CN102167909A - Far infrared and terahertz optical polymer material and preparation method as well as application thereof - Google Patents
Far infrared and terahertz optical polymer material and preparation method as well as application thereof Download PDFInfo
- Publication number
- CN102167909A CN102167909A CN2011100569697A CN201110056969A CN102167909A CN 102167909 A CN102167909 A CN 102167909A CN 2011100569697 A CN2011100569697 A CN 2011100569697A CN 201110056969 A CN201110056969 A CN 201110056969A CN 102167909 A CN102167909 A CN 102167909A
- Authority
- CN
- China
- Prior art keywords
- far infrared
- polymer materials
- terahertz
- density polyethylene
- optics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a far infrared and terahertz optical polymer material and a preparation method as well as application thereof. The far infrared and terahertz optical polymer material comprises high-density polyethylene organic silicone resin and micron-grade monocrystalline silicon grains in a free state, wherein the high-density polyethylene silicone resin has a molecular formula of [C8H12Si2O3]n and a functional group thereof comprises two closed four-membered ring type carbon-silicon-oxygen chains. The preparation method comprises the following steps of: mixing materials and grinding into powder; layering a catalyst; loading the powder; performing olefin polymerization reaction; and collecting polymerization reactants and drying. A light transmitting region of a prepared optical component is formed by curing the prepared polymer material; and the optical component is arranged in a prepared optical device. The preparation method is simple and is convenient to realize; and the prepared far infrared and terahertz optical polymer material has superior performance indexes; the prepared optical component and the corresponding optical device have good application effects and are extremely suitable for far infrared and terahertz waves.
Description
Technical field
The invention belongs to far infrared, terahertz optics element material and applied technical field, especially relate to a kind of far infrared, terahertz optics polymer materials and preparation method and application.
Background technology
Far infrared wave is that wavelength is 40 microns～1000 microns a hertzian wave.Terahertz (THz, 1THz=10
12Hz) ripple refers to the hertzian wave of radiation frequency at 0.1THz-10THz, and THz wave has following characteristics: the first, the wave band of THz wave belongs to far infrared rays and sub-millimeter wave category between microwave and infrared light; It can be deep into many organic materialss inside and not injure material, a lot of dielectric materials and non-polar liquid is had good penetrance, and can have an X-rayed detection to opaque article; Its photon energy is very low, and is very safe to organism, and this makes terahertz imaging be fit to very much be used for biology sample detection and safety detection; The second, the rotation or the vibrational level that have comprised most of molecules in the THz wave band, promptly the THz ripple has comprised the abundant spectral signature information of many organic molecules, has good spectrum and divides the pigtail characteristic, and it can discern organic molecule effectively by the THz spectral line characteristic.Thereby the THz technology all has special advantages in fields such as remote sensing, biomedicine, military affairs, national defence and safety monitorings.
At present, the material as optical elements such as far infrared, THz wave lens mainly uses thermoplastics, for example polyethylene.Polymer materials is cheap, lightweight material, and handling ease is applicable to optical material.But polyethylene is very sensitive for environmental stress, and heat-resistant aging is poor.Simultaneously, poly character is different because of kind, and its physicochemical property alter a great deal, and the polyethylene that is fit to do far infrared and THz wave lens is high density polyethylene(HDPE) (HDPE), but its shortcoming is also arranged.High density polyethylene(HDPE) is a white wax shape translucent material, gentle and tough, lighter than water, nontoxic, have superior dielectric properties, its transparency increases with degree of crystallinity and descends, under certain degree of crystallinity, transparency increases with molecular weight and improves, its easy firing and burning away behind fire, permeability rate is low, and is bigger to the organic steam transmitance.The melting range of high density polyethylene(HDPE) is 132 ℃～135 ℃, be not soluble in the usual vehicle under the normal temperature, but more than 70 ℃ minimal amounts of dissolved in toluene, pentyl acetate, trieline equal solvent.
In addition, high density polyethylene(HDPE) has excellent chemical stability, various chemical substances such as salt tolerant acid, hydrofluoric acid, phosphoric acid, formic acid, amine, sodium hydroxide, potassium hydroxide under the room temperature, but nitric acid and sulfuric acid have stronger destruction to polyethylene.The easy photoxidation of polyethylene, thermooxidizing, ozone are decomposed, and degrade easily under action of ultraviolet radiation, and carbon black has the light shield effect to polyethylene, and crosslinked, chain rupture, formation unsaturated group can take place after the raying.Usually the specific refractory power of high density polyethylene polyethylene polymers material is low, and Abbe number is big.If will carry out the achromatism of lens class, need the big material of difference of Abbe number to make up with it.In addition, make the thin optics of integral thickness if will reduce the quantity of lens, should preferably make compound lens.For convenience and accurately carry out the shaping of compound lens, need to use ultraviolet curing resin or radiation-curing type and low viscous resin usually.
Disclose in invention disclosed patent application on the 24th September in 2008 CN 101270175A that a kind of viscosity before solidifying is low, the specific refractory power height of cured article, the hot and humid down optical polymer material that variations in refractive index is little and resistance to sudden heating is excellent and use the optics of this material.Disclosed this optical polymer material contains Xun's compound with 4 (methyl) propylene phthalidyls and (methyl) acrylate with phenyl phenol in the foregoing invention patent application, can also contain to have-organometallic polymer of M-O-M-key (M is an atoms metal) and aryl and simple function (methyl) acrylate, multifunctional (methyl) acrylate.But, utilize this polymkeric substance to carry out far infrared, the test of Terahertz light wave permeability, poor effect, this optical resin are not suitable for making the special lenses that can see through far infrared, terahertz light, main because its have at far infrared band that susceptibility is poor, a little less than the perviousness, easy defective such as aging.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provides that viscosity before a kind of the curing is low, cured article specific refractory power height, hot and humid variations in refractive index down is few and have far infrared, the terahertz optics polymer materials of good resistance to sudden heating.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of far infrared, terahertz optics polymer materials is characterized in that: comprise the high density polyethylene(HDPE) silicone resin, the molecular formula of this high density polyethylene(HDPE) silicone resin is [C
8H
12Si
2O
3]
n, density is 1.67g/cm
3～1.95g/cm
3, structural formula is:
Above-mentioned a kind of far infrared, terahertz optics polymer materials, it is characterized in that: also comprise uniform mixing in the high density polyethylene(HDPE) silicone resin and be in the micron order silicon single crystal crystal grain of unbound state, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96 ± 2: 3 ± 0.1.
Above-mentioned a kind of far infrared, terahertz optics polymer materials is characterized in that: the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96: 3.
Simultaneously, the invention also discloses a kind of method steps simple, easy and simple to handle and prepare effective, realize the preparation method of far infrared, terahertz optics polymer materials easily, it is characterized in that this method may further comprise the steps:
Step 1, batch mixing and grinding: be behind 27～40: 10～15 the ratio uniform mixing, to adopt milling equipment that compound is carried out grinding, till median size is less than 0.01mm by weight with organosilicon and silicon single crystal;
Step 2, olefinic polyreaction, its reaction process is as follows:
201, catalyzer shop layer: olefin polymerization catalysis is tiled on the flat chassis of dress powder dish, and forms the olefin polymerization catalysis shop layer that a layer thickness is 4mm～7mm;
Described dress powder dish is for by flat chassis be laid in the glassiness disk body that the side shield on the outer edge is formed around the described flat chassis, have a plurality of through holes that are evenly distributed on the described flat chassis, the spacing between all identical and adjacent two through holes of the size of a plurality of described through holes is 4mm～7mm; Described through hole is manhole or square through hole, and the aperture of described manhole is 1mm～2mm, and the length of side of described square through hole is 1mm～2mm;
202, dress powder: the mixed powder through obtaining behind the grinding in the step 1 evenly is tiled on the olefin polymerization catalysis shop layer described in the step 201, and obtaining a layer thickness is the mixed powder shop layer of 1mm～3mm;
203, olefinic polyreaction: the dress powder dish that inside is covered with olefin polymerization catalysis shop layer and mixed powder shop layer is steadily put into Gas-phase reactor, and when feeding ethylene gas continuously, organosilicon and the silicon single crystal of being adorned in the dress powder dish is carried out olefinic polyreaction by described Gas-phase reactor; When carrying out olefinic polyreaction, the internal pressure of described Gas-phase reactor is 2.5MPa～3MPa, and Heating temperature is 100 ℃～145 ℃, and the flow of the ethylene gas that feeds is 800L/s～1300L/s, and the olefinic polyreaction time is 10 seconds～25 seconds;
204, polymerization reactant is collected: to collecting through the polymerization reactant that olefinic polyreaction generated in the step 203;
Step 3, drying treatment: adopt UV curing equipment that the polymerization reactant of collecting in the step 204 is carried out drying treatment, till the humidity of described polymerization reactant was less than 10%, the quality purity that then obtains the high density polyethylene(HDPE) silicone resin was greater than 94% far infrared, terahertz optics polymer materials.
Above-mentioned a kind of far infrared, the preparation method of terahertz optics polymer materials is characterized in that: the olefin polymerization catalysis described in the step 201 is a metallocene catalyst.
Above-mentioned a kind of far infrared, the preparation method of terahertz optics polymer materials, it is characterized in that: described metallocene catalyst is for to close zirconium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging, close zirconium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging, close chromium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging or close chromium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging.
Above-mentioned a kind of far infrared, the preparation method of terahertz optics polymer materials is characterized in that: Gas-phase reactor described in the step 203 is a fluidized-bed reactor.
Above-mentioned a kind of far infrared, the preparation method of terahertz optics polymer materials is characterized in that: after the dress powder finishes in the step 202, also need adopt atomizer evenly to spray ethanol on the layer of described mixed powder shop.
Simultaneously, the invention also discloses that a kind of processing and fabricating is simple, result of use good and far infrared and the strong optics of THz wave perviousness, it is characterized in that: the light transmissive region of this optics is solidified by described far infrared, terahertz optics polymer materials and is formed.
In addition, the invention also discloses a kind of being suitable for far infrared and THz wave are carried out photoprocess and the good Optical devices of treatment effect, it is characterized in that: have the described optics of claim 9.
The present invention compared with prior art has the following advantages:
1, prepared far infrared, the every performance index of terahertz optics polymer materials that go out are good, have high refractive index, hydrophobicity is strong, can suppress hot and humid variations in refractive index down, viscosity before it solidifies is low, the specific refractory power height of cured article, hot and humid variations in refractive index down is little and resistance to sudden heating is excellent, be adapted to far infrared or THz wave sees through, and can reach decades the work-ing life under physical environment.
2 far infrareds, terahertz optics polymeric material preparation method for material simple and realize convenient, workable.
3, the optics processing and fabricating method of made is simple, and result of use is good, and is very strong to the perviousness of far infrared and THz wave, and very low to the perviousness of visible light, thereby is applicable to far infrared and THz wave Optical devices.
4, widely applicable and popularizing application prospect is extensive, can processing and fabricating broad variety optics, and the corresponding Optical devices that are applicable to number of different types.
In sum, preparation method of the present invention far infrared, the every performance index of terahertz optics polymer materials simple, that realization is convenient and prepared are good, the optics of made and corresponding Optical devices result of use are good, and very suitable far infrared and THz wave are used.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is infrared for preparation the present invention, the method flow block diagram of terahertz optics polymer materials.
Embodiment
Embodiment 1
Far infrared described in the present embodiment, terahertz optics polymer materials comprise the high density polyethylene(HDPE) silicone resin, and the molecular formula of this high density polyethylene(HDPE) silicone resin is [C
8H
12Si
2O
3]
n, density is 1.67g/cm
3～1.95g/cm
3And its structural formula is:
This contained functional group of high density polyethylene(HDPE) silicone resin is:
Thereby, the functional group of described high density polyethylene(HDPE) silicone resin comprises 2 the ring-like carbon silica of sealing quaternary chains that structure is identical, and atom is distributed as in the chain link of the ring-like carbon silica of each quaternary chain: 4 carbon atoms, 2 Siliciumatoms, 1 Sauerstoffatom and 4 hydrogen atoms.
Simultaneously, described far infrared, terahertz optics polymer materials also comprise uniform mixing in the high density polyethylene(HDPE) silicone resin and be in the micron order silicon single crystal crystal grain of unbound state, and the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96: 3.
As shown in Figure 1, in the present embodiment, to described far infrared, when the terahertz optics polymer materials is prepared, the preparation method who is adopted may further comprise the steps:
Step 1, batch mixing and grinding: behind 27g organosilicon and 10g silicon single crystal uniform mixing, adopt milling equipment that compound is carried out grinding, till median size is less than 0.01mm.
In the present embodiment, earlier the compound of organosilicon and silicon single crystal being formed with pulverizer is milled into fine powder, adds after the collection again and carries out meticulous the milling second time in the meticulous pulverizer, stops during less than 0.01mm until the particle diameter of mixed powder.
Step 2, olefinic polyreaction, its reaction process is as follows:
201, catalyzer shop layer: olefin polymerization catalysis is tiled on the flat chassis of dress powder dish, and forms the olefin polymerization catalysis shop layer that a layer thickness is 5mm.
Described olefin polymerization catalysis is a metallocene catalyst.In the present embodiment, described metallocene catalyst is for to close zirconium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging, close zirconium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging, close chromium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging or close chromium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging.
Described dress powder dish is for by flat chassis be laid in the glassiness disk body that the side shield on the outer edge is formed around the described flat chassis, have a plurality of through holes that are evenly distributed on the described flat chassis, the spacing between all identical and adjacent two through holes of the size of a plurality of described through holes is 5mm.In the present embodiment, described dress powder dish is a circular discs, and promptly described flat chassis is a disk.Described through hole is that the aperture of manhole and described manhole is 2mm.In the actual use, also can adopt square through hole, and according to the concrete needs of reality, the length of side of institute's family square through hole is adjusted accordingly in 1mm～2mm scope.And the disk body that described glassiness disk body is made for the toughened glass material.
202, dress powder: the mixed powder through obtaining behind the grinding in the step 1 evenly is tiled on the olefin polymerization catalysis shop layer described in the step 201, and obtaining a layer thickness is the mixed powder shop layer of 2mm.
203, olefinic polyreaction: the dress powder dish that inside is covered with olefin polymerization catalysis shop layer and mixed powder shop layer is steadily put into Gas-phase reactor, and when feeding ethylene gas continuously, organosilicon and the silicon single crystal of being adorned in the dress powder dish is carried out olefinic polyreaction by described Gas-phase reactor; When carrying out olefinic polyreaction, the internal pressure of described Gas-phase reactor is 2.8MPa, and Heating temperature is 120 ℃, and the flow of the ethylene gas that feeds is 1000L/s, and the olefinic polyreaction time is 15 seconds.
204, polymerization reactant is collected: to collecting through the polymerization reactant that olefinic polyreaction generated in the step 203.
In the present embodiment, described Gas-phase reactor is a fluidized-bed reactor.Correspondingly, to when the polymerization reactant that olefinic polyreaction generated is collected, collect polymerization reactant in the step 204 at the low pressure hopper place of fluidized-bed reactor.During actual fabrication, also can adopt the Gas-phase reactor of other type to carry out olefinic polyreaction.
In the present embodiment, after the dress powder finishes in the step 202, also need adopt atomizer on the layer of described mixed powder shop, evenly to spray ethanol, lubricant and reaction bridge when carrying out olefinic polyreaction in the step 203.When reality is sprayed ethanol, even sprinkling 10mL～30mL ethanol on every square decimeter of described mixed powder shop layer.Specifically, when carrying out olefinic polyreaction in step 203, the ethanol of sprinkling can carry out effectively lubricating to organosilicon in the mixed powder layer and silicon single crystal, thus make in the mixed powder layer organosilicon and silicon single crystal organically combines and in conjunction with closely.And when organosilicon and silicon single crystal carried out olefinic polyreaction, ethanol was further strengthened the speed and the level of response of olefinic polyreaction as the bridge that carries out olefinic polyreaction between organosilicon and the silicon single crystal, improved the quality of polymerization reactant.
Step 3, drying treatment: adopt UV curing equipment that the polymerization reactant of collecting in the step 204 is carried out drying treatment, till the humidity of described polymerization reactant was less than 10%, the quality purity that then obtains the high density polyethylene(HDPE) silicone resin was greater than 96% far infrared, terahertz optics polymer materials.
High density polyethylene(HDPE) silicone resin appearance in prepared far infrared, the terahertz optics polymer materials is white in color, cylindric or oblate shape particle, and particle is bright and clean, and the size of particle is 2mm～5mm in any direction, does not have mechanical impurity, has thermoplasticity.Described high density polyethylene(HDPE) silicone resin has good resistance to chemical attack characteristic, for example erosion resistance oxygenant (concentrated nitric acid), aromatic hydrocarbon (dimethylbenzene) and halon, tetracol phenixin etc.Simultaneously, this polymkeric substance is non-hygroscopic and have excellent waterproof steam, can be used for making the special optical instrument.Insulative dielectric intensity height makes it be applicable to very much electric wire.The high molecular grade has strong shock resistance, at normal temperature even all like this under-90 ℃ of low temperatures.
The arbitrary unit structure functional group of described high density polyethylene(HDPE) silicone resin, include 2 the ring-like carbon silica of sealing quaternary chains that structure is identical, and atom is distributed as in the chain link of the ring-like carbon silica of each sealing quaternary chain: 4 carbon atoms, 2 Siliciumatoms, 1 Sauerstoffatom and 4 hydrogen atoms, low, the cured article specific refractory power height of viscosity before making the high density polyethylene(HDPE) silicone resin solidify, hot and humid variations in refractive index is few down, and has good resistance to sudden heating.High density polyethylene(HDPE) silicone resin with 2 the ring-like carbon silica of sealing quaternary chains is compared with the polyvinyl compound that only has the carbon carbochain, it can increase cross-linking density, make the strength of materials uprise, therefore can improve resistance to sudden heating, major cause is: the high density polyethylene(HDPE) silicone resin is with silicon-oxygen (Si-O-Si) key, C-C key and Si-C key are the netted non-linear skeleton of backbone structure, the bond energy of C-C key is 82.6 a kilocalories/mol, the bond energy of Si-O key is 121 a kilocalories/mol, its thermostability height, the chemical bond of high temperature molecule down or under the radiation irradiation is easy fracture not, be difficult for decomposing, thereby not only can be high temperature resistant, and low temperature resistant, can in a very wide temperature range, use.The chemical property and the physical and mechanical properties of high density polyethylene(HDPE) silicone resin are all very little with variation of temperature, and unparalleled key exists in the main chain, are difficult for being decomposed by UV-light and ozone.To sum up, the high density polyethylene(HDPE) silicone resin has than the better thermostability of other vinyl polymer materials and anti-irradiation and corrosion resistance; While is because it has the ring-like carbon silica of sealing quaternary chain, thereby its polymer crystals has high refractive index, hydrophobicity is strong, can suppress hot and humid variations in refractive index down, and can reach decades its work-ing life under physical environment.
Simultaneously, in prepared far infrared, the terahertz optics polymer materials except that the high density polyethylene(HDPE) silicone resin, also comprise micron order silicon single crystal crystal grain, owing in the ring-like carbon silica of sealing quaternary chain backbone, contain the silicon single crystal particulate of free state, can make the high density polyethylene(HDPE) silicone resin littler, make cure shrinkage diminish, make the precision of shaping to improve simultaneously in the variations in refractive index under hot and humid.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymer materials (comprising that specifically mass percent is that 96% high density polyethylene(HDPE) silicone resin and mass percent are 3% micron order silicon single crystal crystal grain) to make the optics of suitable far infrared and THz wave, the light transmissive region of this optics (can see through the photic zone of light) is solidified by described far infrared, terahertz optics polymer materials and is formed.During this optical element of actual fabrication, the conventional curing that adopts when the curing of described far infrared, terahertz optics polymer materials is made light transmissive region with the employing thermoplastics is identical, thereby manufacture craft is very simple.The optics of made comprises the multiple optical element that suitable far infrared and THz wave are used, and mainly comprises spectroscope, set of lenses, integration lens, microlens array, light guiding plate etc.
Simultaneously, have the above-mentioned optics that is made and make Optical devices, that is to say above-mentioned optics is applied in the Optical devices to have above-mentioned optics in the Optical devices that adopted.During actual the use, the Optical devices of made mainly comprise digital product, optical filter, diffraction grid, interferometer, optical branching filter, optical sensor, holographic optical elements (HOE), photosensors etc. such as the optics system that is used for glasses, Terahertz digital camera.
Below the performance of prepared far infrared, terahertz optics polymer materials in the present embodiment is carried out test experiments, its experimental result is as follows:
[density of material reckoning]
The density of prepared far infrared, terahertz optics polymer materials calculates by the chemical structure and the shared separately composition of high density polyethylene(HDPE) silicone resin and silicon single crystal.In the present embodiment, the density of prepared far infrared, terahertz optics polymer materials is 1.67g/cm
3～1.95g/cm
3, calculate that the result sees table 1 for details.
[test of viscosity before solidifying]
Adopt the viscosity test method of conventional resin combination, and under 25 ℃ of temperature condition, far infrared, terahertz optics polymer materials are solidified preceding viscosity test.In the present embodiment, the viscosity before prepared far infrared, terahertz optics polymer materials solidify is 8Pas, and test result sees table 1 for details.
[mensuration of cured article specific refractory power]
After between above-mentioned prepared far infrared, the terahertz optics polymer materials quartz glass plate that to be clipped in two thickness be 1mm, the UV-lamp that with centre wavelength is 365nm is with about 45mW/cm
2Intensity irradiation it is solidified, and adopt the refraction index test method of conventional resin combination cured article, the specific refractory power of solidifying the back cured article that obtains this moment is measured.In the present embodiment, the specific refractory power of the cured article (being the refraction index test sample) after prepared far infrared, terahertz optics polymer materials solidify is 2.28, and its test result sees table 1 for details.
[mensuration of cured article variations in refractive index under the hot and humid condition]
With above-mentioned refraction index test sample is under the hot and humid condition of 90 ℃ and humidity 90% in temperature, place after 1000 hours, described refraction index test sample has been carried out high temperature and humidity test, and the variations in refractive index situation of described refraction index test sample under hot and humid condition tested.In the present embodiment, the specific refractory power of refraction index test sample under hot and humid condition that test draws becomes 0.0011, and its test result sees table 1 for details.
[measuring substance ingredient]
With above-mentioned under hot and humid condition the refraction index test sample of cured article variations in refractive index test usefulness, use mass spectrometer at normal temperatures and carry out measuring substance ingredient.In the present embodiment, the content of the refraction index test sample middle-high density polyethylene silicone resin that test draws is 96wt%, and the content of silicon single crystal is 3wt%, and the content of other material is 1wt%, and its test result sees table 1 for details.
[light transmission mensuration]
The refraction index test sample that the above-mentioned substance composition measurement is used, under same temperature and same pressure (specifically being normal temperature and pressure), carry out THz wave irradiation, far-infrared radiation and radiation of visible light respectively, correspondingly then measure with Terahertz power measurement instrument, far infrared resistance dynamometer and visible light illumination photometry instrument respectively.In the present embodiment, the refraction index test sample that test draws is respectively 95.5%, 95% and 0.06% to the transmitance of THz wave, the transmitance of far red light and the transmitance of visible light.
[fusing point test]
With the refraction index test sample of above-mentioned light transmission mensuration usefulness, under the same light intensity and under the same pressure, use electronic crucible heating, and measure the fusing point of polymer materials with the automatic temperature measurement instrument.In the present embodiment, the fusing point of the refraction index test sample that test draws is 510 ℃～610 ℃, and its test result sees table 1 for details.Said herein fusing point is meant the origin temp that polymer materials begins to melt.
[thermal shock test mensuration]
The refraction index test sample that above-mentioned fusing point test is used carries out the thermal shock test thermal shock resistance properties of the optical element that formed by the refraction index test sample making (promptly to), in the present embodiment, concrete thermal shock test process is: adopt thermal shock rig and so that the refraction index test sample is being placed 30min and is being under the round-robin situation placing 30min under 85 ℃ of temperature condition under-40 ℃ of temperature condition, after through 328 circulations, the surface of refraction index test sample just begins to occur fracture phenomena, and its test result sees table 1 for details.
[surface hardness test]
Adopt conventional surface hardness test set, the surface hardness of above-mentioned refraction index test sample is tested, in the present embodiment, the surface hardness (being mohs hardness) of the refraction index test sample that test draws is 2.4, and its test result sees table 1 for details.
To sum up, prepared far infrared, the density of terahertz optics polymer materials are 1.67g/cm in the present embodiment
3～1.95g/cm
3Mole hardness is 2.4, fusing point is 510 ℃～610 ℃, specific refractory power is 2.28, thereby its specific refractory power is higher than the specific refractory power of high density polyethylene(HDPE), but its Abbe number is less than high density polyethylene(HDPE), the erosion of far infrared, terahertz optics polymer materials energy acid and alkali-resistance simultaneously, be insoluble to common solvent, also be insoluble to organic solvent, water-absorbent is very little, electrical insulation capability is good, and it has functions such as anti-photooxidation, thermal oxidation resistance, anti-ozone decomposition, the difficult degraded under ultraviolet ray and far red light effect.In addition, far infrared, terahertz optics polymer materials cured article are all very strong to the transmitance of far infrared and THz wave, and its transmitance to far red light and THz wave is respectively 95% and 95.5%, and are 0.06% to the transmitance of visible light.
Table 1 far infrared, terahertz optics polymer materials The performance test results table
Embodiment 2
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: only comprise the high density polyethylene(HDPE) silicone resin in described far infrared, the terahertz optics polymer materials, do not comprise micron order silicon single crystal crystal grain, the molecular structure of described high density polyethylene(HDPE) silicone resin is all identical with embodiment 1 with performance etc.
In the present embodiment, the method for preparing far infrared, terahertz optics polymer materials is all identical with embodiment 1.
In the present embodiment, the optics that adopts described far infrared, terahertz optics polymeric material is as different from Example 1: need isolate the high density polyethylene(HDPE) silicone resin earlier in the far infrared of preparing, terahertz optics polymer materials, adopt the high density polyethylene(HDPE) silicone resin to make the optics of suitable far infrared and THz wave again, that is to say that the light transmissive region of this optics is formed by the curing of high density polyethylene(HDPE) silicone resin.
Correspondingly, in the present embodiment, the Optical devices of made as different from Example 1: the light transmissive region of the optics that is had in the Optical devices, solidify by the high density polyethylene(HDPE) silicone resin and to form.
Embodiment 3
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: in described far infrared, the terahertz optics polymer materials, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 98: 2.9, and the molecular structure of described far infrared, terahertz optics polymer materials middle-high density polyethylene silicone resin and micron order silicon single crystal crystal grain and performance etc. are all identical with embodiment 1.
In the present embodiment, prepare described far infrared, the method of terahertz optics polymer materials is as different from Example 1: will carry out grinding behind 40g organosilicon and the 10g silicon single crystal uniform mixing in the step 1, forming a layer thickness after being tiled in olefin polymerization catalysis on the flat chassis of adorning the powder dish in the step 201 is the olefin polymerization catalysis shop layer of 6mm, the aperture of institute's opened round through hole is that the spacing between 1.5mm and adjacent two manholes is 6mm on the flat chassis of the dress powder dish that adopts, the thickness of the shop of mixed powder described in the step 202 layer is 2.5mm, when carrying out olefinic polyreaction in the step 203, the internal pressure of described Gas-phase reactor is 3MPa, Heating temperature is 145 ℃, the flow of the ethylene gas that feeds is 1100L/s, and the olefinic polyreaction time is 14 seconds, and all the other preparation processes are all identical with embodiment 1 with processing parameter.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymeric material optics, and the light transmissive region of this optics is formed by far infrared, the curing of terahertz optics polymer materials.Correspondingly, correspondingly, the light transmissive region of the optics that has in the made Optical devices is formed by the above-mentioned far infrared of preparing, the curing of terahertz optics polymer materials.
Embodiment 4
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: in described far infrared, the terahertz optics polymer materials, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 94: 3.1, and the molecular structure of described far infrared, terahertz optics polymer materials middle-high density polyethylene silicone resin and micron order silicon single crystal crystal grain and performance etc. are all identical with embodiment 1.
In the present embodiment, prepare described far infrared, the method of terahertz optics polymer materials is as different from Example 1: will carry out grinding behind 40g organosilicon and the 15g silicon single crystal uniform mixing in the step 1, forming a layer thickness after being tiled in olefin polymerization catalysis on the flat chassis of adorning the powder dish in the step 201 is the olefin polymerization catalysis shop layer of 7mm, the aperture of institute's opened round through hole is that the spacing between 1mm and adjacent two manholes is 4mm on the flat chassis of the dress powder dish that adopts, the thickness of the shop of mixed powder described in the step 202 layer is 1mm, when carrying out olefinic polyreaction in the step 203, the internal pressure of described Gas-phase reactor is 2.5MPa, Heating temperature is 100 ℃, the flow of the ethylene gas that feeds is 800L/s, and the olefinic polyreaction time is 13 seconds, and all the other preparation processes are all identical with embodiment 1 with processing parameter.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymeric material optics, and the light transmissive region of this optics is formed by far infrared, the curing of terahertz optics polymer materials.Correspondingly, correspondingly, the light transmissive region of the optics that has in the made Optical devices is formed by the above-mentioned far infrared of preparing, the curing of terahertz optics polymer materials.
Embodiment 5
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: in described far infrared, the terahertz optics polymer materials, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 95: 3.05, and the molecular structure of described far infrared, terahertz optics polymer materials middle-high density polyethylene silicone resin and micron order silicon single crystal crystal grain and performance etc. are all identical with embodiment 1.
In the present embodiment, prepare described far infrared, the method of terahertz optics polymer materials is as different from Example 1: will carry out grinding behind 30g organosilicon and the 12g silicon single crystal uniform mixing in the step 1, forming a layer thickness after being tiled in olefin polymerization catalysis on the flat chassis of adorning the powder dish in the step 201 is the olefin polymerization catalysis shop layer of 4mm, the aperture of institute's opened round through hole is that the spacing between 1.25mm and adjacent two manholes is 5mm on the flat chassis of the dress powder dish that adopts, the thickness of the shop of mixed powder described in the step 202 layer is 2mm, when carrying out olefinic polyreaction in the step 203, the internal pressure of described Gas-phase reactor is 2.8MPa, Heating temperature is 130 ℃, the flow of the ethylene gas that feeds is 1200L/s, and the olefinic polyreaction time is 10 seconds, and all the other preparation processes are all identical with embodiment 1 with processing parameter.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymeric material optics, and the light transmissive region of this optics is formed by far infrared, the curing of terahertz optics polymer materials.Correspondingly, correspondingly, the light transmissive region of the optics that has in the made Optical devices is formed by the above-mentioned far infrared of preparing, the curing of terahertz optics polymer materials.
Embodiment 6
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: in described far infrared, the terahertz optics polymer materials, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 94: 2.95, and the molecular structure of described far infrared, terahertz optics polymer materials middle-high density polyethylene silicone resin and micron order silicon single crystal crystal grain and performance etc. are all identical with embodiment 1.
In the present embodiment, prepare described far infrared, the method of terahertz optics polymer materials is as different from Example 1: will carry out grinding behind 27g organosilicon and the 15g silicon single crystal uniform mixing in the step 1, forming a layer thickness after being tiled in olefin polymerization catalysis on the flat chassis of adorning the powder dish in the step 201 is the olefin polymerization catalysis shop layer of 7mm, the aperture of institute's opened round through hole is that the spacing between 2mm and adjacent two manholes is 7mm on the flat chassis of the dress powder dish that adopts, the thickness of the shop of mixed powder described in the step 202 layer is 3mm, when carrying out olefinic polyreaction in the step 203, the internal pressure of described Gas-phase reactor is 3MPa, Heating temperature is 110 ℃, the flow of the ethylene gas that feeds is 1300L/s, and the olefinic polyreaction time is 20 seconds, and all the other preparation processes are all identical with embodiment 1 with processing parameter.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymeric material optics, and the light transmissive region of this optics is formed by far infrared, the curing of terahertz optics polymer materials.Correspondingly, correspondingly, the light transmissive region of the optics that has in the made Optical devices is formed by the above-mentioned far infrared of preparing, the curing of terahertz optics polymer materials.
Embodiment 7
In the present embodiment, described far infrared, terahertz optics polymer materials be as different from Example 1: in described far infrared, the terahertz optics polymer materials, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96: 2.9, and the molecular structure of described far infrared, terahertz optics polymer materials middle-high density polyethylene silicone resin and micron order silicon single crystal crystal grain and performance etc. are all identical with embodiment 1.
In the present embodiment, prepare described far infrared, the method of terahertz optics polymer materials is as different from Example 1: will carry out grinding behind 35g organosilicon and the 13g silicon single crystal uniform mixing in the step 1, forming a layer thickness after being tiled in olefin polymerization catalysis on the flat chassis of adorning the powder dish in the step 201 is the olefin polymerization catalysis shop layer of 6mm, the aperture of institute's opened round through hole is that the spacing between 1.5mm and adjacent two manholes is 6mm on the flat chassis of the dress powder dish that adopts, the thickness of the shop of mixed powder described in the step 202 layer is 2.5mm, when carrying out olefinic polyreaction in the step 203, the internal pressure of described Gas-phase reactor is 3MPa, Heating temperature is 140 ℃, the flow of the ethylene gas that feeds is 1100L/s, and the olefinic polyreaction time is 25 seconds, and all the other preparation processes are all identical with embodiment 1 with processing parameter.
In the present embodiment, adopt the above-mentioned far infrared of preparing, terahertz optics polymeric material optics, and the light transmissive region of this optics is formed by far infrared, the curing of terahertz optics polymer materials.Correspondingly, correspondingly, the light transmissive region of the optics that has in the made Optical devices is formed by the above-mentioned far infrared of preparing, the curing of terahertz optics polymer materials.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, everyly any simple modification that above embodiment did, change and equivalent structure changed, all still belong in the protection domain of technical solution of the present invention according to the technology of the present invention essence.
Claims (10)
1. a far infrared, terahertz optics polymer materials, it is characterized in that: comprise the high density polyethylene(HDPE) silicone resin, the molecular formula of this high density polyethylene(HDPE) silicone resin is [C
8H
12Si
2O
3]
n, density is 1.67g/cm
3～1.95g/cm
3, structural formula is:
2. according to the described a kind of far infrared of claim 1, terahertz optics polymer materials, it is characterized in that: also comprise uniform mixing in the high density polyethylene(HDPE) silicone resin and be in the micron order silicon single crystal crystal grain of unbound state, the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96 ± 2: 3 ± 0.1.
3. according to the described a kind of far infrared of claim 2, terahertz optics polymer materials, it is characterized in that: the mass ratio of described high density polyethylene(HDPE) silicone resin and micron order silicon single crystal intergranule is 96: 3.
4. one kind prepares the method for far infrared, terahertz optics polymer materials as claimed in claim 1 or 2, it is characterized in that this method may further comprise the steps:
Step 1, batch mixing and grinding: be behind 27～40: 10～15 the ratio uniform mixing, to adopt milling equipment that compound is carried out grinding, till median size is less than 0.01mm by weight with organosilicon and silicon single crystal;
Step 2, olefinic polyreaction, its reaction process is as follows:
201, catalyzer shop layer: olefin polymerization catalysis is tiled on the flat chassis of dress powder dish, and forms the olefin polymerization catalysis shop layer that a layer thickness is 4mm～7mm;
Described dress powder dish is for by flat chassis be laid in the glassiness disk body that the side shield on the outer edge is formed around the described flat chassis, have a plurality of through holes that are evenly distributed on the described flat chassis, the spacing between all identical and adjacent two through holes of the size of a plurality of described through holes is 4mm～7mm; Described through hole is manhole or square through hole, and the aperture of described manhole is 1mm～2mm, and the length of side of described square through hole is 1mm～2mm;
202, dress powder: the mixed powder through obtaining behind the grinding in the step 1 evenly is tiled on the olefin polymerization catalysis shop layer described in the step 201, and obtaining a layer thickness is the mixed powder shop layer of 1mm～3mm;
203, olefinic polyreaction: the dress powder dish that inside is covered with olefin polymerization catalysis shop layer and mixed powder shop layer is steadily put into Gas-phase reactor, and when feeding ethylene gas continuously, organosilicon and the silicon single crystal of being adorned in the dress powder dish is carried out olefinic polyreaction by described Gas-phase reactor; When carrying out olefinic polyreaction, the internal pressure of described Gas-phase reactor is 2.5MPa～3MPa, and Heating temperature is 100 ℃～145 ℃, and the flow of the ethylene gas that feeds is 800L/s～1300L/s, and the olefinic polyreaction time is 10 seconds～25 seconds;
204, polymerization reactant is collected: to collecting through the polymerization reactant that olefinic polyreaction generated in the step 203;
Step 3, drying treatment: adopt UV curing equipment that the polymerization reactant of collecting in the step 204 is carried out drying treatment, till the humidity of described polymerization reactant was less than 10%, the quality purity that then obtains the high density polyethylene(HDPE) silicone resin was greater than 94% far infrared, terahertz optics polymer materials.
5. according to the preparation method of the described a kind of far infrared of claim 4, terahertz optics polymer materials, it is characterized in that: the olefin polymerization catalysis described in the step 201 is a metallocene catalyst.
6. according to the preparation method of the described a kind of far infrared of claim 5, terahertz optics polymer materials, it is characterized in that: described metallocene catalyst is for to close zirconium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging, close zirconium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging, close chromium and methyl alumina (CH by the dicyclopentadienyl dichloro
3OAl) catalyzer of Zu Chenging or close chromium and methyl iron oxygen (CH by the dicyclopentadienyl dichloro
3OFe) catalyzer of Zu Chenging.
7. according to the preparation method of the described a kind of far infrared of claim 4, terahertz optics polymer materials, it is characterized in that: Gas-phase reactor described in the step 203 is a fluidized-bed reactor.
8. according to the preparation method of the described a kind of far infrared of claim 4, terahertz optics polymer materials, it is characterized in that: after the dress powder finishes in the step 202, also need adopt atomizer on the layer of described mixed powder shop, evenly to spray ethanol.
9. one kind is utilized the optics of far infrared, terahertz optics polymeric material as claimed in claim 1 or 2, it is characterized in that: the light transmissive region of this optics is formed by described far infrared, the curing of terahertz optics polymer materials.
10. Optical devices is characterized in that: have the described optics of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100569697A CN102167909A (en) | 2011-03-10 | 2011-03-10 | Far infrared and terahertz optical polymer material and preparation method as well as application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100569697A CN102167909A (en) | 2011-03-10 | 2011-03-10 | Far infrared and terahertz optical polymer material and preparation method as well as application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102167909A true CN102167909A (en) | 2011-08-31 |
Family
ID=44489236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100569697A Pending CN102167909A (en) | 2011-03-10 | 2011-03-10 | Far infrared and terahertz optical polymer material and preparation method as well as application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167909A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111282158A (en) * | 2020-03-13 | 2020-06-16 | 福建省立东信科技发展有限公司 | Far infrared ray luminous device and method for processing product by using same |
| CN113185829A (en) * | 2021-06-03 | 2021-07-30 | 苏州星起源新材料科技有限公司 | Broadband terahertz wave-absorbing material and preparation method thereof |
-
2011
- 2011-03-10 CN CN2011100569697A patent/CN102167909A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111282158A (en) * | 2020-03-13 | 2020-06-16 | 福建省立东信科技发展有限公司 | Far infrared ray luminous device and method for processing product by using same |
| CN113185829A (en) * | 2021-06-03 | 2021-07-30 | 苏州星起源新材料科技有限公司 | Broadband terahertz wave-absorbing material and preparation method thereof |
| CN113185829B (en) * | 2021-06-03 | 2022-04-19 | 南京星起源新材料科技有限公司 | Broadband terahertz wave-absorbing material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102318433B1 (en) | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film | |
| CN108503740B (en) | Blue-light-proof resin monomer, resin material, lens and preparation method thereof | |
| Medda et al. | Inorganic–organic hybrid coatings on polycarbonate.: Spectroscopic studies on the simultaneous polymerizations of methacrylate and silica networks | |
| JP7055166B2 (en) | Resin film, laminate, optical member, display member and front plate | |
| KR20180056758A (en) | An infrared absorbing composition, an infrared cut filter, and an imaging optical system | |
| CN106565955B (en) | Polyimide polymer containing selenium and its preparation method and application | |
| CN1616523B (en) | Organometallic polymer material and process for preparing the same | |
| CN102643501A (en) | Transparent high-refractivity graphene quantum-dot/polymer nano composite film and preparation method thereof | |
| Wang et al. | A Polytriazole Synthesized by 1, 3‐Dipolar Polycycloaddition Showing Aggregation‐Enhanced Emission and Utility in Explosive Detection | |
| KR101876524B1 (en) | Polyimide film | |
| Kuo et al. | Silicone resin synthesized by tetraethoxysilane and chlorotrimethylsilane through hydrolysis–condensation reaction | |
| CN104730605B (en) | Light diffusion membrane for display and preparation method thereof | |
| CN102167909A (en) | Far infrared and terahertz optical polymer material and preparation method as well as application thereof | |
| El‐Gamal et al. | Electrical and optical properties of novel brilliant cresyl blue dye‐doped poly (methyl methacrylate) as selective cut‐off laser filters | |
| CN115322641A (en) | High-absorptivity stray light inhibition coating and preparation method and application thereof | |
| Li et al. | Facile Preparation of Light Refractive Poly (aroxycarbonyltriazole) s by Metal‐Free Click Polymerization | |
| KR101295653B1 (en) | Polyimide film and method for preparing same | |
| CN1328605C (en) | Optical waveguide, optical transmitter and receiver module, and laminated structure | |
| CN102174263A (en) | Far-infrared terahertz optical polymer material and preparation method and application thereof | |
| CN115304552A (en) | Reversible photochromic dihydroxy functional monomer and preparation method and application thereof | |
| CN108467361B (en) | Quinophthalone compound, preparation method thereof and application of quinophthalone compound as light absorption material | |
| Yi et al. | Facile fabrication of eugenol-containing polysiloxane films with good optical properties and excellent thermal stability via Si–H chemistry | |
| RU2503103C1 (en) | Method of making absorbent coating | |
| CN104829848A (en) | Dissoluble nitrogenous hyperbranched polymer and manufacturing method and application therefor | |
| KR20130078307A (en) | Polyimide film and method for preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110831 |