CN104419076A - Thermosensitive temperature-sensing composite high molecular material and preparation method thereof - Google Patents
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Abstract
A thermosensitive temperature-sensing composite high molecular material and a preparation method thereof. The thermosensitive temperature-sensing composite high molecular material comprises a thermosensitive temperature-sensing high molecular material, a composite antistatic agent and a solvent with a weight ratio of 100:0.1-30:2-80. According to the thermosensitive temperature-sensing composite high molecular material provided by the invention, the composite antistatic agent is added into the thermosensitive temperature-sensing high molecular material, and the composite antistatic agent provides effective channel for pyroelectric electrons to enable the property that the resistance value decreases as the temperature increases to be more obvious. In addition, the preparation method of the invention performs stirring firstly at a low speed of 300-1500 rpm at 100 DEG C-140 DEG C and then stirring at a high speed of 1500-3000 rpm, which enables raw materials forming the thermosensitive temperature-sensing composite high molecular material to be mixed better, and thus the formed thermosensitive temperature-sensing composite high molecular material has improved mechanical property, and more stable electrical performance indexes such as resistance value and pyroelectric coefficient.
Description
Technical field
The invention belongs to macromolecular material and preparing technical field thereof, particularly relate to a kind of thermosensitive temperature-sensing composite high-molecular material and preparation method thereof.
Background technology
Thermosensitive temperature-sensing macromolecular material is a class non-demolition warning temperature sensing material; have the advantages that the electricity function index such as resistance value, pyroelectric coefficient is controlled; the temperature-sensing element material of the devices such as heat detector, alarm cable, apparatus overheat protector, temperature regulator can be used as; use temperature scope is at-10 ~ 250 DEG C, and reusable.Pyroelectric effect is the one nature physical influence of some thermosensitive temperature-sensing macromolecular material.For the thermosensitive temperature-sensing macromolecular material with self start type polarization performance, after it is heated or cools, cause self start type polarizability to change due to the change of temperature, thus the phenomenon of Surface Polarized Charge is produced in certain direction of thermosensitive temperature-sensing macromolecular material, this phenomenon is called pyroelectric effect, can by following equation expression:
△Ps=P△T
In formula, △ Ps is self start type polarizability variable quantity; △ T is temperature variation; P is pyroelectric coefficient.The generation of Surface Polarized Charge will cause the change of thermosensitive temperature-sensing macromolecular material resistance value.
Specifically, when the temperature increases, the intrinsic polarization of thermosensitive temperature-sensing macromolecular material will change, thus make shielded packaged food overbalance, unnecessary shielded packaged food is released, and transmitted by pyroelectricity electron channel, now the resistance value of thermosensitive temperature-sensing macromolecular material also can change.But because thermosensitive temperature-sensing macromolecular material inside conventional does not at present have effective electron channel, therefore the change of decline is not obvious with temperature rising for resistance value.
In order to reduce the bulk resistivity of thermosensitive temperature-sensing macromolecular material, accelerate the transmission speed of pyroelectricity electronics, make resistance value increase with temperature and the performance that declines is more obvious, usually add when preparing thermosensitive temperature-sensing macromolecular material some can for it in pyroelectricity electronics the material of passage is provided.Pyroelectricity electron channel material conventional is at present by common metal powder, metal oxide powder, one or more in the materials such as conductive polymers powder are composite to be formed, but, because the particle of these materials is larger, dispersing property is poor, consumption is large, generally, in the thermosensitive temperature-sensing macromolecular material of 100 parts of weight, the number of required pyroelectricity electron channel material is more than or equal to 5 parts, under normal circumstances between 10 ~ 15 parts, therefore, the thermosensitive temperature-sensing composite high-molecular material structure made through extruding process thereof with the mixture that thermosensitive temperature-sensing macromolecular material and pyroelectricity electron channel material form as shown in Figure 1, number in the figure 1 is thermosensitive temperature-sensing macromolecular material, label 2 is pyroelectricity electron channel material, as can be seen from the figure, pyroelectricity electron channel material 2 is in bulk distribution, this distribution is unfavorable for the electron channel of the rear thermosensitive temperature-sensing macromolecular material pyroelectricity of formation temperature rising, and it is little to mechanical impact such as the tensile strength of thermosensitive temperature-sensing macromolecular material, and its resistance value, the electricity function indexs such as pyroelectric coefficient are unstable.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide a kind of thermosensitive temperature-sensing composite high-molecular material that can form good pyroelectricity electron channel.
Another object of the present invention is the preparation method providing a kind of above-mentioned thermosensitive temperature-sensing composite high-molecular material.
In order to achieve the above object, thermosensitive temperature-sensing composite high-molecular material provided by the invention by thermosensitive temperature-sensing macromolecular material, composite antistatic agent and solvent with 100: 0.1 ~ 30: 2 ~ 80 weight ratio form; Wherein thermosensitive temperature-sensing macromolecular material is selected from least one of polyethylene, polyethylene/vinyl-acetic ester EVA, ethylene-propylene terpolymer EPDM, chloroprene rubber, polypropylene, polyvinyl chloride, polyvinylidene chloride and tetrafluoroethylene; At least one that composite antistatic agent is selected from least one in nanosize metal oxide, nano semiconductor oxide compound, nanoscale antimony and stannic oxide mixture and ionic, non-ionic type, amphoteric, Polymer Antistatic Agent mixes; Wherein nanosize metal oxide is nano titanium oxide, nano aluminium oxide, nano-cerium oxide, nano zircite or nano oxidized terbium; Nano semiconductor oxide compound is nano silicon or nanometer titanium dioxide germanium; Ionic anti-static agent is halogen, nitric acid, carboxylic acid,-sulfinic acid, lipid acid or polyoxyethylene
;non-ionic antistatic agent is glycerol, Polyglycerine, sorb essence alcohol, ethylene glycol, glycerine, sorbyl alcohol, octadecylamine, hexadecyldimethyl benzyl ammonium tertiary amine, hexadecyl amide, hydroxyalkyl amide or polyoxyethylene; Amphoteric static inhibitor is amine, hexadecyl amide, hydroxyalkyl amide, carbonic acid or sulfonic acid; Polymer Antistatic Agent is polyoxyethylene, carbonic acid, sulfonic acid, octadecyldimethyl hydroxyethyl quaternary ammonium nitrate, alkylphosphonic, alkyl-sulphate or alkyl nitrate
;solvent is ethanol, ethylene glycol, propyl alcohol, butanols, acetone, butanone, methylethylketone, pimelinketone, positive propyl ether, b-butyl ether, n-butyl ether, vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate, dibutyl phthalate or dioctyl phthalate (DOP).
By above-mentioned weighing scale and the thermosensitive temperature-sensing macromolecular material of granulating and forming first joins in homogenizer by the preparation method of thermosensitive temperature-sensing composite high-molecular material provided by the invention, then composite antistatic agent is dissolved in a solvent, to join afterwards in homogenizer and to be heated to 100 DEG C ~ 140 DEG C, low speed mixing 3 ~ 5 minutes under the rotating speed of 300 ~ 1500 revs/min, then high-speed mixing 10 ~ 15 minutes under the rotating speed of 1500 ~ 3000 revs/min, namely makes described thermosensitive temperature-sensing composite high-molecular material.
Composite antistatic agent by above-mentioned weighing scale first dissolves in a solvent by the preparation method of another kind of thermosensitive temperature-sensing composite high-molecular material provided by the invention, then add Powdered thermosensitive temperature-sensing macromolecular material, finally make described thermosensitive temperature-sensing composite high-molecular material according to Polymer materialspreparation technique granulating and forming.
Thermosensitive temperature-sensing composite high-molecular material provided by the invention is insulation in normal temps situation, and when envrionment temperature reaches between 303K ~ 313K, its resistance value can obviously decline.Although some macromolecular material with pyroelectric effect of the performance that the resistivity of this thermosensitive temperature-sensing composite high-molecular material rises with temperature and declines itself also has, just these macromolecular material inside do not have effective electron channel, therefore the change that resistance value rises with temperature and declines is not obvious, after the present invention with the addition of composite antistatic agent in thermosensitive temperature-sensing macromolecular material, composite antistatic agent provides effective passage can to these pyroelectricity electronics, and the performance that its resistance value is declined with temperature rising can be more obvious.In addition, this preparation method to adopt 100 DEG C ~ 140 DEG C time the first low speed of 300 ~ 1500 revs/min then high-speed stirring of 1500 ~ 3000 revs/min, the each raw material forming thermosensitive temperature-sensing composite high-molecular material can be mixed better, the mechanical property of the thermosensitive temperature-sensing composite high-molecular material formed strengthens, and the electricity function index such as resistance value, pyroelectric coefficient is more stable.
Accompanying drawing explanation
Fig. 1 is common thermosensitive temperature-sensing composite high-molecular material internal structure schematic diagram;
Fig. 2 is thermosensitive temperature-sensing composite high-molecular material internal structure schematic diagram provided by the invention;
Fig. 3 is the temperature resistance curve comparison figure of the heat detector adopting common thermosensitive temperature-sensing composite high-molecular material to make and the heat detector adopting thermosensitive temperature-sensing composite high-molecular material provided by the invention to make.
Embodiment
Below in conjunction with the drawings and specific embodiments, thermosensitive temperature-sensing composite high-molecular material provided by the invention and preparation method thereof is described in detail.
Embodiment 1:
First 25000g ethylene-propylene terpolymer EPDM particle is joined in homogenizer; separately 20g nano titanium oxide and 5g hexadecyl amide are joined in 1L container; in 1L container, add 500g ethylene glycol again and stir 3 minutes; then the mixture in 1L container is poured in homogenizer and mix with 25000g ethylene-propylene terpolymer EPDM particle; and be heated to 100 DEG C; first low speed mixing 3 minutes under the rotating speed of 300 revs/min; then high-speed mixing 10 minutes under the rotating speed of 1500 revs/min, namely obtains thermosensitive temperature-sensing composite high-molecular material.
Embodiment 2:
First 25000g polyvinyl chloride particles is joined in homogenizer, another by 250g nano aluminium oxide, 250g nanoscale antimony and stannic oxide mixture (are called for short ATO, factory is Hangzhou Wanjing New Material Co., Ltd., model is VK-G06 nano ATO), 55g stearic acid joins in 1L container, in 1L container, add 2000g dibutyl phthalate again and stir 3 minutes, then the mixture in 1L container is poured in homogenizer and mix with 25000g polyvinyl chloride particles, and be heated to 120 DEG C, first low speed mixing 4 minutes under the rotating speed of 400 revs/min, then high-speed mixing 12 minutes under the rotating speed of 2000 revs/min, namely thermosensitive temperature-sensing composite high-molecular material is obtained.
Embodiment 3:
First 25000g polyethylene/vinyl-acetic ester (being called for short EVA) particle is joined in homogenizer, separately by 500g nanoscale antimony and stannic oxide mixture (being called for short ATO), 60g sorbyl alcohol joins in 1L container, in 1L container, add 3000g acetone again and stir 3 minutes, then the mixture in 1000mL container is poured in homogenizer and mix with 25000g polyethylene/vinyl-acetic ester (being called for short EVA) particle, and be heated to 120 DEG C, first low speed mixing 5 minutes under the rotating speed of 500 revs/min, then high-speed mixing 12 minutes under the rotating speed of 2500 revs/min, namely thermosensitive temperature-sensing composite high-molecular material is obtained.
Embodiment 4:
First 25000g polyvinylidene difluoride (PVDF) particle is joined in homogenizer, another by 500g nano silicon, 1000g nanoscale antimony and stannic oxide mixture (being called for short ATO), 2000g hexadecyldimethyl benzyl ammonium tertiary amine joins in 2L container, in 2L container, add 5000g dioctyl phthalate (DOP) again and stir 3 minutes, then the mixture in 2L container is poured in homogenizer and mix with 25000g polyvinylidene difluoride (PVDF) particle, and be heated to 140 DEG C, first low speed mixing 5 minutes under the rotating speed of 1500 revs/min, then high-speed mixing 15 minutes under the rotating speed of 3000 revs/min, namely thermosensitive temperature-sensing composite high-molecular material is obtained.
Embodiment 5:
First 25000g polypropylene GRANULES is joined in homogenizer; separately 5000g nano zircite, 2500g octadecyldimethyl hydroxyethyl quaternary ammonium nitrate are joined in 10L container; in 10L container, add 20000g positive propyl ether again and stir 5 minutes; then the mixture in 10L container is poured in homogenizer and mix with 25000g polypropylene GRANULES; and be heated to 140 DEG C; first low speed mixing 5 minutes under the rotating speed of 1500 revs/min; then high-speed mixing 15 minutes under the rotating speed of 3000 revs/min, namely obtains thermosensitive temperature-sensing composite high-molecular material.
Embodiment 6:
Nano oxidized for 500g terbium, 60g alkylphosphonic are joined in 1L container, in 1L container, add 3000g ethylene glycol again and stir 3 minutes, join in the raw material for the preparation of 25000g polyvinylidene chloride particle again, obtain thermosensitive temperature-sensing composite high-molecular material by polyvinylidene chloride granule preparing process granulating and forming.
The raw material that thermosensitive temperature-sensing composite high-molecular material embodiment 1-6 uses prepared by table one
Fig. 2 is thermosensitive temperature-sensing composite high-molecular material internal structure schematic diagram provided by the invention, as seen from the figure, nanoscale composition granule 3 as pyroelectricity electron channel material is spot distribution, obvious contrast is formed with the pyroelectricity electron channel material 2 becoming bulk to distribute in Fig. 1, the passage of such formation can make pyroelectricity electronics more easily pass through, the therefore corresponding raising of the sensitivity of material.
Fig. 3 is the temperature resistance curve comparison figure of the heat detector adopting common thermosensitive temperature-sensing composite high-molecular material to make and the heat detector adopting thermosensitive temperature-sensing composite high-molecular material provided by the invention to make.In figure, X-coordinate is absolute temperature T (K), ordinate zou is resistance value R(M Ω), curve A is the temperature resistance curve of the heat detector adopting common thermosensitive temperature-sensing composite high-molecular material to make, the temperature resistance curve of the heat detector that the thermosensitive temperature-sensing composite high-molecular material that curve B provides for the embodiment of the present invention 2 is made.Shown in figure two kind are positive usual amounts for the number of the pyroelectricity electron channel material in the thermosensitive temperature-sensing composite high-molecular material of heat detector.As seen from the figure, when absolute temperature T rises to 323K from 303K, the resistance change rate △ R/R=211.51/310.72=0.68 of common heat detector, the resistance change rate △ R/R=181.6/198.3=0.92 of this heat detector.In fact, prepare material difference due to what adopt, the resistivity of thermosensitive temperature-sensing composite high-molecular material of the present invention is 0.75 ~ 0.95, apparently higher than common thermosensitive temperature-sensing composite high-molecular material.Visible, when absolute temperature variable quantity is consistent, the resistance change rate of the heat detector adopting thermosensitive temperature-sensing composite high-molecular material provided by the invention to make is larger than the resistance change rate of common heat detector.
Claims (3)
1. a thermosensitive temperature-sensing composite high-molecular material, is characterized in that: its by thermosensitive temperature-sensing macromolecular material, composite antistatic agent and solvent with 100: 0.1 ~ 30: 2 ~ 80 weight ratio form; Wherein thermosensitive temperature-sensing macromolecular material is selected from least one of polyethylene, polyethylene/vinyl-acetic ester EVA, ethylene-propylene terpolymer EPDM, chloroprene rubber, polypropylene, polyvinyl chloride, polyvinylidene chloride and tetrafluoroethylene; At least one that composite antistatic agent is selected from least one in nanosize metal oxide, nano semiconductor oxide compound, nanoscale antimony and stannic oxide mixture and ionic, non-ionic type, amphoteric, Polymer Antistatic Agent mixes; Wherein nanosize metal oxide is nano titanium oxide, nano aluminium oxide, nano-cerium oxide, nano zircite or nano oxidized terbium; Nano semiconductor oxide compound is nano silicon or nanometer titanium dioxide germanium; Ionic anti-static agent is halogen, nitric acid, carboxylic acid,-sulfinic acid, lipid acid or polyoxyethylene
;non-ionic antistatic agent is glycerol, Polyglycerine, sorb essence alcohol, ethylene glycol, glycerine, sorbyl alcohol, octadecylamine, hexadecyldimethyl benzyl ammonium tertiary amine, hexadecyl amide, hydroxyalkyl amide or polyoxyethylene; Amphoteric static inhibitor is amine, hexadecyl amide, hydroxyalkyl amide, carbonic acid or sulfonic acid; Polymer Antistatic Agent is polyoxyethylene, carbonic acid, sulfonic acid, octadecyldimethyl hydroxyethyl quaternary ammonium nitrate, alkylphosphonic, alkyl-sulphate or alkyl nitrate
;solvent is ethanol, ethylene glycol, propyl alcohol, butanols, acetone, butanone, methylethylketone, pimelinketone, positive propyl ether, b-butyl ether, n-butyl ether, vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate, dibutyl phthalate or dioctyl phthalate (DOP).
2. the preparation method of a thermosensitive temperature-sensing composite high-molecular material as claimed in claim 1, it is characterized in that: by above-mentioned weighing scale and the thermosensitive temperature-sensing macromolecular material of granulating and forming first joins in homogenizer by described preparation method, then composite antistatic agent is dissolved in a solvent, to join afterwards in homogenizer and to be heated to 100 DEG C ~ 140 DEG C, low speed mixing 3 ~ 5 minutes under the rotating speed of 300 ~ 1500 revs/min, then high-speed mixing 10 ~ 15 minutes under the rotating speed of 1500 ~ 3000 revs/min, namely described thermosensitive temperature-sensing composite high-molecular material is made.
3. the preparation method of a thermosensitive temperature-sensing composite high-molecular material as claimed in claim 1, it is characterized in that: the composite antistatic agent by above-mentioned weighing scale first dissolves in a solvent by described preparation method, then add Powdered thermosensitive temperature-sensing macromolecular material, finally make described thermosensitive temperature-sensing composite high-molecular material according to Polymer materialspreparation technique granulating and forming.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104788805A (en) * | 2015-03-24 | 2015-07-22 | 昆山金华安电子科技有限公司 | Special PP protecting membrane formula for ITO |
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| CN104788805A (en) * | 2015-03-24 | 2015-07-22 | 昆山金华安电子科技有限公司 | Special PP protecting membrane formula for ITO |
| CN104788805B (en) * | 2015-03-24 | 2017-11-14 | 昆山金华安电子科技有限公司 | A kind of special PP protections film formulations of ITO |
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