CN114805998A - Thermochromic composition, preparation method thereof and application of thermochromic composition in sockets, power strips and switches - Google Patents
Thermochromic composition, preparation method thereof and application of thermochromic composition in sockets, power strips and switches Download PDFInfo
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Abstract
The application provides a thermochromic composition, which comprises the following components in parts by weight: 25-40 parts of resin; 5-30 parts of a flame retardant; 10-30 parts of an auxiliary agent; 1-10 parts of temperature-sensitive color-changing material; 20-40 parts of a filler; 0.5-1 part of lubricant; 0.5-3 parts of a crosslinking agent; 0.1-0.5 part of antioxidant. The thermochromic material comprises a capsule core and a modified coating layer coated on the outer layer of the capsule core, wherein the capsule core is prepared from a pigment mixture, ethylene, tetrafluoroethylene, an initiator and a chain transfer agent. The application also provides a preparation method of the thermochromic composition, application of the thermochromic composition in preparation of wire and cable materials and thermochromic sizing materials, and application of the thermochromic composition in preparation of early-warning wires and cables, early-warning sockets, power strips and switches.
Description
Technical Field
The application relates to the field of preparation and application of new materials for electric wires and cables, in particular to a thermochromic composition and a preparation method and application thereof.
Background
Along with the social development and the improvement of the living standard of people, the demand of electric equipment in daily life is more and more, and the extension socket enables people to enjoy the operation of multiple equipment at the same time, but brings about a plurality of potential safety hazards at the same time. Particularly, most of ordinary people cannot calculate the load of the wire when the ordinary people use the electric appliance daily due to the harm caused by local current overload. Especially when using row to insert, people often only pay close attention to the jack number, and often neglect to the power of consumer, so the problem that electric wire current overload appears very easily, if light then leads to row to insert and scrap, if heavy then arouses that the cable temperature is too high leads to burning, short circuit etc. and then triggers the conflagration, causes serious harm to people's lives and property.
At present, a black sheath is generally adopted by a household mobile flexible electric wire, a color sheath is adopted in special industries to mark the importance of a cable, and the protection of the cable at the position by people is improved. The white home appliance industry generally adopts grey-white sheathed cables, and various other home appliances such as electric kettles, microwave ovens, ovens and the like adopt black sheaths made of PVC materials as sheath layers. When the product is used for a long time, if the maintenance is not good or the product is left unused for a long time, the product is easy to be affected with damp to cause poor contact of parts of the original parts, so that electric leakage causes heat damage of the electric wire. In such cases, the existing cables are temporarily unable to perform self-checking or provide a warning signal to the user, so that in a short time, overheating and short-circuiting of the wires may occur and eventually cause a fire risk.
The temperature sensing color-changing powder used by the traditional color-changing cable is not resistant to high temperature and radiation, can not meet the long-term working requirements of working temperatures of 70 ℃, 90 ℃, 105 ℃, 125 ℃, 150 ℃ and the like of most cables on the market, and limits the application of the temperature sensing color-changing powder. The existing temperature-sensitive color-changing powder has the problems that the reversible temperature-sensitive color-changing function is easy to lose efficacy and lose efficacy in the processing process because the existing temperature-sensitive color-changing powder cannot resist high temperature. For example, in some cables, after the conductor temperature reaches 70 ℃, the reversible thermochromic function fails, and only the irreversible toner can change the color, so that the change is single. In addition, the processing temperature of general resin is more than 150 ℃, while the using temperature of the conventional temperature-sensitive discoloring powder is not more than 80 ℃ and the using temperature of the irreversible temperature-sensitive discoloring powder is not more than 120 ℃, so that many temperature-sensitive discoloring powders lose the effect in the processing process and cannot play the normal temperature-sensitive discoloring function when the cable works.
Therefore, it is necessary to develop a new high temperature resistant thermochromic material, so that the new high temperature resistant thermochromic material can be applied to the preparation of cables with warning functions, when the conductor is heated due to overload, the color of the cable can be changed according to the difference of the heating temperature of the cable load, for example, the difference of the heating temperature corresponds to different danger levels, and different danger levels are presented correspondingly through different colors such as yellowing, orange, reddening, and the like, so that the timely warning and discoloration of the cable are realized, the overload of the cable of a user is visually prompted, and the potential safety hazard of the fire house is timely eliminated by the user.
Content of application
The application aims to provide a thermochromic composition with good high-temperature resistance, compatibility and mechanical properties, and a preparation method and application thereof.
In order to achieve the above object, the present application provides the following technical solutions:
a thermochromic composition comprises the following components in parts by weight:
the thermochromic material comprises a capsule core and a modified coating layer coated on the outer layer of the capsule core, wherein the capsule core is prepared from a pigment mixture, ethylene, tetrafluoroethylene, an initiator and a chain transfer agent;
in the capsule core, the pigment mixture comprises a non-thermochromic pigment and a reversible thermochromic pigment, and the weight ratio of the non-thermochromic pigment to the reversible thermochromic pigment is 1 (1-3); the mass ratio of the ethylene to the tetrafluoroethylene is 1 (2-4); the quantity ratio of the initiator to the chain transfer agent is 1 (0.3-3); the modified coating layer is prepared from tetrafluoroethylene and ethylene, and the amount ratio of the tetrafluoroethylene to the ethylene in the modified coating layer is 1 (0.85-1.25).
Preferably, the amount ratio of the tetrafluoroethylene to the ethylene species in the modified coating layer is 1: 1.
Preferably, the thermochromic material is thermochromic microparticles.
Preferably, in the thermochromic composition, the thermochromic material is prepared by:
adding a reaction medium, heating to 50-70 ℃, and stirring at the speed of 200-;
adding the pigment mixture, introducing the ethylene and the tetrafluoroethylene, and filling the initiator and the chain transfer agent to prepare the capsule core;
continuously introducing the tetrafluoroethylene and the ethylene, maintaining the reaction pressure at 2-4.5MPa and the reaction time at 1-2h, and preparing a modified coating layer coated on the outer layer of the capsule core;
filtering and drying to obtain the ETFE-coated thermochromic material.
Preferably, the preparation of the thermochromic material is carried out in a polymerization kettle, and nitrogen is introduced to exhaust oxygen before the reaction is carried out.
Preferably, in the preparation of the thermochromic material, the reaction medium is perfluoroalkane or water.
The present application also provides a method for preparing the thermochromic composition, which is prepared by blending and extruding the components of the thermochromic composition.
The application also provides application of the thermochromic composition in preparation of wire and cable materials and thermochromic sizing materials.
The application also provides application of the thermochromic composition in preparation of early warning wires and cables.
The application also provides application of the thermochromic composition in preparation of early warning sockets, power strips and switches.
Compared with the prior art, the scheme of the application has the following advantages:
1. according to the thermochromic composition, the thermochromic material is adopted, the ethylene-tetrafluoroethylene with high temperature resistance is taken as a capsule material, and the capsule core and the modified coating layer are both treated by ethylene and tetrafluoroethylene, so that the thermochromic composition has good high temperature resistance, the long-term working temperature of the thermochromic composition can reach 220 ℃, and the thermochromic composition can adapt to the reaction environment of most of high polymer materials when being further processed.
2. In the thermochromic composition, the thermochromic material is prepared by wrapping the capsule core with ethylene-tetrafluoroethylene to prepare the modified coating layer, so that the organic treatment of the capsule core is realized, the thermochromic material can be better compatible with base materials such as PVC (polyvinyl chloride) and PE (polyethylene), and the influence of the thermochromic material on the mechanical property of the thermochromic composition is avoided.
3. In the thermochromic composition, the thermochromic material adopts ethylene-tetrafluoroethylene as a capsule material, and the ethylene-tetrafluoroethylene has a crosslinkable mechanism, so that the thermochromic composition is particularly suitable for the cable industry and can be subjected to irradiation crosslinking, so that the thermochromic material can be further processed into the thermochromic composition, such as a cable material, and not only can good mechanical properties be maintained, but also the elongation at break can reach 180% after irradiation.
4. In the thermochromic composition, the capsule core of the thermochromic material adopts the non-thermochromic pigment and the reversible thermochromic pigment, so that the dispersion can be more uniform, the property stability of the material is ensured, and the function is more stable when the thermochromic material is used for realizing thermochromic. Meanwhile, the reversible thermochromic pigment and the non-thermochromic pigment are matched with each other, and multi-section color mixing can be performed according to different emergency situations, so that forecasting of different scenes, such as early warning, warning and scrapping, can be realized, and yellow, orange and red can be adopted for warning in sequence.
5. In the thermochromic composition of the application, the thermochromic material used does not have adverse effect on the performance of the thermochromic composition, the cost is very low, but the thermochromic material is added when electric materials such as wires, cables, sockets, power strips and switches are prepared, multi-section temperature sensing color change can be realized, visual display of temperature change can be realized, the working conditions of the wires, cables, sockets, power strips and switches can be visually judged, the thermochromic composition is very convenient, and low-cost and high-benefit are really realized. Furthermore, the working conditions of the power distribution box can be visually judged through the appearances of the electric wire and cable, the socket, the power strip and the switch, and the color change early warning is realized to play a vital role in ensuring the safety of power utilization. As a common user, it is difficult to know whether the socket, the socket strip and the switch are fully loaded, overloaded or heavily overloaded when the power is used, and whether the heating abnormality occurs can be judged only by touching the surfaces of the cable, the socket strip and the switch when the power is used, which is especially a great potential safety hazard for the old. The application of the temperature sensing color-changing material can prevent the accident if being pushed out comprehensively, greatly improves the power utilization safety, and can avoid the fire hazard caused by power utilization overload to a great extent.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
FIG. 1 is a schematic product diagram of an exemplary embodiment of the application of the thermochromic composition of the present application in the preparation of wire and cable materials, warning wires and cables;
FIG. 2 is a schematic product diagram of another exemplary embodiment of the application of the thermochromic composition of the present application in the preparation of wire and cable materials, warning wires and cables;
FIG. 3 is a schematic product diagram of another exemplary embodiment of the application of the thermochromic composition of the present application in the preparation of wire and cable materials, warning wires and cables;
FIG. 4 is a schematic product diagram of another exemplary embodiment of the application of the thermochromic composition of the present application in the preparation of wire and cable materials, warning wires and cables;
FIG. 5 is a schematic product diagram of one exemplary embodiment of the application of the thermochromic compositions of the present application in the preparation of thermochromic compositions, pre-warning receptacles, pre-warning jacks, and the like;
FIG. 6 is a schematic product diagram of another exemplary embodiment of the application of the thermochromic compositions of the present application to the preparation of thermochromic compositions, pre-warning receptacles, pre-warning jacks, and the like;
FIG. 7 is a schematic product diagram of an exemplary embodiment of an application of the thermochromic composition of the present application in preparing a thermochromic adhesive and a warning switch.
Detailed Description
The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application. In addition, if a detailed description of the known art is not necessary for illustrating the features of the present application, it is omitted.
The application provides a thermochromic composition, which comprises the following components in parts by weight:
the resin is selected from one or more of ethylene-vinyl acetate copolymer, linear low-density polyethylene, polyvinyl chloride, chlorinated polyethylene, ethylene propylene diene monomer rubber and silicon rubber.
The flame retardant is selected from one or more of chlorinated paraffin, liquid phosphate flame retardant, aluminum hydroxide and magnesium hydroxide.
The auxiliary agent is selected from one or more of polyolefin elastomer, metallocene low-density polyethylene, dioctyl phthalate (DOP) and dioctyl terephthalate (DOTP).
The filler is selected from one or more of calcium carbonate, kaolin and talcum powder.
The lubricant is selected from one or more of zinc stearate, calcium stearate, PE wax, EBS and PETS.
The cross-linking agent is selected from one or more of TAIC, DCP, BIBP, bis-di-penta and platinum vulcanizing agent. Preferably, the crosslinking agent is selected from one of TAIC, DCP, BIBP, bis-penta, platinum vulcanizing agent.
The antioxidant is selected from one or more of 1010, 168, 1076 and 246.
The thermochromic material comprises a capsule core and a modified coating layer coated on the outer layer of the capsule core, wherein the capsule core is prepared from a pigment mixture, ethylene, tetrafluoroethylene, an initiator and a chain transfer agent;
in the capsule core, the pigment mixture comprises a non-thermochromic pigment and a reversible thermochromic pigment, and the weight ratio of the non-thermochromic pigment to the reversible thermochromic pigment is 1 (1-3); the mass ratio of the ethylene to the tetrafluoroethylene is 1 (2-4); the quantity ratio of the initiator to the chain transfer agent is 1 (0.3-3); the quantity ratio of the tetrafluoroethylene to the ethylene substance in the modified coating layer is 1 (0.85-1.25).
In one embodiment of the present application, the modified coating layer is prepared from tetrafluoroethylene and ethylene, and the amount ratio of the tetrafluoroethylene to the ethylene species in the modified coating layer is 1: 1.
The application also provides a preparation method of the thermochromic composition, and the thermochromic composition is prepared by blending and extruding the components of the thermochromic composition.
Specifically, in an embodiment of the present application, a method for preparing the thermochromic composition includes the steps of:
taking the components of the thermochromic composition, banburying the components in an internal mixer for 30min, then extruding the mixture by a screw machine, and extruding and granulating the mixture to obtain the thermochromic composition.
In the thermochromic composition, the thermochromic material is adopted, the ethylene-tetrafluoroethylene with high temperature resistance is adopted as the capsule material, and the capsule core and the modified coating layer are both treated by ethylene and tetrafluoroethylene, so that the thermochromic material has good high temperature resistance, the temperature resistance can reach above 220 ℃, and the thermochromic material can adapt to the reaction environment of most of high polymer materials when being further processed.
The thermochromic composition adopts a thermochromic material, and the thermochromic function of the thermochromic material is completed by matching a uniform system consisting of a leuco dye, a temperature regulator and a color developing agent. The leuco dye provides electrons, the temperature regulator absorbs heat from the phase change material after the temperature rises, so that the phase state is changed from solid state to liquid state, the leuco dye and the color developing agent are uniformly mixed, and the color developing agent receives the electrons provided by the leuco dye to realize temperature sensing color change. The modified coating layer of the thermochromic material, namely the microcapsule, takes ethylene-tetrafluoroethylene as a capsule material, and is similar to a superfine container, so that the leuco dye, the temperature regulator and the color developing agent can be uniformly dispersed together, and thermochromic is realized. The capsule material of the temperature-sensitive color-changing powder in the market is melamine formaldehyde, and when the processing temperature is higher than 150 ℃, the conventional microcapsule loses the effect, so that the leuco dye, the temperature regulator and the color developing agent cannot be matched with each other in a unified system to realize temperature-sensitive color change. The temperature-sensitive allochroic material adopts ethylene-tetrafluoroethylene as a capsule material, and the temperature resistance of the material can reach more than 220 ℃, so that the processing requirements of most materials can be met.
And the capsule core is wrapped by the ethylene-tetrafluoroethylene to prepare the modified coating layer, so that the organic treatment of the capsule core is realized, the thermochromic material can be better compatible with base materials such as PVC, PE and the like, and the influence of the thermochromic material on the mechanical property of the cable material is avoided. In addition, the thermochromic material simultaneously adopts the non-thermochromic pigment and the reversible thermochromic pigment, so that the toner in the material is dispersed more uniformly, the property stability of the material is ensured, and the function is more stable when the thermochromic material is used for realizing thermochromic. The reversible temperature-sensitive color-changing pigment and the non-temperature-sensitive color-changing pigment are matched with each other, and multi-section color mixing can be carried out according to different emergency situations, so that the forecast of different scenes, such as early warning, warning and scrapping, can be realized, and yellow, orange and red can be adopted for warning in sequence.
In the thermochromic composition, the thermochromic material is adopted, so that the performance of the product is not adversely affected, the cost is very low, the thermochromic material is added when the wire and the cable are prepared, the convenience of visually judging the working condition of the wire and the cable can be realized, and the low-cost and high-benefit are really realized.
Because the ethylene-tetrafluoroethylene has a crosslinkable mechanism, is particularly suitable for the cable industry, and can be subjected to irradiation crosslinking, the thermochromic material can maintain good mechanical properties when being further processed into materials such as cable materials and the like, and the elongation at break can reach 180% after irradiation.
In the thermochromic composition of the present application, the modified coating layer of the thermochromic material preferably has a ratio of the amount of the tetrafluoroethylene to the amount of the ethylene of 1: 1. The capsule core can be uniformly wrapped by adopting the ethylene-tetrafluoroethylene substance with the mass ratio of 1:1 to obtain the modified coating layer with stable property, and the thermochromic material has good high-temperature resistance.
In one embodiment of the present application, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, and dimethyl azobisisobutyrate, and the chain transfer agent is selected from one or more of aliphatic mercaptans, dodecyl mercaptan, sodium bisulfite, mercaptoethanol, and mercaptoacetic acid.
In one embodiment of the present application, the thermochromic material is thermochromic microparticles.
In one embodiment of the present application, the particle size D50 of the thermochromic material is 10 μm or less. Preferably, the particle size D50 of the thermochromic material is 2 micrometers.
The non-thermochromic pigment refers to a pigment which contains a certain color and does not have a thermochromic function, the reversible thermochromic pigment refers to a toner which is conventional in the market and has the thermochromic function, and the reversible thermochromic pigment is also called thermochromic powder and is also called thermochromic pigment, thermochromic powder or thermochromic powder. In one embodiment of the present application, the non-thermochromic pigment is selected from one or more commercially available conventional inorganic toners, may also be selected from one or more commercially available conventional organic toners, and may also be selected from a mixture of one or more of any of the inorganic toners and the organic toners;
in one embodiment of the present application, the color of the reversible thermochromic pigment is selected from one or more of colorless to colored, i.e., the reversible thermochromic pigment is darker as the temperature increases; it is also possible to select one or more colors of color to colorlessness, i.e., the temperature-sensitive toner is gradually lighter in color as the temperature increases.
The particle size D50 of the non-temperature-sensitive color-changing pigment and the reversible temperature-sensitive color-changing pigment is 1-10 microns, and preferably, the particle size D50 of the non-temperature-sensitive color-changing pigment and the reversible temperature-sensitive color-changing pigment is 2 microns.
The application also provides a preparation method of the thermochromic material, which comprises the following steps:
adding a reaction medium, heating to 50-70 ℃, and stirring at the speed of 200-;
adding the pigment mixture, introducing the ethylene and the tetrafluoroethylene, and filling the initiator and the chain transfer agent to prepare the capsule core;
continuously introducing the tetrafluoroethylene and ethylene, maintaining the reaction pressure at 2-4.5MPa and the reaction time at 1-2h, and preparing a modified coating layer coated on the outer layer of the capsule core;
filtering and drying to obtain the ETFE-coated thermochromic material.
Wherein, ETFE is an abbreviation of ethylene-tetrafluoroethylene copolymer (ethylene-tetra-fluoro-ethylene).
In a specific embodiment of the present application, the preparation method of the thermochromic material includes the following steps:
adding 100-200 g of reaction medium, heating to 50-70 ℃, and stirring at the speed of 200-500 r/min;
adding 200-300g of the pigment mixture, introducing 20-50mol of the ethylene and the tetrafluoroethylene, introducing 0.5-1mol of the initiator and 0.3-1.5mol of the chain transfer agent to prepare a capsule core;
continuously introducing the tetrafluoroethylene and ethylene, maintaining the reaction pressure at 2-4.5MPa and the reaction time at 1-2h, and preparing a modified coating layer coated on the outer layer of the capsule core;
filtering and drying to obtain the ETFE-coated thermochromic material.
In one embodiment of the present application, the preparation is carried out in a polymerization vessel, into which nitrogen is introduced to remove oxygen before the reaction is carried out.
In one embodiment of the present application, in the preparation of the thermochromic material, the reaction medium is perfluoroalkane or water.
The application also provides application of the thermochromic composition in preparation of electric wire and cable materials.
Referring to fig. 1, the application also provides an application of the thermochromic composition in preparing an early warning wire and cable insulation layer. In the cable, the outer layer of a conductor 1 is a thermochromic insulating layer 2, and the thermochromic insulating layer 2 is prepared by heating, melting and plasticizing a thermochromic composition containing the thermochromic material by a single-screw extruder and then uniformly extruding the thermochromic composition.
Further, referring to fig. 2, fig. 3 and fig. 4, the application also provides an application of the thermochromic material in preparing a sheath of an early warning electric wire.
In one embodiment of the present application, referring to fig. 2, the outer layer of the cable core 11 in the cable is a thermochromic sheath 22, and the thermochromic sheath 22 is prepared by heating, melting and plasticizing a thermochromic composition containing the thermochromic material by using a single screw extruder, and then uniformly extruding the thermochromic composition.
In another embodiment of the present application, referring to fig. 3, the thermochromic composition containing the thermochromic material and the conventional commercially available cable material are heated, melted and plasticized by a single screw extruder, and then uniformly extruded on the cabled wire core 11 to form the conventional sheath 31 and the thermochromic sheath 32 which are arranged at intervals.
In another embodiment of the present application, referring to fig. 4, when the sheath 41 of the extruded cable is heated, melted and plasticized by an extruder, the thermochromic composition containing the thermochromic material is extruded as the identification ribbon injection strip 42 on the surface of the sheath 41 of the cable, and is shaped after being cooled by water. Similarly, when an extruder is used for heating, melting, plasticizing and extruding other cable materials such as an insulating layer of a cable, the thermochromic composition containing the thermochromic material can also be used as an identification ribbon injection strip to be extruded on the surface of other cable materials such as an insulating layer of a cable, and details are not repeated here.
In the above embodiments, the linear low density polyethylene and polyvinyl chloride are finished products of cable insulation layers or sheaths after being extruded and cooled. The ethylene-vinyl acetate copolymer is extruded and then irradiated and crosslinked to form a finished product of the cable insulating layer or the sheath. The rubber is a cable insulation layer or sheath finished product after vulcanization and crosslinking.
The application also provides application of the thermochromic composition in preparation of early warning wires and cables.
Referring to fig. 1, in an embodiment of the present application, a thermochromic composition prepared from the thermochromic material is heated, melted, plasticized and then uniformly extruded outside a conductor 1 to form a thermochromic insulating layer 2, so as to prepare an early warning cable.
Referring to fig. 2, in another embodiment of the present application, a thermochromic composition prepared from the thermochromic material is heated, melted and plasticized by a single screw extruder, and then uniformly extruded on a cable core 11 to form a thermochromic sheath 22, so as to obtain an early warning cable.
Referring to fig. 3, in another embodiment of the present application, a thermochromic composition prepared from the thermochromic material and a conventional commercially available cable material are heated, melted and plasticized by a single screw extruder, and then uniformly extruded on a cabling core 11 to form a conventional sheath 31 and a thermochromic sheath 32 which are arranged at an interval, so as to prepare the warning cable.
Referring to fig. 4, in another embodiment of the present application, when an extruder is used to heat, melt and plasticize a sheath 41 of an extruded cable, a thermochromic composition prepared from the thermochromic material is extruded on the surface of the sheath 41 of the cable as an identification ribbon injection strip 42, and is shaped after water cooling to prepare the warning cable. Similarly, when an extruder is used for heating, melting and plasticizing other cable materials such as an insulating layer of an extruded cable, the thermochromic composition can also be used as an identification ribbon injection strip to be extruded on the surface of other cable materials such as an insulating layer of a cable, and details are not repeated here.
In the above embodiments, the linear low density polyethylene and the polyvinyl chloride are cable finished products after being extruded and cooled. The ethylene-vinyl acetate copolymer is extruded and then irradiated and crosslinked to form a finished product of the early warning cable. And the rubber is a finished product of the early warning cable after vulcanization and crosslinking.
Further, the application also provides the application of the thermochromic composition in preparation of thermochromic sizing materials, preparation of early warning sockets, power strips and switches.
The application also provides a preparation method of the thermochromic sizing material, which is prepared by blending and injection molding the components of the thermochromic composition.
Specifically, in an embodiment of the present application, the preparation method of the thermochromic sizing material includes the following steps:
and (3) taking the components of the thermochromic composition, banburying the components in a banbury mixer for 30min, and extruding the mixture by using an injection molding machine to obtain the thermochromic rubber material.
In one embodiment of the application, a thermochromic rubber material prepared from the thermochromic composition is heated, melted and plasticized by a single-screw injection molding machine, then low-density polyethylene and polyvinyl chloride are subjected to injection molding and cooling, ethylene-vinyl acetate copolymer is subjected to injection molding and irradiation crosslinking, and rubber is subjected to vulcanization crosslinking, so that various electric materials such as shell materials of sockets, power strips and the like and keys of switches and the like can be prepared.
Specifically, referring to fig. 5 and 6, the socket includes a socket housing 6, one surface of the socket housing 6 is a panel 61 provided with a plurality of insertion holes 62, and one side of the insertion holes 62 facing away from the panel 61 is connected with a socket terminal 63. The socket shell 6 is prepared from thermochromic sizing materials, and thermochromic early warning of the socket can be achieved. Preferably, the socket terminal 63 and the socket housing 6 can be connected by a heat conducting material to improve the sensitivity of the thermochromic early warning function. The thermochromic sizing material is used for preparing the power strip shell material in a similar manner, and is not described in detail herein.
Specifically, referring to fig. 7, the switch includes a switch button 7, one side of the switch, which faces away from the switch button 7, is connected with a plurality of wiring holes 71, the wiring holes 71 are connected with switch wiring terminals 72, and the switch button 7 is prepared from a thermochromic adhesive material, so that thermochromic warning of the switch can be realized. Preferably, the switch wiring terminal 72 and the switch button 7 can be connected by a heat conducting material to improve the sensitivity of the temperature sensing color-changing early warning function.
The reagents used in the following examples of the present application are conventionally available from the market unless otherwise specified.
Example 1
The thermochromic composition comprises the following components in parts by weight:
and (3) banburying the materials in a banbury mixer for 30min, then extruding by a screw machine, and carrying out extrusion and granulation to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 100g of perfluoroalkane medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 70 ℃, stirring at the speed of 250r/min, adding 100g of non-thermochromic pigment and 100g of reversible thermochromic pigment, then introducing 6.67mol of ethylene and 13.33mol of tetrafluoroethylene, filling 0.5mol of azobisisobutyronitrile into the polymerization kettle for reaction, introducing 0.3mol of aliphatic mercaptan, continuously adding tetrafluoroethylene and ethylene into the polymerization kettle according to the regulated molecular weight ratio of 1:1 to maintain the reaction pressure at 4.5MPa for reaction time of 1h, filtering and drying to obtain the ETFE-coated thermochromic material.
Example 2
The thermochromic composition comprises the following components in parts by weight:
and (3) banburying the formula materials in a banbury mixer for 10min, then extruding by a screw machine, and carrying out extrusion and granulation to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 200g of water medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 50 ℃, stirring at the speed of 500r/min, adding 75g of non-thermochromic pigment and 225g of reversible thermochromic pigment, then introducing 10mol of ethylene and 30mol of tetrafluoroethylene, filling 1mol of azodiisobutyl amidine hydrochloride into the polymerization kettle for reaction, simultaneously introducing 0.75mol of sodium bisulfite and 0.75mol of mercaptoethanol, continuously adding tetrafluoroethylene and ethylene with the mass ratio of 1:1 into the polymerization kettle according to the adjusted molecular weight so as to maintain the reaction pressure at 2MPa, reacting for 2h, filtering and drying to obtain the ETFE coated thermochromic material.
Example 3
The thermochromic composition comprises the following components in parts by weight:
taking the materials of the formula, except the vulcanizing agent, placing the materials in an internal mixer, banburying for 10min, then continuously mixing the materials by using an open mill, rolling down, placing the materials for cooling, adding the film and the vulcanizing agent cooled to be below 80 ℃ into the internal mixer, banburying for 1min, then drawing through the materials by using the open mill to press the materials into sheets of about 1.0mm, and isolating the two sides by using talcum powder to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 150g of perfluoroalkane medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 60 ℃, stirring at the speed of 200r/min, adding 83.3g of non-thermochromic pigment and 166.7g of reversible thermochromic pigment, then introducing 10mol of ethylene and 30mol of tetrafluoroethylene, filling 0.6mol of azobisisoheptonitrile into the polymerization kettle for reaction, introducing 1mol of dodecyl mercaptan, continuously adding tetrafluoroethylene and ethylene into the polymerization kettle according to the regulated molecular weight ratio of 1:1 so as to maintain the reaction pressure at 2.5MPa, reacting for 1.5h, filtering and drying to obtain the ETFE coated thermochromic material.
Example 4
A thermochromic composition comprises the following components in parts by weight:
and (3) banburying the materials in a banbury mixer for 30min, then extruding by a screw machine, and carrying out extrusion and granulation to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 200g of perfluoroalkane medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 60 ℃, stirring at the speed of 400r/min, adding 66.7g of non-thermochromic pigment and 133.3g of reversible thermochromic pigment, then filling 7.5mol of ethylene and 22.5mol of tetrafluoroethylene, filling 0.4mol of azobisisobutyronitrile and 0.4mol of dimethyl azobisisobutyrate into the polymerization kettle for reaction, simultaneously introducing 1.2mol of dodecyl mercaptan, continuously adding tetrafluoroethylene and ethylene with the mass ratio of 1:1 into the polymerization kettle by adjusting the molecular weight so as to maintain the reaction pressure at 2.5MPa, reacting for 1.5h, filtering and drying to obtain the ETFE-coated thermochromic material.
Example 5-1
The thermochromic composition comprises the following components in parts by weight:
and (3) banburying the materials in a banbury mixer for 30min, then extruding by a screw machine, and carrying out extrusion and granulation to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 200g of perfluoroalkane medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 60 ℃, stirring at the speed of 400r/min, adding 66.7g of non-thermochromic pigment and 133.3g of reversible thermochromic pigment, then filling 7.5mol of ethylene and 22.5mol of tetrafluoroethylene, filling 0.4mol of azobisisobutyronitrile and 0.4mol of dimethyl azobisisobutyrate into the polymerization kettle for reaction, simultaneously introducing 1.2mol of dodecyl mercaptan, continuously adding tetrafluoroethylene and ethylene with the mass ratio of 1: 0.85 into the polymerization kettle by adjusting the molecular weight so as to maintain the reaction pressure at 2.5MPa, reacting for 1.5h, filtering and drying to obtain the ETFE-coated thermochromic material.
Examples 5 and 2
The thermochromic composition comprises the following components in parts by weight:
and (3) banburying the formula materials in a banbury mixer for 30min, then extruding by a screw machine, and carrying out extrusion and granulation to obtain the thermochromic composition.
The thermochromic material is prepared by the following steps:
adding 200g of perfluoroalkane medium into a polymerization kettle which is filled with nitrogen and exhausted of oxygen, heating to 60 ℃, stirring at the speed of 400r/min, adding 66.7g of non-thermochromic pigment and 133.3g of reversible thermochromic pigment, then filling 7.5mol of ethylene and 22.5mol of tetrafluoroethylene, filling 0.4mol of azobisisobutyronitrile and 0.4mol of dimethyl azobisisobutyrate into the polymerization kettle for reaction, simultaneously introducing 1.2mol of dodecyl mercaptan, continuously adding tetrafluoroethylene and ethylene with the mass ratio of 1: 1.25 into the polymerization kettle by adjusting the molecular weight so as to maintain the reaction pressure at 2.5MPa, reacting for 1.5h, filtering and drying to obtain the ETFE-coated thermochromic material.
Example 6
The thermochromic composition prepared in example 1 is processed, melted and plasticized by a phi 70 single-screw extruder at the following temperature, and extruded to prepare a blue-surface halogen-free low-smoke flame-retardant cable WDZ-BYJ2.5mm 2 (ii) a After cooling, 8Mred irradiation dose is adopted for irradiation crosslinking.
| Position of | A segment of | Two segment | Three sections | Four sections | Flange | Machine head | Mould hole |
| Heating temperature (. degree.C.) | 120 | 140 | 150 | 155 | 155 | 160 | 150 |
Wherein the conductor is single bare copper with the outer diameter of 1.73 mm; the insulation is cross-linked polyolefin containing temperature-sensitive color-changing particles, the thickness is 0.8mm, and the outer diameter is 3.4 mm.
Example 7
The thermochromic composition prepared in example 2 was processed by a phi 70 single-screw extruder at the following temperature for melt plasticization, and extruded to prepare a general-purpose single-core hard conductor unsheathed cable 60227IEC 01(BV)2.5mm with a black surface 2 And after extrusion, rapidly cooling the extruded product by using circulating cooling water, and then detecting the product through spark safety to obtain a finished product.
| Position of | A segment of | Two segment | Three sections | Four sections | Flange | Machine head | Mould hole |
| Heating temperature (. degree.C.) | 120 | 145 | 160 | 165 | 165 | 170 | 165 |
Wherein the conductor is single bare copper with the outer diameter of 1.73 mm; the insulation is polyvinyl chloride containing temperature sensing color changing particles, the thickness is 0.8mm, and the outer diameter is 3.4 mm.
Example 8
The thermochromic composition prepared in example 3 was processed, melted and plasticized at a temperature controlled by a thermostat by a phi 90 single-screw extruder and extruded to prepare a black-surfaced heavy-duty cabtyre flexible cable insulated wire core 120mm in thickness 2 (ii) a Extruding at a speed of 50 m/min, passing through a 120m vulcanization pipeline, introducing saturated high-temperature water vapor at a pressure of 1.6Mpa and a temperature of 180 ℃ into the pipeline, rapidly cooling with circulating cooling water, and performing spark safety detection to obtain the final product.
| Position of | A segment of | Two segment | Three stages | Four sections | Flange | Machine head |
| Heating temperature (. degree.C.) | 40 | 65 | 70 | 80 | 80 | 80 |
Wherein the conductor is stranded bare soft copper, and the outer diameter is 15.4 mm; the insulation is ethylene-propylene mixed rubber containing temperature-sensing color-changing particles, the thickness is 1.8mm, and the outer diameter is 19.0 mm.
Example 9
120mm of heavy rubber jacketed flexible cable with green surface prepared by extrusion and plasticization of the thermochromic composition prepared in example 4 by a phi 90 single-screw extruder at the temperature controlled by a thermostat at the following temperature 2 (ii) a Extruding at 30 m/min, passing through a 120m vulcanization pipeline, introducing saturated high-temperature water vapor at a pressure of 1.8Mpa and a temperature of 210 ℃ into the pipeline, and rapidly cooling with circulating cooling water to obtain the final product.
| Position of | A section of | Two segment | Three sections | Four sections | Flange | Machine head |
| Heating temperature (. degree. C.) | 45 | 65 | 70 | 75 | 75 | 75 |
The outer diameter of the insulated wire core is 19.0 mm; the sheath is chlorinated polyethylene mixed glue containing temperature-sensitive color-changing particles, the thickness is 3.0mm, and the outer diameter is 25.0 mm.
Example 10
Taking the components of the thermochromic composition in example 1, banburying the components in a banbury mixer for 30min, and extruding the mixture by an injection molding machine to obtain the thermochromic rubber material.
Example 11
The components of the thermochromic composition of example 2 are taken and put into an internal mixer to be internally mixed for 30min, and then extruded by an injection molding machine to obtain the thermochromic rubber material.
Example 12
The components of the thermochromic composition of example 3 are mixed in an internal mixer for 30min, and extruded by an injection molding machine to obtain the thermochromic sizing material.
Example 13
Taking the components of the thermochromic composition of example 4, banburying the components in a banbury mixer for 30min, and extruding the mixture by an injection molding machine to obtain the thermochromic rubber material.
Example 14
Taking the thermochromic rubber material prepared in the embodiment 10, processing, melting and plasticizing the thermochromic rubber material by using a phi 90 single-screw extruder at the following temperature, and manufacturing the socket panel with a blue surface by injection molding; after cooling, 8Mred irradiation dose is adopted for irradiation crosslinking.
| Position of | A segment of | Two segment | Three sections | Four sections | Flange | Machine head | Mould hole |
| Heating temperature (. degree.C.) | 120 | 140 | 150 | 155 | 155 | 160 | 150 |
Example 15
The thermochromic rubber compound prepared in example 11 was processed, melted and plasticized by a single screw extruder of phi 90 at the following temperature and injection molded into a socket panel having a black surface, and the socket panel was cooled to obtain a finished product.
| Position of | A segment of | Two segment | Three sections | Four sections | Flange | Machine head | Die hole |
| Heating temperature (. degree.C.) | 120 | 145 | 160 | 165 | 165 | 170 | 165 |
Example 16
The thermochromic rubber compound prepared in example 12 was processed, melted and plasticized by a single screw extruder of phi 90 at the following temperature and injection molded into a socket with a black surface, and the socket was cooled to obtain a finished product.
| Position of | A section of | Two segment | Three sections | Four sections | Flange | Machine head |
| Heating temperature (. degree.C.) | 40 | 65 | 70 | 80 | 80 | 80 |
Example 17
The thermochromic rubber material prepared in example 13 was processed, melted and plasticized by a single screw extruder of phi 90 at the following temperature and injection molded into a socket having a green surface, and the socket was cooled to obtain a finished product.
| Position of | A section of | Two segment | Three sections | Four sections | Flange | Machine head |
| Heating temperature (. degree.C.) | 45 | 65 | 70 | 75 | 75 | 75 |
Comparative example 1
A common thermochromic composition comprises the following components in parts by weight:
and (3) banburying the above formula materials in a banbury mixer for 30min, then extruding by a screw machine, extruding and granulating to obtain the common thermochromic composition.
Comparative example 2
A common cable material comprises the following components in parts by weight:
and (3) banburying the above formula materials in a banbury mixer for 30min, then extruding by a screw machine, extruding and granulating to obtain the common thermochromic composition.
The thermochromic materials in the thermochromic compositions of examples 1 to 4 herein were subjected to performance tests, and the results are shown in table 1 below:
TABLE 1
As can be seen from table 1, it is found that the failure temperature of the thermochromic material in the thermochromic composition of the embodiments of the present application is generally higher than 220 ℃, that is, the long-term working temperature of the thermochromic material in the thermochromic composition of the embodiments of the present application can reach 220 ℃ or even above. Compared with the reversible thermochromic pigment, the thermochromic pigment has better temperature resistance and more various discoloration conditions, and is more favorable for realizing discoloration warning under various conditions such as early warning, scrapping and the like.
The thermochromic compositions of examples 1 to 4 of the present application, and the ordinary thermochromic compositions and ordinary cable materials prepared in comparative examples 1 and 2 were tested, and the results are shown in the following table 2:
TABLE 2
As can be seen from Table 2, the thermochromic compositions of examples of the present application have better mechanical properties by comparison with the conventional thermochromic compositions of comparative examples. Comparative example 1 and example 1 are all at the same resin content, but the thermochromic composition of example 1 contains ethylene-tetrafluoroethylene and can participate in crosslinking, so that the mechanical properties after irradiation are better maintained, and the cooling shrinkage rate also shows that the thermochromic composition of example 1 has a better degree of irradiation crosslinking. This conclusion is also reached by comparing the data of comparative example 2 and example 2.
The test was carried out on the conventional allochromatic and general rubber compounds prepared in the present application (examples 10 to 13) and comparative examples 3 and 4, and the results are shown in the following table 3:
TABLE 3
As can be seen from table 3, the thermochromic rubber compound of the examples of the present application has better mechanical properties by comparing with the ordinary thermochromic rubber compound and the ordinary rubber compound of the comparative examples. The comparative example 3 and the example 10 are both under the same resin content, but the temperature-sensitive color-changing rubber material of the example 10 can participate in crosslinking because of containing ethylene-tetrafluoroethylene, so that the mechanical property is better maintained after irradiation, and the cooling shrinkage rate also shows that the temperature-sensitive color-changing rubber material of the example 10 is better in irradiation crosslinking degree. This conclusion is also reached by comparing the data of comparative example 4 and example 11.
In conclusion, the thermochromic composition has good high temperature resistance, compatibility and mechanical properties, so that the thermochromic composition can be widely applied to preparation of wire and cable materials and thermochromic sizing materials, can be applied to preparation of electric materials such as early warning wires and cables, early warning sockets, power strips, switches and the like, and can play excellent high temperature resistance, compatibility and mechanical properties in the products.
The foregoing is only a partial embodiment of the present application, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the principle of the present application, and these modifications and decorations should also be regarded as the protection scope of the present application.
Claims (10)
1. The thermochromic composition is characterized by comprising the following components in parts by weight:
the thermochromic material comprises a capsule core and a modified coating layer coated on the outer layer of the capsule core, wherein the capsule core is prepared from a pigment mixture, ethylene, tetrafluoroethylene, an initiator and a chain transfer agent;
in the capsule core, the pigment mixture comprises a non-thermochromic pigment and a reversible thermochromic pigment, and the weight ratio of the non-thermochromic pigment to the reversible thermochromic pigment is 1 (1-3); the mass ratio of the ethylene to the tetrafluoroethylene is 1 (2-4); the quantity ratio of the initiator to the chain transfer agent is 1 (0.3-3); the modified coating layer is prepared from tetrafluoroethylene and ethylene, and the mass ratio of the tetrafluoroethylene to the ethylene in the modified coating layer is 1 (0.85-1.25).
2. The thermochromic composition according to claim 1, wherein the amount ratio of the tetrafluoroethylene and the ethylene substance in the modified coating layer is 1: 1.
3. The thermochromic composition of claim 1, wherein the thermochromic material is thermochromic microparticles.
4. The thermochromic composition according to claim 1, wherein the thermochromic material is prepared by:
adding a reaction medium, heating to 50-70 ℃, and stirring at the speed of 200-;
adding the pigment mixture, introducing the ethylene and the tetrafluoroethylene, and filling the initiator and the chain transfer agent to prepare the capsule core;
continuously introducing the tetrafluoroethylene and ethylene, maintaining the reaction pressure at 2-4.5MPa and the reaction time at 1-2h, and preparing a modified coating layer coated on the outer layer of the capsule core;
filtering and drying to obtain the ETFE-coated thermochromic material.
5. The thermochromic composition of claim 4, wherein the thermochromic material is prepared in a polymerization kettle, and nitrogen is introduced to exhaust oxygen before the reaction.
6. The thermochromic composition according to claim 4, wherein in the preparation of the thermochromic material, the reaction medium is perfluoroalkane or water.
7. The method of preparing a thermochromic composition according to any of claims 1-6, wherein the thermochromic composition is prepared by blending and extruding the components of the thermochromic composition.
8. Use of a thermochromic composition according to any of claims 1-6 for the preparation of a wire and cable material, a thermochromic sizing.
9. Use of the thermochromic composition according to any one of claims 1 to 6 for preparing an early warning wire or cable.
10. Use of the thermochromic composition according to any one of claims 1 to 6 for preparing early warning sockets, power strips, switches.
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