CN101613504B - Temperature sensing cable material with CRT characteristics and preparation method thereof - Google Patents
Temperature sensing cable material with CRT characteristics and preparation method thereof Download PDFInfo
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Abstract
The invention relates to technical fields of materials, chemical engineering and electronics, in particular to a cable material with a polymer substrate and CTR effect and a preparation method thereof. The temperature sensing cable material with CRT characteristics consists of thermoplastic polymer, a filling agent, a plasticizer, functional additives, a stabilizing agent, a flame retardant, a lubricant, an antioxidant and a processing agent, has the use temperature range between -30 and 150 DEG C, and can be applied on occasions such as recoverable line-type temperature sensing cables, fire prewarning and alarm devices, temperature measurement, overheating alarm and protection and the like. The temperature sensing cable material with the CRT characteristics takes a polymer material as a substrate, and is added with multiple organic and inorganic compounds with special CTR characteristics taken as the functional additives, and has the characteristics of flexibility, and capacities of being continuously processed and being used like a common cable material.
Description
Technical field
The present invention relates to material, chemical industry, electronic technology field, be specifically related to a kind of have negative critical temperature-resistance (Critical Temperature Resistance, CTR) CABLE MATERIALS of the polymer matrix of effect and preparation method thereof.The use temperature scope of this CABLE MATERIALS is-30～150 ℃, can in can recovering molded lines shape temperature sensing cable, fire alarm and occasions such as warning device, temperature survey, temperature alarm and protection, use.
Background technology
At present; The semi-conductor fire disaster alarming device is spot distribution often; Can only realize the heat detection in the definite dotted region; For needing big area, the long distance occasion of monitoring in real time, be difficult to play a role like pipe laying, building cable well, large-size chemical storage tank, pipeline and chemical plant installations etc.The advanced more practice is to use linear temperature sensing cable to realize the monitoring in the two dimensional surface through specific arranging rule, and (Negative Temperature Coefficient NTC) is the groundwork principle of this type cable to negative temperature-specific resistance effect.Just disclose a kind of temperature sensing material and preparation method thereof like Chinese invention patent application (application number 200410067588.9), can be applied in occasions such as restorability alarm cable, heat detection, apparatus overheat protector and temperature regulator with negative temperature specific resistance effect.
But the resistivity of sensing device can't be implemented in the sudden change under the specified temp along with temperature raises and linear the reduction in the NTC characteristic, thereby the sensitivity of reporting to the police receives certain restriction.The CTR characteristic is the gordian technique that addresses this problem.The CTR characteristic is meant under a certain temperature; The resistivity of material reduces rapidly with the increase of temperature, has very big NTC, thereby makes interlock circuit change conducting state into from blocking state rapidly; Thereby realization realizes reporting to the police and warning function because of the signal output that temperature change causes.
The material of CTR characteristic commonly used mainly is MOX or semiconductor type material; A kind of linear critical NTC thermistor thermometric element and preparation method thereof is disclosed like Chinese invention patent application (application number 200710017713.9); The ceramics powder that has adopted MOXs such as containing Fe, Cr, In, Ni to process is because the rigidity characteristic of stupalith can't realize the manufacturing of flexible cable.Thereby also be difficult to utilize the said material preparation to reach the linear temperature sensing cable with common handling characteristics of hundreds of meters flexibility.
Summary of the invention
In view of this, the present invention provides a kind of temperature sensing cable material with negative critical temperature-resistance characteristic, can't realize the problem of the manufacturing of flexible cable with the rigidity characteristic that realize to solve stupalith, and resistivity is along with temperature raises and the linear problem that reduces.
For realizing above-mentioned purpose; The present invention provides a kind of temperature sensing cable material with negative critical temperature-resistance characteristic; This CABLE MATERIALS is made up of thermoplastic polymer, weighting agent, softening agent, functional additive, stablizer, fire retardant, lubricant, oxidation inhibitor and processing aid; Wherein, the weight proportion of each component is following:
Said functional additive comprises that inorganic, metal oxide is fired, pulverize the powder mass that obtains, and said powder mass is specially one or more in Natural manganese dioxide, chromic oxide, red stone, vanadium oxide, powder blue, nickel oxide, White tin oxide and the rare earth metal oxide compound
Preferably; In above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said thermoplastic polymer comprises one or more the mixture in Vilaterm, Vestolen PP 7052, chlorinatedpolyethylene, chlorinated rubber, X 050, Injecatable EVA Copolymer, ethylene-propylene rubber(EPR), pvdf, urethane and the chlorinated polyvinyl chloride polymkeric substance; Said stablizer comprises one or more in lead sulfate tribasic, dibasic lead stearate, dibasic lead phosphite, lead stearate, barium stearate, calcium stearate, dibutyl tin laurate, toxilic acid dibutyl tin, rare-earth stabilizer, liquid calcium zinc complex stabilizer and the powdery barium cadmium lead stabilizer.
Preferably, in above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said weighting agent comprises one or more in light calcium carbonate, gas-phase silica, carbon black, titanium oxide, talcum powder, wollastonite, polynite and the mica; Said softening agent comprises one or more in phthalic acid ester class, polyester, phosphoric acid ester and the epoxy soybean oils.
Preferably; In above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said fire retardant comprises one or more in white lake, Antimony Trioxide: 99.5Min, boride, Marinco H, volatile salt, ammonium chloride, trioctyl phosphate, trichloroethyl phosphate, clorafin, tetrabromo-bisphenol and the PBDE.
Preferably, in above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said lubricant comprises one or more in Zinic stearas, barium stearate, calcium stearate, Triple Pressed Stearic Acid, butyl stearate, paraffin, microcrystalline wax and the silicone oil.
Preferably, in above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said oxidation inhibitor comprises one or more in antioxidant 264, antioxidant 1010, oxidation inhibitor 1024 and the oxidation inhibitor 246.
Preferably, in above-mentioned temperature sensing cable material with negative critical temperature-resistance characteristic, said processing aid comprises one or more the mixture in releasing agent, tinting material, UV stabilizer, anti-aging agent, sterilant, static inhibitor, the coupling agent etc.
The present invention also provides a kind of preparation method with temperature sensing cable material of negative critical temperature-resistance characteristic; These method concrete steps are following: thermoplastic polymer, weighting agent, softening agent, functional additive, stablizer, fire retardant, lubricant, oxidation inhibitor and processing aid are added the high-speed mixer low speed mixing by following proportioning obtained mixed powder in mixed at high speed 5-10 minute after 3-10 minute, said mixed powder is obtained to have the temperature sensing cable material of negative critical temperature-resistance characteristic through forcing machine in 120-200 ℃ of extruding pelletization, moulding;
Said functional additive comprises that inorganic, metal oxide is fired, pulverize the powder mass that obtains, and said powder mass is specially one or more in Natural manganese dioxide, chromic oxide, red stone, vanadium oxide, powder blue, nickel oxide, White tin oxide and the rare earth metal oxide compound.
Can find out from above-mentioned technical scheme; This CABLE MATERIALS of temperature sensing cable material that the embodiment of the invention has the CTR characteristic is to be matrix with the macromolecular material; And add have special CTR characteristic polynary organic-inorganic composite body as functional additive, the characteristics that have flexibility, can process continuously, can use as the common cable material.Preparing method with temperature sensing cable material of CTR characteristic, the characteristic of this method be adopt high-speed mixer with each mixing of materials evenly after extrude, granulating and forming obtains temperature sensing cable material with CTR characteristic.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is that critical temperature is the resistivity-temperature curve of 50 ℃ CTR CABLE MATERIALS;
Fig. 2 is that critical temperature is the resistivity-temperature curve of 60 ℃ CTR CABLE MATERIALS;
Fig. 3 is that critical temperature is the resistivity-temperature curve of 70 ℃ CTR CABLE MATERIALS;
Fig. 4 is that critical temperature is the resistivity-temperature curve of 80 ℃ CTR CABLE MATERIALS;
Fig. 5 is that critical temperature is the resistivity-temperature curve of 90 ℃ CTR CABLE MATERIALS;
Fig. 6 is that critical temperature is the resistivity-temperature curve of 100 ℃ CTR CABLE MATERIALS.
Embodiment
To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The embodiment of the invention provides a kind of temperature sensing cable material with negative critical temperature-resistance characteristic to be made up of thermoplastic polymer, weighting agent, softening agent, functional additive, stablizer, fire retardant, lubricant, oxidation inhibitor and processing aid; Wherein, the weight proportion of each component is following:
The embodiment of the invention also provides a kind of preparation method with temperature sensing cable material of negative critical temperature-resistance characteristic, and its concrete steps are: utilize high-speed mixer that each material was added the back first low speed mixing 3-10 minute by proportioning;
Obtained mixed powder then in mixed at high speed 5-10 minute, with mixed powder through forcing machine at 120-200 ℃ of extruding pelletization, moulding obtains temperature sensing cable material with CTR characteristic.
Embodiment 1:
Get 100 parts of SE, 10 parts of gas-phase silicas, 20 parts of Witcizer 300s; With zinc oxide 10 parts of the main compound functional additives of organic-inorganic, 2 parts of dibutyl tin laurates, 1 part of Antimony Trioxide: 99.5Min; In 1 part of adding high-speed mixer of antioxidant 1010, under low speed 200rpm, mixed 3 minutes earlier, under high speed 1000rpm, mixed 5 minutes then; Obtain mixed powder, obtain cable granules at 160 ℃ of following extruding pelletizations through single screw extrusion machine.Get sample of pellets at 160 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 50 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 1.
Embodiment 2:
Get 50 parts of SE, 50 parts of chlorinatedpolyethylenees, 10 parts of gas-phase silicas; 10 parts of triphenyl phosphites, 10 parts of DOPs are master's 5 parts of compound functional additives of organic-inorganic with chromic oxide and vanadium oxide; 2 parts of toxilic acid dibutyl tins, 2 parts of microcrystalline waxes, 5 parts of Marinco Hs; In 1 part of adding high-speed mixer of antioxidant 264, under low speed 200rpm, mixed 3 minutes earlier, under high speed 1000rpm, mixed 5 minutes then; Obtain mixed powder, obtain cable granules at 160 ℃ of following extruding pelletizations through single screw extrusion machine.Get sample of pellets at 160 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 60 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 2.
Embodiment 3:
Get 70 parts of chlorinated polyvinyl chlorides, 30 parts of chlorinatedpolyethylenees, 10 parts of talcum powder; 10 parts of DOPs, 5 parts of octyl epoxy stearates are master's 10 parts of compound functional additives of organic-inorganic with vanadium oxide, lanthanum trioxide and Natural manganese dioxide; 5 parts of Zinic stearass, 5 parts of barium stearates, each 1 part in oxidation inhibitor 1024 and antioxidant 1010; With Pigment red 179 is that tinting material adds 0.1 part; In high-speed mixer, mixed 5 minutes with low speed 300rpm earlier, high speed 800rpm mixed 5 minutes then, obtained red CABLE MATERIALS pellet through single screw extrusion machine 150 ℃ of following extruding pelletization moulding.Get sample of pellets at 150 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 70 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 3.
Embodiment 4:
70 parts of line taking type new LDPE (film grade)s, 30 parts of highly-chlorinated polyethylenes, 10 parts of titanium oxide; With cupric oxide, red stone, powder blue is master's 15 parts of compound functional additives of organic-inorganic, 10 parts of epoxy soybean oils, 5 parts of clorafins; 5 parts of Triple Pressed Stearic Acid, 5 parts of barium stearates, each 1 part in oxidation inhibitor 246 and antioxidant 1010; With 1 part of cobalt blue dye is tinting material; In high-speed mixer, mixed 5 minutes with low speed 300rpm earlier, high speed 800rpm mixed 5 minutes then, obtained the CABLE MATERIALS pellet through single screw extrusion machine 150 ℃ of following extruding pelletization moulding.Get sample of pellets at 150 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 80 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 4.
Embodiment 5:
Get 60 parts in ethylene-propylene rubber(EPR), 20 parts of chlorinatedpolyethylenees, 20 parts of high chlorinated polyvinyl chlorides; 10 parts of polynites, 10 parts of DOPs are master's 15 parts of compound functional additives of organic-inorganic with White tin oxide, nickel oxide and gadolinium sesquioxide; 5 parts of Triple Pressed Stearic Acid, 5 parts of barium stearates, 2 parts of antioxidant 1010s; In high-speed mixer, mixed 5 minutes with low speed 300rpm earlier, high speed 800rpm mixed 5 minutes then, obtained red CABLE MATERIALS pellet through single screw extrusion machine 160 ℃ of following extruding pelletization moulding.Get sample of pellets at 160 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 90 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 5.
Embodiment 6:
Get 80 parts of Injecatable EVA Copolymers, 10 parts of chlorinated rubbers, 10 parts of SE; 10 parts of wollastonites, 20 parts of DOPs are master's 20 parts of compound functional additives of organic-inorganic with nickel oxide, cerium oxide and Neodymium trioxide; 2 parts of powdery barium cadmium lead stabilizers, 3 parts of Antimony Trioxide: 99.5Mins are in 1 part of adding high-speed mixer of antioxidant 1010; Under low speed 200rpm, mixed 3 minutes earlier; Under high speed 1000rpm, mixed 5 minutes then, obtain mixed powder, obtain cable granules at 160 ℃ of following extruding pelletizations through single screw extrusion machine.Get sample of pellets at 160 ℃ of prints that are hot pressed into thickness 1mm, measured resistivity-temperature variation on megger obtains the CABLE MATERIALS with CTR characteristic of 100 ℃ of critical temperatures.Resistivity-temperature variation curve such as Fig. 6.
Embodiment 7-30:
Below with the basic recipe of the more embodiment of tabulated form explanation.
The various materials of each prescription utilize high-speed mixer to add the back first low speed mixing 3-10 minute by proportioning in the form; Obtained mixed powder then in mixed at high speed 5-10 minute, mixed powder is obtained temperature sensing cable material through forcing machine in 120-200 ℃ of extruding pelletization, moulding with CTR characteristic.
There is the foregoing description can find out under different material proportions and measures material resistance with the variation of temperature value with megger; Be converted into variation relation between resistivity and the temperature; The resistivity of material begins to occur the characteristic of decline rapidly in the time of 50-110 ℃; And before these temperature, the change in resistance of material is very little.Before and after critical temperature, the rangeability of resistivity of material is the 2-5 one magnitude.
Can find out from above-mentioned technical scheme; This CABLE MATERIALS of temperature sensing cable material that the embodiment of the invention has the CTR characteristic is to be matrix with the macromolecular material; And add have special CTR characteristic polynary organic-inorganic composite body as functional additive, the characteristics that have flexibility, can process continuously, can use as the common cable material.Preparing method with temperature sensing cable material of CTR characteristic, the characteristic of this method be adopt high-speed mixer with each mixing of materials evenly after extrude, granulating and forming obtains temperature sensing cable material with CTR characteristic.
Each embodiment adopts the mode of going forward one by one to describe in this specification sheets, and what each embodiment stressed all is and the difference of other embodiment that identical similar part is mutually referring to getting final product between each embodiment.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (8)
1. temperature sensing cable material with negative critical temperature-resistance characteristic; It is characterized in that; Be made up of thermoplastic polymer, weighting agent, softening agent, functional additive, stablizer, fire retardant, lubricant, oxidation inhibitor and processing aid, wherein, the weight proportion of each component is following:
Said functional additive comprises that inorganic, metal oxide is fired, pulverize the powder mass that obtains, and said powder mass is specially one or more in Natural manganese dioxide, chromic oxide, red stone, vanadium oxide, powder blue, nickel oxide, White tin oxide and the rare earth metal oxide compound.
2. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1; It is characterized in that said thermoplastic polymer comprises one or more the mixture in Vilaterm, Vestolen PP 7052, chlorinatedpolyethylene, chlorinated rubber, X 050, Injecatable EVA Copolymer, ethylene-propylene rubber(EPR), pvdf, urethane and the chlorinated polyvinyl chloride polymkeric substance; Said stablizer comprises one or more in lead sulfate tribasic, dibasic lead stearate, dibasic lead phosphite, lead stearate, barium stearate, calcium stearate, dibutyl tin laurate, toxilic acid dibutyl tin, rare-earth stabilizer, liquid calcium zinc complex stabilizer and the powdery barium cadmium lead stabilizer.
3. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1; It is characterized in that said weighting agent comprises one or more in light calcium carbonate, gas-phase silica, carbon black, titanium oxide, talcum powder, wollastonite, polynite and the mica; Said softening agent comprises one or more in phthalic acid ester class, polyester, phosphoric acid ester and the epoxy soybean oils.
4. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1; It is characterized in that said fire retardant comprises one or more in white lake, Antimony Trioxide: 99.5Min, boride, Marinco H, volatile salt, ammonium chloride, trioctyl phosphate, trichloroethyl phosphate, clorafin, tetrabromo-bisphenol and the PBDE.
5. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1; It is characterized in that said lubricant comprises one or more in Zinic stearas, barium stearate, calcium stearate, Triple Pressed Stearic Acid, butyl stearate, paraffin, microcrystalline wax and the silicone oil.
6. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1 is characterized in that said oxidation inhibitor comprises one or more in antioxidant 264, antioxidant 1010, oxidation inhibitor 1024 and the oxidation inhibitor 246.
7. the temperature sensing cable material with negative critical temperature-resistance characteristic according to claim 1; It is characterized in that said processing aid comprises one or more the mixture in releasing agent, tinting material, UV stabilizer, anti-aging agent, sterilant, static inhibitor, the coupling agent etc.
8. preparation method with temperature sensing cable material of negative critical temperature-resistance characteristic; It is characterized in that; Concrete steps are following: thermoplastic polymer, weighting agent, softening agent, functional additive, stablizer, fire retardant, lubricant, oxidation inhibitor and processing aid are added behind the high-speed mixer after low speed mixing 3-10 minute by following proportioning obtained mixed powder in mixed at high speed 5-10 minute, said mixed powder is obtained to have the temperature sensing cable material of negative critical temperature-resistance characteristic through forcing machine in 120-200 ℃ of extruding pelletization, moulding;
Said functional additive comprises that inorganic, metal oxide is fired, pulverize the powder mass that obtains, and said powder mass is specially one or more in Natural manganese dioxide, chromic oxide, red stone, vanadium oxide, powder blue, nickel oxide, White tin oxide and the rare earth metal oxide compound.
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| CN105837960A (en) * | 2016-05-31 | 2016-08-10 | 李小涛 | Halogen-free flame-retardant ethylene propylene rubber cable material and preparation method thereof |
| CN105837915A (en) * | 2016-05-31 | 2016-08-10 | 李小涛 | Polyethylene insulated cable material and preparation method thereof |
| CN105885196A (en) * | 2016-05-31 | 2016-08-24 | 李小涛 | Halogen-free flame-retardant cable material and preparation method thereof |
| CN105924781A (en) * | 2016-05-31 | 2016-09-07 | 李小涛 | Halogen-free and flame-retardant polypropylene cable material and preparation method thereof |
| CN105924807A (en) * | 2016-05-31 | 2016-09-07 | 李小涛 | Environment-friendly ethylene propylene rubber cable material and preparation method thereof |
| CN105924757A (en) * | 2016-05-31 | 2016-09-07 | 李小涛 | Halogen-free and high-flame-retardancy cable material and preparation method thereof |
| CN105968565A (en) * | 2016-05-31 | 2016-09-28 | 李小涛 | High-fire-retardant polypropylene insulating cable material and preparation method thereof |
| CN106009151A (en) * | 2016-05-31 | 2016-10-12 | 李小涛 | High-flame retardation polyethylene cable material and preparation method thereof |
| CN106009261A (en) * | 2016-05-31 | 2016-10-12 | 李小涛 | Flame retardation polypropylene insulation cable material and preparation method thereof |
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| CN101613504A (en) | 2009-12-30 |
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