compactness, good carbonization performance and excellent mechanical property and flame retardant performance.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
1. 3.5 parts of layered graphite is dispersed in a mixed solution of deionized water and absolute ethyl alcohol (90 parts by mass of water and 30 parts by mass of ethyl alcohol), 1 part of dispersing agent is added under the condition of continuous stirring, and the mixture is continuously stirred for 6 min. And then adding 7 parts of cellulose nano-fiber into the mixed solution, continuously stirring for 12min, and adding 35 parts of type II ammonium polyphosphate. Stirring for 20min, and evaporating the solvent to obtain the flame retardant.
2. Weighing 35 parts of EVA resin (brand: 2803), 5 parts of compatilizer EVA-g-MAH, 54 parts of flame retardant, 1 part of antioxidant 1010 and 5 parts of lubricant silicon dioxide, adding the materials into a high-speed stirrer, stirring for 5min, then placing the mixture into an internal mixer, mixing until the material temperature is 150 ℃, discharging, extruding and granulating by a single-screw extruder, and fully drying to obtain the low-smoke halogen-free flame-retardant cable material.
Comparative example 1
1. 3.5 parts of layered graphite is dispersed in a mixed solution of deionized water and absolute ethyl alcohol (90 parts by mass of water and 30 parts by mass of ethyl alcohol), 1 part of dispersing agent is added under the condition of continuous stirring, and the mixture is continuously stirred for 6 min. And then 35 parts of type II ammonium polyphosphate is added, stirred for 20min, and the solvent is evaporated to obtain the flame retardant.
2. Weighing 35 parts of EVA resin (brand: 2803), 5 parts of compatilizer EVA-g-MAH, 54 parts of flame retardant, 1 part of antioxidant 1010 and 5 parts of lubricant silicon dioxide, adding the materials into a high-speed stirrer, stirring for 5min, then placing the mixture into an internal mixer, mixing until the material temperature is 150 ℃, discharging, extruding and granulating by a single-screw extruder, and fully drying to obtain the low-smoke halogen-free flame-retardant cable material.
Performance testing
The low-smoke halogen-free flame-retardant cable materials prepared in the example 1 and the comparative example 1 are respectively subjected to performance tests, and the test indexes comprise tensile strength, elongation at break, oxygen index, UL-94, residual carbon content and char formation condition. Wherein the tensile strength and the elongation at break are tested according to GB/T1040.1-2018 standard, the oxygen index is tested according to GB/T2406.2-2009 standard, the UL-94 is tested according to GB/T2951.41-2008 standard, and the residual carbon content is tested according to GB/T2408-2008 standard. Specific test results are shown in table 1.
Table 1 results of performance test of cable materials of examples and comparative examples
| Name of test | Unit of | Example 1 | Comparative example 1 |
| Tensile strength | MPa | 9 | 7 |
| Elongation at break | ％ | 180 | 160 |
| Oxygen index | ％ | 34.8 | 30 |
| UL-94 | V-0 | V-0 | |
| Residual carbon content | ％ | 35 | 15 |
| Char formation | The surface is filiform and the inside is dense | Surface and interior bulk |
From the results in the table, it can be seen that the amount of residual carbon and char formation of the cable material in example 1 are significantly better than those of the cable material in comparative example 1 due to the addition of the cellulose nanofibers, and the indexes such as tensile strength, elongation at break, and oxygen index are also better than those of comparative example 1.
In conclusion, the low-smoke halogen-free flame-retardant cable material disclosed by the invention has the advantages that the compatibility of the EVA base material and the flame retardant is good, the carbonization speed is high, the compactness is realized, the carbonization performance is good, and the excellent mechanical property and the flame retardant property are both considered.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (9)
1. A low-smoke halogen-free flame-retardant cable material with good char forming property is characterized by comprising the following components in parts by weight: 40 parts of matrix resin, 50-60 parts of flame retardant, 0.5-1.5 parts of antioxidant and 1-5 parts of lubricant;
the base resin consists of EVA and a compatilizer, wherein the VA content in the EVA is 0.28; the flame retardant comprises the following components in parts by weight: 35-40 parts of II-type ammonium polyphosphate, 7-10 parts of cellulose nano-fiber, 1-5 parts of a dispersing agent, 5-10 parts of layered graphite and 35-50 parts of a solvent, wherein the crystallinity of the cellulose nano-fiber is more than or equal to 75%.
2. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein the compatilizer is at least one of POE-g-MAH, EVA-g-MAH and PE-g-MAH.
3. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein in the flame retardant, the weight ratio of the type II ammonium polyphosphate, the cellulose nano-fiber and the layered graphite is 10:2: 1.
4. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 300 and antioxidant 168.
5. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein the dispersant is at least one of fatty acid amide dispersant and surfactant.
6. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein the lubricant is at least one of calcium stearate, silicone and silicon dioxide.
7. The low-smoke halogen-free flame-retardant cable material with good char forming property according to claim 1, wherein the solvent is a mixed solution of deionized water and absolute ethyl alcohol, and the mass ratio of the deionized water to the absolute ethyl alcohol is 3: 1.
8. The preparation method of the low-smoke halogen-free flame-retardant cable material with good char forming property according to any one of claims 1 to 7, characterized by comprising the following steps:
dispersing the layered graphite in a solvent, stirring, adding a dispersing agent, stirring for 5-10min, adding cellulose nanofiber, stirring for 10-20min, adding type II ammonium polyphosphate, and continuously stirring for 20-30 min; removing the solvent to obtain the flame retardant;
stirring EVA, compatilizer, antioxidant, lubricant and flame retardant for 3-5min, adding the obtained mixture into an internal mixer, extruding and granulating by a single screw at the temperature of 150-.
9. A cable prepared from the low-smoke halogen-free flame-retardant cable material with good char forming property according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010864571.5A CN111961277A (en) | 2020-08-25 | 2020-08-25 | Low-smoke halogen-free flame-retardant cable material with good char formation, preparation method thereof and cable |
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| CN202010864571.5A CN111961277A (en) | 2020-08-25 | 2020-08-25 | Low-smoke halogen-free flame-retardant cable material with good char formation, preparation method thereof and cable |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN104650446A (en) * | 2015-01-20 | 2015-05-27 | 江苏上上电缆集团有限公司 | Nano-clay-containing irradiation crosslinked polyolefin cable material and preparation method thereof |
| CN104804166A (en) * | 2015-04-28 | 2015-07-29 | 中科院广州化学有限公司南雄材料生产基地 | Flame-retardant composite material of polyurethane and nanocellulose, as well as preparation method and application of flame-retardant composite material |
| CN105968539A (en) * | 2016-07-22 | 2016-09-28 | 铜陵宏正网络科技有限公司 | High-strength cable material for medium-voltage power cables of 35kV and below and preparation method thereof |
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- 2020-08-25 CN CN202010864571.5A patent/CN111961277A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN104650446A (en) * | 2015-01-20 | 2015-05-27 | 江苏上上电缆集团有限公司 | Nano-clay-containing irradiation crosslinked polyolefin cable material and preparation method thereof |
| CN104804166A (en) * | 2015-04-28 | 2015-07-29 | 中科院广州化学有限公司南雄材料生产基地 | Flame-retardant composite material of polyurethane and nanocellulose, as well as preparation method and application of flame-retardant composite material |
| CN105968539A (en) * | 2016-07-22 | 2016-09-28 | 铜陵宏正网络科技有限公司 | High-strength cable material for medium-voltage power cables of 35kV and below and preparation method thereof |
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Application publication date: 20201120 |