CN113121996A - High-molecular polymer material for wires and cables and preparation method thereof - Google Patents
High-molecular polymer material for wires and cables and preparation method thereof Download PDFInfo
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- CN113121996A CN113121996A CN202110417245.4A CN202110417245A CN113121996A CN 113121996 A CN113121996 A CN 113121996A CN 202110417245 A CN202110417245 A CN 202110417245A CN 113121996 A CN113121996 A CN 113121996A
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/0253—Polyamines containing sulfur in the main chain
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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
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high molecular polymer material for wires and cables and a preparation method thereof, and the high molecular polymer material comprises nano titanium dioxide, 4 '-diamino diphenyl disulfide, a modifier, an antioxidant 1010 and polyethylene wax, wherein the mass ratio of the nano titanium dioxide, the 4, 4' -diamino diphenyl disulfide, the modifier, the antioxidant 1010 and the polyethylene wax is as follows: 5-10: 0.3-0.5: 1-2. The product of the invention can realize self-repairing property at room temperature, and the repairing effect reaches more than 100% in 24 hours. The product can be used as a sheath material for manufacturing and producing cable products, can automatically repair and heal after a period of time after the sheath material is damaged, changes the complex process of manual repair after the sheath is damaged, and improves the production efficiency of cables.
Description
Technical Field
The invention relates to a high molecular polymer material for wires and cables and a preparation method thereof, belonging to the technical field of high molecular polymer materials.
Background
At present, during the production, storage, transportation, installation and use of electric wires and cables, the sheath material is often damaged, such as: cracking, scratching, crushing, grinding, etc. The electric wire and cable sheath after the damage is perhaps whole cable and is scrapped, perhaps extrudes the sheath again, or carries out artifical restoration to the sheath, and the artifical degree of difficulty of restoreing is big, and repair effect is not good, can not reach the performance of former sheath material after the restoration, is the weak point of cable operation in the use in later stage. The condition that the sheath is damaged often appears, a large amount of manpower and financial resources are wasted, the production cost is increased for cable manufacturing enterprises, and great economic loss is caused. In order to reduce the above loss caused by the sheath breakage, it is necessary to develop a sheath material capable of self-repairing, that is, when the sheath breakage occurs, the sheath can self-repair to restore the state before breakage, thereby avoiding the loss caused by cable scrap or sheath re-extrusion. The invention aims at the technical problems and designs a high polymer material for wires and cables and a preparation method thereof, the material has a self-healing function, the damage of the material can be repaired after the material is damaged, the repaired material has no difference with the raw material, and the self-healing of the material can be realized within 24 hours at room temperature. The material can be processed and molded by a common extruder like a common sheath material, overcomes the defect that the common sheath material cannot be self-repaired, is favored by a plurality of cable enterprises, and has good market prospect.
Disclosure of Invention
The invention aims to provide a high polymer material for wires and cables and a preparation method thereof, aiming at the problems in the prior art.
A high molecular polymer material for wires and cables comprises nano titanium dioxide, 4 '-diaminodiphenyl disulfide, a modifier, an antioxidant 1010 and polyethylene wax, wherein the mass ratio of the nano titanium dioxide, the 4, 4' -diaminodiphenyl disulfide, the modifier, the antioxidant 1010 and the polyethylene wax is as follows: 5-10: 0.3-0.5: 1-2.
Further: the modifier comprises trihydroxymethyl aminomethane, distilled water, catechol and diethylenetriamine, and the weight ratio of the trihydroxymethyl aminomethane to the distilled water to the catechol to the diethylenetriamine is as follows: 10-15: 100-.
Further: the high molecular polymer material for the wires and cables further comprises color master batches, wherein the color master batches and the residual raw materials are in the following mass ratio: 2-3: 80-100.
The invention also provides a preparation method of the high polymer material for the electric wire and the cable, which comprises the following steps:
the first step is as follows: preparation of the modifier:
adding tris (hydroxymethyl) aminomethane, distilled water, catechol and diethylenetriamine into a container, fully stirring at normal temperature, and fully dissolving;
the second step is that: preparation of self-repairing polymer:
adding nano titanium dioxide, 4' -diaminodiphenyl disulfide, the modifier prepared in the first step, an antioxidant 1010 and polyethylene wax into a container, fully stirring and dissolving, then fully washing with distilled water, filtering and drying to obtain a powdery polymer;
the third step: granulation of self-repairing polymer:
and discharging the powdery polymer and the color master batch prepared in the third step into a double-screw extrusion granulator for extrusion granulation, wherein the working temperature of the double-screw extrusion granulator is as follows: the first zone is 90 +/-5 ℃, the second zone is 110 +/-5 ℃, the third zone is 120 +/-5 ℃, the fourth zone is 130 +/-5 ℃, the fifth zone is 140 +/-5 ℃, the sixth zone is 130 +/-5 ℃ and the head is 135 ℃; the mass ratio of the powdery polymer to the color master batch is as follows: 80-100: 2-3.
The principle and the beneficial effects of the invention are as follows:
1. catechol is easy to be oxidized in alkali solution to form o-benzoquinone and free radical
2. O-benzoquinone and free radicals are subjected to addition reaction with diethylenetriamine to produce substances with the following three structures of catechol/polyamine.
3. The three groups have extremely strong reactivity, can be mutually converted and coupled, are easy to generate addition reaction with amino, and have extremely high reactivity. The reaction is schematically as follows:
4. the three groups are subjected to addition reaction with aromatic diamine containing disulfide bonds to form the reversible covalent bond type self-healing material.
5. The disulfide bond can realize self-repairing function at room temperature in the presence of catechol/polyamine, and the repairing effect reaches over 100 percent in 24 hours; if the damaged sheath is heated to 50-60 ℃, after 1 hour, the crack completely disappears, and the repairing effect reaches more than 100%; if the damaged sheath is heated to 90-100 ℃, after 15-30 minutes, the crack completely disappears, the surface crack is closed, and the healing is 100%. In the repairing process, strong interaction forces such as disulfide chemical bonds, hydrogen bonds, cross-linked networks and the like are formed. The product can be used as a sheath material for manufacturing and producing cable products, can be automatically repaired and healed after a period of time after the sheath material is damaged, changes the complex process of manual repair after the sheath is damaged, and improves the production efficiency of cables.
6. Schematic formula of sulfhydryl and disulfide bond injury-healing
Detailed Description
The essential features and remarkable effects of the present invention can be embodied in the following examples, which are not intended to limit the scope of the present invention in any way. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention.
The following examples illustrate the main raw materials used:
tris (hydroxymethyl) aminomethane: white crystalline particles, buffer;
catechol: colorless crystals, polymerized monomers;
diethylenetriamine; transparent viscous liquid, polymerized monomer;
nano titanium dioxide: white solid powder and carrier;
4, 4' -diaminodiphenyl disulfide: the oil-colored needle-shaped crystal, aromatic diamine containing disulfide bonds and polymerized monomer have reversible covalent bonds;
antioxidant 1010: white powder, resistant to thermo-oxidative aging;
polyethylene wax: lubricants, wax particles;
color master batch: the pigments are black, red, gray and the like according to the requirements of users, and are all particles.
Example 1:
a high molecular polymer material for wires and cables and a preparation method thereof comprise the following steps:
the first step is as follows: preparation of the modifier:
adding 10Kg of tris (hydroxymethyl) aminomethane, 100Kg of distilled water, 5Kg of catechol and 5Kg of diethylenetriamine into a container, and fully stirring at normal temperature to fully dissolve;
the second step is that: preparation of self-repairing polymer:
adding 5Kg of nano titanium dioxide, 5Kg of 4, 4' -diaminodiphenyl disulfide, 5Kg of the modifier prepared in the first step, 0.3Kg of antioxidant 1010 and 1Kg of polyethylene wax into a container, fully stirring and dissolving, then fully washing with distilled water, filtering and drying to obtain a powdery polymer;
the third step: granulation of self-repairing polymer:
and (3) discharging 80Kg of powdery polymer prepared in the third step and 2Kg of color master batch into a double-screw extrusion granulator for extrusion granulation, wherein the working temperature of the double-screw extrusion granulator is as follows: the first zone is 90 +/-5 ℃, the second zone is 110 +/-5 ℃, the third zone is 120 +/-5 ℃, the fourth zone is 130 +/-5 ℃, the fifth zone is 140 +/-5 ℃, the sixth zone is 130 +/-5 ℃ and the head is 135 ℃.
Example 2:
a high molecular polymer material for wires and cables and a preparation method thereof comprise the following steps:
the first step is as follows: preparation of the modifier:
adding 15Kg of tris (hydroxymethyl) aminomethane, 120Kg of distilled water, 10Kg of catechol and 10Kg of diethylenetriamine into a container, and fully stirring at normal temperature to fully dissolve;
the second step is that: preparation of self-repairing polymer:
adding 10Kg of nano titanium dioxide, 10Kg of 4, 4' -diaminodiphenyl disulfide, 10Kg of modifier prepared in the first step, 0.5Kg of antioxidant 1010 and 2Kg of polyethylene wax into a container, fully stirring and dissolving, then fully washing with distilled water, filtering and drying to obtain a powdery polymer;
the third step: granulation of self-repairing polymer:
and (3) discharging 100Kg of the powdery polymer prepared in the third step and 3Kg of the color master batch into a double-screw extrusion granulator for extrusion granulation, wherein the working temperature of the double-screw extrusion granulator is as follows: the first zone is 90 +/-5 ℃, the second zone is 110 +/-5 ℃, the third zone is 120 +/-5 ℃, the fourth zone is 130 +/-5 ℃, the fifth zone is 140 +/-5 ℃, the sixth zone is 130 +/-5 ℃ and the head is 135 ℃.
Example 3:
a high molecular polymer material for wires and cables and a preparation method thereof comprise the following steps:
the first step is as follows: preparation of the modifier:
adding 13Kg of tris (hydroxymethyl) aminomethane, 110Kg of distilled water, 7.5Kg of catechol and 7.5Kg of diethylenetriamine into a container, and fully stirring at normal temperature to fully dissolve;
the second step is that: preparation of self-repairing polymer:
adding 7.5Kg of nano titanium dioxide, 7.5Kg of 4, 4' -diaminodiphenyl disulfide, 7.5Kg of modifier prepared in the first step, 0.34Kg of antioxidant 1010 and 1.5Kg of polyethylene wax into a container, fully stirring and dissolving, then fully washing with distilled water, filtering and drying to obtain a powdery polymer;
the third step: granulation of self-repairing polymer:
and discharging 90Kg of powdery polymer prepared in the third step and 2.5Kg of color master batch into a double-screw extrusion granulator for extrusion granulation, wherein the working temperature of the double-screw extrusion granulator is as follows: the first zone is 90 +/-5 ℃, the second zone is 110 +/-5 ℃, the third zone is 120 +/-5 ℃, the fourth zone is 130 +/-5 ℃, the fifth zone is 140 +/-5 ℃, the sixth zone is 130 +/-5 ℃ and the head is 135 ℃.
Effect test
The materials prepared in examples 1-3 were used to make and measure the properties, and the results are shown in the following table:
TABLE 1 comparison of data after and before repair of material breakage (Black sheath)
TABLE 2 sheath self-repair Performance (sheath sample knife damage)
Although embodiments of the present invention have been described above, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims.
Claims (4)
1. A high molecular polymer material for electric wires and cables is characterized in that: the modified nanometer titanium dioxide/4, 4' -diaminodiphenyl disulfide/polyethylene wax composite material comprises nanometer titanium dioxide, 4' -diaminodiphenyl disulfide, a modifying agent, an antioxidant 1010 and polyethylene wax, wherein the nanometer titanium dioxide, the 4, 4' -diaminodiphenyl disulfide, the modifying agent, the antioxidant 1010 and the polyethylene wax are in mass proportion as follows: 5-10: 0.3-0.5: 1-2.
2. The polymer material for electric wire and cable according to claim 1, wherein: the modifier comprises trihydroxymethyl aminomethane, distilled water, catechol and diethylenetriamine, and the weight ratio of the trihydroxymethyl aminomethane to the distilled water to the catechol to the diethylenetriamine is as follows: 10-15: 100-.
3. A polymer material for electric wires and cables according to claim 1 or 2, wherein: the high molecular polymer material for the wires and cables further comprises color master batches, wherein the color master batches and the residual raw materials are in the following mass ratio: 2-3: 80-100.
4. A method for producing a polymer material for electric wires and cables according to any one of claims 1 to 3, comprising the steps of:
the first step is as follows: preparation of the modifier:
adding tris (hydroxymethyl) aminomethane, distilled water, catechol and diethylenetriamine into a container, fully stirring at normal temperature, and fully dissolving;
the second step is that: preparation of self-repairing polymer:
adding nano titanium dioxide, 4' -diaminodiphenyl disulfide, the modifier prepared in the first step, an antioxidant 1010 and polyethylene wax into a container, fully stirring and dissolving, then fully washing with distilled water, filtering and drying to obtain a powdery polymer;
the third step: granulation of self-repairing polymer:
and discharging the powdery polymer and the color master batch prepared in the third step into a double-screw extrusion granulator for extrusion granulation, wherein the working temperature of the double-screw extrusion granulator is as follows: the first zone is 90 +/-5 ℃, the second zone is 110 +/-5 ℃, the third zone is 120 +/-5 ℃, the fourth zone is 130 +/-5 ℃, the fifth zone is 140 +/-5 ℃, the sixth zone is 130 +/-5 ℃ and the head is 135 ℃; the mass ratio of the powdery polymer to the color master batch is as follows: 80-100: 2-3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110417245.4A CN113121996B (en) | 2021-04-19 | 2021-04-19 | High-molecular polymer material for wires and cables and preparation method thereof |
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| CN202110417245.4A CN113121996B (en) | 2021-04-19 | 2021-04-19 | High-molecular polymer material for wires and cables and preparation method thereof |
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| CN113121996A true CN113121996A (en) | 2021-07-16 |
| CN113121996B CN113121996B (en) | 2023-03-31 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629135A (en) * | 2015-01-27 | 2015-05-20 | 安徽德源电缆集团有限公司 | Modified chlorosulfonated polyethylene cable sheath material |
| WO2016186336A1 (en) * | 2015-05-21 | 2016-11-24 | 한국생산기술연구원 | Uv-sensitive self-healing polymer nanoparticles, preparation method therefor, and film using same |
| US20190315906A1 (en) * | 2016-12-13 | 2019-10-17 | Repsol, S.A. | Disulfide-containing self-healing polymer blend |
| CN112480293A (en) * | 2019-09-12 | 2021-03-12 | 中国科学院化学研究所 | Self-repairing or recyclable photocuring 3D printing part and preparation method and application thereof |
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2021
- 2021-04-19 CN CN202110417245.4A patent/CN113121996B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629135A (en) * | 2015-01-27 | 2015-05-20 | 安徽德源电缆集团有限公司 | Modified chlorosulfonated polyethylene cable sheath material |
| WO2016186336A1 (en) * | 2015-05-21 | 2016-11-24 | 한국생산기술연구원 | Uv-sensitive self-healing polymer nanoparticles, preparation method therefor, and film using same |
| US20190315906A1 (en) * | 2016-12-13 | 2019-10-17 | Repsol, S.A. | Disulfide-containing self-healing polymer blend |
| CN112480293A (en) * | 2019-09-12 | 2021-03-12 | 中国科学院化学研究所 | Self-repairing or recyclable photocuring 3D printing part and preparation method and application thereof |
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| CN113121996B (en) | 2023-03-31 |
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Address after: No.56, Fuju Road, Weishi Industrial Cluster District, Kaifeng City, Henan Province, 475500 Patentee after: Henan State Grid Cable Group Co.,Ltd. Address before: No.56, Fuju Road, Weishi Industrial Cluster District, Zhengzhou City, Henan Province, 475500 Patentee before: Henan State Grid Cable Group Co.,Ltd. |