CN113174094B - Anti-aging flame-retardant cable insulating material and preparation method thereof - Google Patents
Anti-aging flame-retardant cable insulating material and preparation method thereof Download PDFInfo
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- CN113174094B CN113174094B CN202110400560.6A CN202110400560A CN113174094B CN 113174094 B CN113174094 B CN 113174094B CN 202110400560 A CN202110400560 A CN 202110400560A CN 113174094 B CN113174094 B CN 113174094B
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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
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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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
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- 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
- 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 provides an anti-aging flame-retardant cable insulating material which is based on chloroprene rubber and natural rubber, wherein components such as nano-alumina, maleic anhydride grafted polyethylene, 3-butene triethoxysilane and the like are added into raw materials, and the raw materials are matched with other raw materials, so that the prepared cable insulating material has excellent mechanical property, anti-aging property and insulating property. The invention also provides a preparation method of the insulating material.
Description
Technical Field
The invention relates to an anti-aging flame-retardant cable insulating material and a preparation method thereof.
Background
The cable material is an important part for protecting the cable from being damaged by the outside, and is generally made of high molecular functional materials. The cable material must be able to protect the inner and outer conductors and the insulating layer of the cable from the effects of environment, weather, acid and hydrolysis, and at present, the main material of the cable sheath material mainly comprises chlorinated polyethylene, chlorosulfonated polyethylene, polyurethane, polyethylene, various natural or synthetic rubbers, and the like. The existing cable sheath material generally adopts a single high polymer material as a main material.
In addition, in the actual production process, the cable sheath material can be used together with a large amount of inorganic filler (such as inorganic reinforcing agent, inorganic flame retardant and the like), so that the vulcanization performance, physical and mechanical properties, thermal properties and the like of the rubber compound are changed, but the direct addition of the inorganic filler to the rubber compound has two disadvantages: firstly, the surface energy of inorganic filler particles is high, the inorganic filler particles are in a thermodynamically unstable state and are very easy to agglomerate, and the application effect of the inorganic filler particles is directly influenced; and secondly, the surface of inorganic filler particles is hydrophilic and oleophobic and has strong polarity, the inorganic filler particles are difficult to disperse uniformly in the sizing material, and the bonding force between the inorganic filler particles and the sizing material is weak, so that interface defects are caused, and the performance of the cable sheath material is reduced.
Therefore, it is desirable to provide a cable material with excellent combination of properties to solve the problems of the prior art.
Disclosure of Invention
The invention provides an anti-aging flame-retardant cable insulating material which is based on chloroprene rubber and natural rubber, wherein components such as nano-alumina, maleic anhydride grafted polyethylene, 3-butene triethoxysilane and the like are added into raw materials, and the raw materials are matched with other raw materials, so that the prepared cable insulating material has excellent mechanical property, anti-aging property and insulating property. The invention also provides a preparation method of the insulating material.
The above purpose of the invention is realized by the following technical scheme:
an anti-aging flame-retardant cable insulating material is prepared from the following raw materials: chloroprene rubber, natural rubber, a vulcanizing agent, a plasticizer, an anti-aging agent, tributyl phosphate, a filler and 3-butene triethoxysilane;
wherein the vulcanizing agent comprises magnesium oxide, zinc oxide, stearic acid, tetramethylthiuram monosulfide, di-o-tolylguanidine and sulfur;
the plasticizer comprises vaseline and maleic anhydride grafted polyethylene resin;
the filler comprises nano alumina.
The addition of inorganic fillers to cable insulation materials to enhance various properties of the materials is a common method in the art, but the addition of inorganic fillers has problems that the fillers are not easily dispersed and the binding property with other components in the raw materials is poor. The maleic anhydride grafted polyethylene is added in the raw materials, so that the compatibility between high polymers and between the high polymers and inorganic filler particles can be promoted; on the other hand, 3-butylene triethoxy silane is added into the raw materials, so that the binding force between the high polymer and the inorganic filler can be promoted, and the improvement of the mechanical property of the final insulating material is facilitated. The filler contains nano-alumina, and can improve the mechanical property of the insulating material to a small extent, and can improve the flame retardant property of the material by matching with tributyl phosphate.
In the vulcanizing agent, the vulcanizing agent comprises the following components in parts by mass:
the using amount of the magnesium oxide is 3-5 parts by mass;
the using amount of the zinc oxide is 3-5 parts by mass;
the using amount of the stearic acid is 0.5-1 part by mass;
the amount of the tetramethylthiuram monosulfide is 0.5-1 part by mass;
the dosage of the di-o-tolylguanidine is 0.5-1 part by mass;
the amount of the sulfur is 0.5-1 part by mass.
The grafting rate of the maleic anhydride grafted polyethylene is 0.8-1.2%, the number average molecular weight is 2000-3000, and preferably, the grafting rate of the maleic anhydride grafted polyethylene is 0.8%, and the number average molecular weight is 3000.
The number average molecular weight of the maleic anhydride grafted polyethylene is preferably within the range defined by the invention, and exceeding the preferable range influences the contribution of the maleic anhydride grafted polyethylene to the compatibility of each component, thereby being reflected in that the comprehensive performance of the final insulating material cannot reach the optimal standard.
The mass ratio of the vaseline to the maleic anhydride grafted polyethylene resin is 3: 1.
the anti-aging agent is N-phenyl-2-naphthylamine and/or 2-mercaptobenzimidazole. In a preferred embodiment of the invention, the anti-aging agent is N-phenyl-2-naphthylamine and 2-mercaptobenzimidazole, and the mass ratio of the anti-aging agent to the anti-aging agent is 1: 1.
The filler comprises carbon black and white carbon black besides nano alumina, and preferably, the nano alumina in the filler accounts for 20-30% of the total mass of the filler. The dosage of the nano alumina is in the optimized range of the invention, the improvement of the comprehensive performance of the insulating material can be promoted, if the dosage of the nano alumina exceeds the optimized range of the invention, the dispersing capacity of the raw material system of the invention to inorganic particles can be exceeded, and the performance of the final material can not be improved continuously; if the preferred range is lower, the optimum performance improvement level is not attained.
In the raw materials of the insulating material, the relative parts by mass of the following components are as follows:
the dosage of the chloroprene rubber is 70-90 parts by mass;
the amount of the natural rubber is 10-30 parts by mass;
the amount of the vulcanizing agent is 12-15 parts by mass;
the amount of the plasticizer is 12-15 parts by mass;
the using amount of the anti-aging agent is 2-5 parts by mass;
the using amount of the tributyl phosphate is 3-5 parts by mass;
the amount of the filler is 25-35 parts by mass;
the amount of the 3-butene triethoxysilane is 3-5 parts by mass.
The preparation method of the insulating material comprises the steps of mixing and vulcanizing raw materials of the insulating material to obtain the insulating material.
It should be noted that the insulating material is prepared according to the kind and amount of the raw materials defined in the present invention, wherein the specific methods, processes, equipment, parameters, etc. used are all known in the art, and the present invention can also be prepared according to the technical scheme already disclosed, without affecting the implementation of the present invention.
The chemical substances which are not described in the invention can be prepared from commercial products or conventional technical schemes and conventional technical parameters, and the implementation of the invention is not influenced.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
the mixing process comprises the following steps:
(1) plasticating chloroprene rubber and natural rubber in a two-roll open mill at room temperature, and rolling for 3 times;
(2) after plastication, adding the mixture into a 110 internal mixer, wherein the total volume of an internal mixing chamber is 108L, the working volume is 81L, and the charging coefficient is 60%;
a back mixing method is adopted, the rotating speed is 25r/min, and a plasticizer, an anti-aging agent, tributyl phosphate, a filler and 3-butene triethoxysilane are sequentially added into an internal mixer; the mixing time is 8-10 min, and the temperature of first-stage rubber discharge does not exceed 105 ℃;
(3) and (3) cooling the rubber, putting the rubber into an internal mixer again, adding a vulcanizing agent, carrying out secondary vulcanization at the temperature of 96 ℃, uniformly mixing, and discharging the rubber to obtain the rubber compound.
The extrusion vulcanization process comprises the following steps:
(1) and extruding the rubber compound strip by adopting an XJWY-90 cold feed rubber extruder. The diameter of the screw is 90mm, the length-diameter ratio of the screw is as follows: 14:1, screw structure form: double-head composite equidistant deepening; preheating a machine head and a machine body before feeding, and starting the machine head and the machine body at a high rotating speed to generally raise the temperature of each part of an extruder to 80 +/-5 ℃, and reducing the temperature to 60 +/-5 ℃ within about 2min in a short time; temperature range: the temperature of the machine body is 40-60 ℃, the temperature of the machine head is 60-80 ℃, the temperature of the neck mold is 65-90 ℃, the temperature of the machine body is preferably 60 ℃, the temperature of the machine head is 70 ℃, and the temperature of the neck mold is 80 ℃;
(2) vulcanizing by adopting saturated steam; before vulcanization, saturated steam is used for exhausting air, the steam pressure and the vulcanization temperature are depended on, the vulcanization temperature is increased, the crosslinking degree is improved, and the compression permanent deformation is reduced to a certain degree; the total length of the pipeline of the vulcanization production line is 110 m, the pressure of the pipeline is controlled to be 1.0-1.3 MPa, the optimal pressure is 1.3MPa, and the opening speed is 4m/min, so that the insulating material is obtained.
The invention has the following beneficial effects: according to the invention, chloroprene rubber and natural rubber are taken as basic raw materials, besides the conventional raw materials and preparation processes in the field, components such as nano alumina, maleic anhydride grafted polyethylene, 3-butene triethoxysilane and the like are added in the raw materials, and through the mutual matching of the components, the prepared cable insulating material has excellent mechanical property, anti-aging property and insulating property.
Detailed Description
The invention is further illustrated by the following specific examples. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Neoprene, designation CR232, shanxi holo parental synthetic rubber ltd;
natural rubber, beijing xinlidcheng science and technology ltd;
vaseline, Shandong Longhui chemical Co., Ltd;
maleic anhydride-grafted polyethylene, grafting rate 0.8%, number average molecular weight 3000, koies chemical ltd;
maleic anhydride-grafted polypropylene, graft rate 0.8%, number average molecular weight 3000, koies chemical ltd;
nano alumina, beijing german island gold technologies ltd;
carbon black, brand N220, santong wanghua tianhe new materials limited;
white carbon black, trade mark HB-151D, Hubei Hufu nanometer materials GmbH.
The preparation method of the vulcanizing agent 1 and the vulcanizing agent 2 comprises the following steps: the components were mixed uniformly according to the kinds and amounts of the components listed in Table 1.
TABLE 1 dosage of vulcanizing agent (parts by mass)
The preparation methods of the plasticizer 1, the comparative plasticizer 1 and the comparative plasticizer 2 are as follows: the components were mixed uniformly according to the kinds and amounts of the components listed in Table 2.
TABLE 2 plasticizer amounts (parts by mass)
| Categories | Plasticizer 1 | Comparative plasticizer 1 | Comparative plasticizer 2 |
| Vaseline | 3 | 3 | 3 |
| Maleic anhydride grafted polyethylene | 1 | ||
| Maleic anhydride grafted polypropylene | 1 |
The preparation method of the anti-aging agent comprises the following steps: mixing N-phenyl-2-naphthylamine and 2-mercaptobenzimidazole according to a mass ratio of 1: 1 by uniformly mixing.
The preparation method of the filler and the comparative filler comprises the following steps: the components were mixed uniformly according to the kinds and amounts of the components listed in Table 3.
TABLE 3 Filler raw material amounts (parts by mass)
| Categories | Filler material | Contrast fillMaterial |
| Nano alumina | 10 | |
| Carbon black | 20 | 20 |
| White carbon black | 4 | 4 |
Examples and comparative examples the amounts of the respective raw materials are listed in table 4, in relative parts by mass of the respective components.
TABLE 4 insulating Material amounts (parts by mass)
The insulation material samples of examples and comparative examples were prepared by the following method:
firstly, mixing:
(1) plasticating chloroprene rubber and natural rubber in a two-roll open mill at room temperature, and rolling for 3 times;
(2) after plastication, adding the mixture into a 110 internal mixer, wherein the total volume of an internal mixing chamber is 108L, the working volume is 81L, and the charging coefficient is about 60%;
a back mixing method is adopted, the rotating speed is 25r/min, and a plasticizer, an anti-aging agent, tributyl phosphate, a filler and 3-butylene triethoxysilane (if any) are sequentially added into an internal mixer; the mixing time is 10min, and the temperature of first-stage rubber discharge does not exceed 105 ℃;
(3) after the rubber is cooled, putting the rubber into an internal mixer again, adding a vulcanizing agent, carrying out secondary vulcanization at the temperature of 96 ℃, uniformly mixing, and then discharging the rubber to obtain rubber compound;
secondly, extruding and vulcanizing:
(1) extruding the rubber compound strip by adopting an XJWY-90 cold feed rubber extruder; wherein, the screw rod diameter is 90mm, screw rod draw ratio: 14:1, screw structure form: double-head composite equidistant deepening; preheating a machine head and a machine body before feeding, and starting the machine head and the machine body at a high rotating speed to generally raise the temperature of each part of an extruder to 80 +/-5 ℃, and reducing the temperature to 60 +/-5 ℃ within about 2min in a short time; temperature range: the temperature of the machine body is 60 ℃, the temperature of the machine head is 70 ℃, and the temperature of the mouth mold is 80 ℃;
(2) vulcanizing by adopting saturated steam; the total length of the pipeline of the vulcanization production line is 110 meters, the pressure is controlled at 1.3MPa, and the opening speed is 4m/min, so that the insulating material is obtained.
The samples obtained in the examples and comparative examples were subjected to a performance test:
1. the tensile strength test standard is GB/T528-2009;
2. the tearing strength test standard is GB/T529-2008;
3. the volume resistivity test standard is GB/T1410-2006;
4. the aging performance test standard is GB/T2951.12-2008.
The test results of examples and comparative examples are shown in Table 5.
TABLE 5 test results of examples and comparative examples
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. The anti-aging flame-retardant cable insulating material is characterized in that raw materials for preparing the insulating material comprise: chloroprene rubber, natural rubber, a vulcanizing agent, a plasticizer, an anti-aging agent, tributyl phosphate, a filler and 3-butene triethoxysilane;
wherein the vulcanizing agent comprises magnesium oxide, zinc oxide, stearic acid, tetramethylthiuram monosulfide, di-o-tolylguanidine and sulfur;
the plasticizer comprises vaseline and maleic anhydride grafted polyethylene resin;
the filler comprises nano alumina, carbon black and white carbon black;
the grafting rate of the maleic anhydride grafted polyethylene is 0.8-1.2%, and the number average molecular weight is 2000-3000;
the mass ratio of the vaseline to the maleic anhydride grafted polyethylene resin is 3: 1;
the nano alumina in the filler accounts for 20-30% of the total mass of the filler;
in the raw materials of the insulating material, the relative parts by mass of the following components are as follows:
the dosage of the chloroprene rubber is 70-90 parts by mass;
the amount of the natural rubber is 10-30 parts by mass;
the amount of the vulcanizing agent is 12-15 parts by mass;
the amount of the plasticizer is 12-15 parts by mass;
the using amount of the anti-aging agent is 2-5 parts by mass;
the using amount of the tributyl phosphate is 3-5 parts by mass;
the amount of the filler is 25-35 parts by mass;
the amount of the 3-butene triethoxysilane is 3-5 parts by mass.
2. Insulation material according to claim 1, characterized in that in the vulcanising agent the following components are present in relative parts by mass:
the using amount of the magnesium oxide is 3-5 parts by mass;
the using amount of the zinc oxide is 3-5 parts by mass;
the using amount of the stearic acid is 0.5-1 part by mass;
the amount of the tetramethylthiuram monosulfide is 0.5-1 part by mass;
the dosage of the di-o-tolylguanidine is 0.5-1 part by mass;
the amount of the sulfur is 0.5-1 part by mass.
3. The insulation material of claim 1, wherein the maleic anhydride grafted polyethylene has a grafting ratio of 0.8% and a number average molecular weight of 3000.
4. Insulation material according to claim 1, characterized in that the antioxidant is N-phenyl-2-naphthylamine and/or 2-mercaptobenzimidazole.
5. A method for preparing an insulating material according to any one of claims 1 to 4, wherein the insulating material is obtained by kneading and vulcanizing raw materials of the insulating material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585780A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | Flame-retardant thermal-aging-resistant EPDM composite material |
| CN109021337A (en) * | 2018-07-30 | 2018-12-18 | 合肥尚强电气科技有限公司 | Oil-resistant and heat-resistant high-toughness cable material |
| CN110591185A (en) * | 2019-08-15 | 2019-12-20 | 北京化工大学 | Rubber material for full-sea deep watertight cable and preparation method thereof |
| CN110684244A (en) * | 2019-10-12 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber foamed polymer composite material and preparation method thereof |
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- 2021-04-14 CN CN202110400560.6A patent/CN113174094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585780A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | Flame-retardant thermal-aging-resistant EPDM composite material |
| CN109021337A (en) * | 2018-07-30 | 2018-12-18 | 合肥尚强电气科技有限公司 | Oil-resistant and heat-resistant high-toughness cable material |
| CN110591185A (en) * | 2019-08-15 | 2019-12-20 | 北京化工大学 | Rubber material for full-sea deep watertight cable and preparation method thereof |
| CN110684244A (en) * | 2019-10-12 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber foamed polymer composite material and preparation method thereof |
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