CN116084174A - Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof - Google Patents
Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN116084174A CN116084174A CN202310198470.2A CN202310198470A CN116084174A CN 116084174 A CN116084174 A CN 116084174A CN 202310198470 A CN202310198470 A CN 202310198470A CN 116084174 A CN116084174 A CN 116084174A
- Authority
- CN
- China
- Prior art keywords
- optical fiber
- light stabilizer
- fluorescent dye
- dye
- doped
- 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
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 73
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 64
- 239000013308 plastic optical fiber Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000013307 optical fiber Substances 0.000 claims abstract description 38
- 239000006184 cosolvent Substances 0.000 claims abstract description 37
- 239000012530 fluid Substances 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 21
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 17
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 75
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000012973 diazabicyclooctane Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously and a preparation method thereof, and belongs to the technical field of polymer optical fibers. The polymer optical fiber doped with the fluorescent dye and the light stabilizer is prepared according to the following steps: and (3) placing the polymethyl methacrylate (PMMA) optical fiber in a high-pressure fluid device, placing the fluorescent dye, the light stabilizer and the cosolvent, injecting high-pressure carbon dioxide fluid after the temperature reaches 18-20 ℃ until the pressure rises to 8-12MPa, and processing to obtain the polymer optical fiber doped with the fluorescent dye and the light stabilizer. The preparation method of the invention can improve the photostability of the dye-doped polymer optical fiber.
Description
Technical Field
The invention relates to the technical field of polymer optical fibers, in particular to a polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously and a preparation method thereof.
Background
The fluorescent dye doped polymer optical fiber (PMMA optical fiber at present) provides optical feedback through multiple scattering of radiation light in a medium, so that a larger gain is obtained, and the wavelength range of an emission spectrum is greatly expanded according to different doped dyes. Studies have shown that the incorporation of gain media (e.g. fluorescent dyes) in polymer optical fibers makes it possible to produce polymer optical fiber amplifiers with signal amplification.
Two advantages of the current dye doped optical fiber are focused, namely energy conversion efficiency, especially pyrrole methylene dye (Prromeheie family) has very high fluorescence quantum efficiency compared with other fluorescent dyes, and the dye can obtain very high fluorescence efficiency, so that the important point of research and focus is recently. A disadvantage of such dyes is the problem of photostability. The polymer dye can emit light waves with other wavelengths after absorbing the excitation light waves with one wavelength, and after being irradiated by the excitation light for a long time, the luminous intensity of the dye in the optical fiber can be reduced along with the increase of the irradiation time of the excitation light, which is called as poor light stability of the dye. The decrease in the photostability of the dye is caused by photochemical reactions, and is mainly caused by various reasons such as damage to the dye by high temperature, oxygen in the polymer, free radical, and the like.
The existing method for manufacturing fluorescent dye doped Polymer (PMMA) optical fiber is a doping method by utilizing free radical polymerization reaction. Firstly, dissolving fluorescent dye in Monomer Methacrylic Acid (MMA) monomer solution of a polymer, taking Azobisisobutyronitrile (AIBN) or Benzoyl Peroxide (BPO) as an initiator of free radical polymerization, carrying out polymerization at a high temperature of between 90 and 110 ℃ for 70 to 80 hours to prepare an optical fiber preform doped with the dye, and heating the preform to 200 ℃ to draw the polymer optical fiber. In the process, pyrrole methylene dye is subjected to double damage of free radical and high temperature environment to be attenuated, so that the light stability of solid fluorescent dye in the polymer optical fiber is poor, the practicability is directly influenced, and the problem to be solved is urgent.
In the earlier work, we injected fluorescent dye into polymer fiber with the help of mild condition high pressure carbon dioxide fluid, avoided the damage of high temperature and free radical to dye in dye doped fiber preparation.
In addition to high temperature and radical factors during fiber preparation, studies have shown that such dyes are susceptible to oxidative damage in the triplet state under operating conditions. The existence of oxygen in the preparation process of the dye-doped optical device can trigger the photooxidation reaction of the dye, and a certain amount of oxygen is reserved in the finished optical fiber, so that the decomposition of the dye in the working process can be accelerated, and the service life and the light stability of the dye are seriously affected. Aiming at the influence of oxygen, the current method for improving the light stability of the doped dye is to fill argon, nitrogen or vacuumize the environment in the preparation to improve the influence of oxygen on the dye stability, but the method has too high requirement on the preparation condition and limits the industrialized application.
Disclosure of Invention
Aiming at the problems, in order to improve the light stability of the doped dye in the polymer optical fiber, the invention provides a polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously and a preparation method thereof, and according to different dye types, different light stabilizers are doped simultaneously for improving the light stability of the polymer optical fiber doped with dye.
The first object of the invention is to provide a method for preparing a polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer, which comprises the following steps:
and (3) placing the PMMA optical fiber in a high-pressure fluid device, placing the fluorescent dye, the light stabilizer and the cosolvent, injecting high-pressure carbon dioxide fluid when the temperature reaches 18-20 ℃ until the pressure is increased to 8-12MPa, and processing to obtain the polymer optical fiber doped with the fluorescent dye and the light stabilizer.
Preferably, the light stabilizer is triethylenediamine or triphenylamine.
Preferably, the fluorescent dye is Pyrromethene580.
Preferably, the fluorescent dye and the light stabilizer are added into the cosolvent to obtain a mixed solution, and after the fluorescent dye and the light stabilizer are dissolved, the mixed solution is added into a high-pressure fluid device.
Preferably, the cosolvent is a mixture of methanol and ethanol, the volume ratio of the methanol to the ethanol is 1:1.9-2.1, and the dosage of the cosolvent is 2-3% of the volume of the high-pressure carbon dioxide fluid.
Preferably, the doping amount of the fluorescent dye is 1% -2% of the PMMA optical fiber; the molar ratio of the fluorescent dye to the light stabilizer is 1:10-15.
Preferably, the treatment time is 18-20 hours.
The second object of the present invention is to provide a polymer optical fiber prepared by the above preparation method and doped with fluorescent dye and light stabilizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) Carbon dioxide gas has excellent characteristics such as environmental friendliness, no toxicity, and easy transition from a gaseous state to a liquid-like state by controlling the pressure and temperature. According to different temperatures, the carbon dioxide gas enters a subcritical state or a supercritical state after being pressurized, and the high-pressure carbon dioxide fluid has the characteristics of low polarity, low viscosity, good diffusivity and the like, has a strong permeation effect on nonpolar or hydrophobic polymers, has good diffusivity in the polymers, and can enable functional single-molecule substances dissolved in the high-pressure carbon dioxide fluid to be injected or doped into the polymers. The invention utilizes the principle, is different from the prior preparation condition using free radical initiator and high temperature, realizes the non-damaging doping of fluorescent dye and light stabilizer into polymer optical fiber at room temperature, improves the working medium of dye innovatively, and greatly improves the light stability of pyrrole methylene fluorescent dye in solid medium.
(2) Light stabilizer doping is currently used for various dye-doped optical components, but polymer optical fibers for dye doping are not seen. When the dye-doped polymer optical fiber is prepared, the light stabilizer triethylenediamine (DABCO) or Triphenylamine (TPA) is doped into the optical fiber for the first time, so that the microenvironment of the dye is improved, the quenching effect of the light stabilizer on the triplet state of the pyrrole methylene dye is improved, and the light stability of the dye can be remarkably improved. The results show a longer service life relative to polymer fiber conditions of a single doped Pyrromethene580 (PM 580) dye, while a light stabilizer doped dye doped fiber.
(3) The high-pressure carbon dioxide is nonpolar fluid, has poor solubility to polar substances, and influences the doping effect of dyes and light stabilizers. According to the invention, ethanol and methanol are used as cosolvent, the cosolvent can improve the polarity of the carbon dioxide fluid, and increase the solubility of the high-pressure carbon dioxide fluid to the dye and the light stabilizer, so that the dye and the light stabilizer enter the polymer optical fiber through adsorption and diffusion effects, and damage to the dye and the light stabilizer caused by free radicals and high temperature conditions is avoided.
(4) The photostability of the dye after doping is mainly influenced by the doping process and the microenvironment in the working state, in particular the presence of oxygen. Besides the quenching effect of the light stabilizer doped at the same time on the triplet state of the pyrrole methylene dye, the doping process disclosed by the invention adopts inert carbon dioxide high-pressure gas fluid as working fluid, after the high-pressure carbon dioxide treatment, the original residual oxygen in the PMMA optical fiber is removed, and meanwhile, a small amount of inert carbon dioxide remains in the optical fiber, so that the influence of the existence of micro-environmental oxygen in the dye can be reduced as much as possible in the use process, and the two factors are helpful for improving the light stability of the dye in the work;
(5) In order to improve the photostability of the doped dye in the polymer, different light stabilizers are doped simultaneously according to the types of the dye, such as a proper amount of triplet quencher, free radical quencher and the like, so as to improve the photostability of the doped dye, and the method is an effective method.
Drawings
FIG. 1 shows a PM580 structure
FIG. 2 is a schematic illustration of a high pressure fluid device according to the present invention;
FIG. 3 is the fluorescence stability of PM580 and DABCO doped polymer optical fiber prepared in example 1;
fig. 4 is the fluorescence stability of PM580 and TPA doped polymer optical fibers prepared in example 2.
Reference numerals: 1-a steel cylinder; 2-high pressure pump; 3-a front and rear inlet and outlet valve of the high-pressure pump; 4-an internal circulation pump; 5-U-shaped pipes; 6-a temperature measurement probe; 7-needle valve; 8-flowmeter.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a high-pressure fluid device (see figure 2) for carbon dioxide fluid treatment experiments. In fig. 1, the oven with the temperature measuring probe 6 controls the oven temperature to be within ±1 ℃ of the desired temperature. A high pressure resistant stainless steel U-tube 5, which is used to house polymethyl methacrylate (PMMA) optical fiber (maximum receivable length 2 m), has an internal diameter of 5 mm and can withstand pressures up to 20MPa. A typical high pressure carbon dioxide fluid treatment process is as follows, a length of PMMA fiber is first placed into a U-tube, wherein one end of the PMMA fiber is secured to a stainless steel tube with a metal mesh.
The fluorescent dye is dissolved in a cosolvent (a mixture of methanol and ethanol), and the light stabilizer triethylenediamine (DABCO) or Triphenylamine (TPA) is dissolved in the cosolvent, wherein the cosolvent is used in an amount of 2-3 wt% of the whole circulation loop volume. According to different varieties, the molar ratio of the fluorescent dye to the light stabilizer is 1:10-15, and after the dye and the light stabilizer are dissolved, the cosolvent is injected into the stainless steel tube through a syringe.
And then closing the whole pipeline, adjusting the temperature of the incubator, and injecting high-pressure carbon dioxide fluid into the pipeline through the high-pressure pump 2 when the whole system reaches the preset temperature, wherein the pressure of the whole pipeline continuously rises along with the injection of the carbon dioxide fluid. When the pressure reaches a set value, the high-pressure delivery pump is closed, the air inlet and the closed circulation pipeline are closed through the valves of the high-pressure pump front and back inlet valve and the air outlet valve 3, the internal circulation pump 4 is started to work, the high-pressure carbon dioxide fluid circularly flows in the stainless steel U-shaped pipe 5, the existence of the cosolvent plays two roles, 1 is to dissolve the dye and the light stabilizer, 2 is to increase the polarity of the carbon dioxide fluid, the cosolvent and the carbon dioxide fluid form homogeneous phase liquid, the dye and the light stabilizer are dissolved in the homogeneous phase liquid, adsorbed on the surface of the optical fiber and gradually diffused into the optical fiber core layer, and the dye and the light stabilizer are kept to be diffused in the optical fiber for about 18-20 hours. In order to avoid foaming, the bleed rate was observed with a flow meter 8 by using a high pressure valve and a needle valve 7 for 3-4 hours to very slowly and uniformly vent carbon dioxide while maintaining the process temperature.
The PMMA fiber used in the present invention is CK30 fiber from Mitsubishi corporation. The optical fiber structure is of an SI structure, the outer layer part is made of fluorine resin, the diameter of the optical fiber is about 750 mu m, the core part is made of PMMA, the diameter of the core is 738 mu m, and the core accounts for 97% of the whole optical fiber volume.
Example 1
Step 1, the dosage of the fluorescent dye PM580 (the structural formula of the PM580 is shown in figure 1) is 2wt% of the weight of the PMMA optical fiber, the fluorescent dye PM580 is dissolved in 3mL of cosolvent solution, and the cosolvent is mixed by methanol and ethanol in a volume ratio of 1:2. meanwhile, the light stabilizer is as follows: dye mole ratio 15:1, simultaneously dissolving the light stabilizer DABCO and the dye PM580 in a cosolvent;
wherein the cosolvent is used in an amount of 3% of the volume of the high-pressure carbon dioxide fluid (i.e., the volume of the entire circulation loop). The PMMA fiber was added to a length of 1 m, and after the dye and the light stabilizer were dissolved in the cosolvent, they were injected into a stainless steel tube by syringe.
Step 2, placing the PMMA optical fiber in a high-pressure fluid device, injecting a dye auxiliary agent, injecting a carbon dioxide fluid after the temperature reaches 18 ℃, until the pressure rises to 10MPa, and keeping the diffusion of the dye and the light stabilizer in the optical fiber for about 18 hours to finish, thereby obtaining the polymer optical fiber doped with the fluorescent dye and the light stabilizer simultaneously;
example 2
Step 1, the dosage of fluorescent dye PM580 is 2wt% of the weight of the optical fiber, the fluorescent dye PM580 is dissolved in 3mL of cosolvent solution, and the cosolvent is mixed with methanol and ethanol in a volume ratio of 1:2. meanwhile, the light stabilizer is as follows: dye mole ratio 10:1, the light stabilizer TPA and the dye PM580 are simultaneously dissolved in the cosolvent;
wherein, the cosolvent dosage is 3% of the whole circulation loop volume. After the dye and light stabilizer are dissolved in the co-solvent, they are injected into the stainless steel tube by syringe.
Step 2, placing PMMA optical fiber with the length of 1 meter in a high-pressure fluid device, injecting a dye auxiliary agent, injecting carbon dioxide fluid after the temperature reaches 18 ℃, until the pressure is increased to 10MPa, and keeping the diffusion of dye and light stabilizer in the optical fiber for about 18 hours to obtain polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously;
example 3
Step 1, the dosage of fluorescent dye PM580 is 1wt% of the weight of the optical fiber, the fluorescent dye PM580 is dissolved in 2mL of cosolvent solution, and the cosolvent is mixed with methanol and ethanol in a volume ratio of 1:1.9. meanwhile, the light stabilizer is as follows: dye mole ratio 12:1, simultaneously dissolving the light stabilizer DABCO and the dye PM580 in a cosolvent;
wherein, the cosolvent dosage is 2% of the whole circulation loop volume. After the dye and photostabilizer are dissolved, the cosolvent is injected into the stainless steel tube by syringe.
Step 2, placing PMMA optical fiber with the length of 1 meter in a high-pressure fluid device, injecting a dye auxiliary agent, injecting carbon dioxide fluid after the temperature reaches 20 ℃, until the pressure is increased to 8MPa, keeping the diffusion of dye and light stabilizer in the optical fiber for about 19 hours, and processing to obtain polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously;
example 4
Step 1, the dosage of the fluorescent dye PM580 is 1.5wt% of the weight of the optical fiber, the fluorescent dye PM580 is dissolved in 2.5mL of cosolvent solution, and the cosolvent is mixed with methanol and ethanol in a volume ratio of 1:2.1. meanwhile, the light stabilizer is as follows: dye mole ratio 14:1, simultaneously dissolving the light stabilizer DABCO and the dye PM580 in a cosolvent;
wherein, the cosolvent dosage is 2.5% of the whole circulation loop volume. After the dye and photostabilizer are dissolved, the cosolvent is injected into the stainless steel tube by syringe.
Step 2, placing PMMA optical fiber with the length of 1 meter in a high-pressure fluid device, injecting a dye auxiliary agent, injecting carbon dioxide fluid after the temperature reaches 19 ℃, until the pressure is increased to 12MPa, and keeping the diffusion of dye and light stabilizer in the optical fiber for about 20 hours to finish, so as to obtain the polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously;
for the measurement of the light stability of the polymer optical fiber prepared in example 1 and doped with the fluorescent dye and the light stabilizer, the fluorescence intensity of the dye in the optical fiber was measured after the optical fiber sample doped with the dye was continuously irradiated with a 30W ultraviolet lamp, and the wavelength of the ultraviolet lamp was 254nm. As can be seen from fig. 3, the effect of doping the light stabilizer can significantly improve the light stabilization effect of PM580 of the fluorescent dye after doping DABCO. The fluorescence attenuation in the optical fiber is about 15% after the ultraviolet lamp is continuously irradiated for 300 hours, and the fluorescence intensity of the fluorescent dye PM580 without the doping stabilizer can be maintained to be more than 50% of the initial intensity value after the ultraviolet lamp is continuously irradiated for 500 hours, compared with the fluorescent dye PM580 without the doping stabilizer, the fluorescence intensity of the fluorescent dye PM580 is only about 20% of the initial intensity, and the added light stabilizer DABCO plays an important role in improving the service life of the dye.
For the measurement of the light stability of the polymer optical fiber prepared in example 2 and doped with the dye and the light stabilizer, the fluorescence intensity of the dye in the optical fiber was measured after the optical fiber sample doped with the dye was continuously irradiated with a 30W ultraviolet lamp, and the wavelength of the ultraviolet lamp was 254nm. As can be seen from fig. 4, the effect of doping the light stabilizer can significantly improve the light stabilization effect of PM580 of the fluorescent dye after doping TPA. The fluorescence intensity of the fluorescent dye PM580 without the doping stabilizer can be maintained to be more than 70% of the initial intensity value after the ultraviolet lamp continuously irradiates for 300 hours and the fluorescence attenuation amplitude is about 10% after the ultraviolet lamp continuously irradiates for 500 hours, compared with the fluorescent dye PM580 without the doping stabilizer, the fluorescence intensity of the fluorescent dye PM580 is only about 20% of the initial intensity, and the added light stabilizer TPA plays an important role in improving the service life of the dye.
The experimental results show that the addition of DABCO and TPA can effectively quench the triplet state of PM580 dye, lighten the damage of oxygen to pyrrole methylene dye under the triplet state, and improve the light stability of PM580 dye in polymer optical fiber. The polymer optical fiber prepared by the PM580 and the light stabilizer under the mild condition of high-pressure carbon dioxide has high efficiency, improves the light stability of the PM580, and provides a new way for prolonging the service life of the dye-doped polymer optical fiber.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of the polymer optical fiber doped with the fluorescent dye and the light stabilizer simultaneously is characterized by comprising the following steps of:
and (3) placing the PMMA optical fiber in a high-pressure fluid device, placing the fluorescent dye, the light stabilizer and the cosolvent, injecting high-pressure carbon dioxide fluid when the temperature reaches 18-20 ℃ until the pressure is increased to 8-12MPa, and processing to obtain the polymer optical fiber doped with the fluorescent dye and the light stabilizer.
2. The method for preparing a polymer optical fiber simultaneously doped with a fluorescent dye and a light stabilizer according to claim 1, wherein the light stabilizer is triethylenediamine or triphenylamine.
3. The method of preparing a polymer optical fiber doped with both a fluorescent dye and a light stabilizer according to claim 1, wherein the fluorescent dye is pyretomethene 580.
4. The method for preparing a polymer optical fiber simultaneously doped with a fluorescent dye and a light stabilizer according to claim 1, wherein the fluorescent dye and the light stabilizer are added into a cosolvent to obtain a mixed solution, and the mixed solution is added into a high-pressure fluid device after the fluorescent dye and the light stabilizer are dissolved.
5. The method for preparing the polymer optical fiber doped with the fluorescent dye and the light stabilizer simultaneously according to claim 1, wherein the cosolvent is a mixture of methanol and ethanol, the volume ratio of the methanol to the ethanol is 1:1.9-2.1, and the use amount of the cosolvent is 2-3% of the volume of the high-pressure carbon dioxide fluid.
6. The method for preparing the polymer optical fiber doped with the fluorescent dye and the light stabilizer simultaneously according to claim 5, wherein the doping amount of the fluorescent dye is 1% -2% of the mass of the PMMA optical fiber; the molar ratio of the fluorescent dye to the light stabilizer is 1:10-15.
7. The method for preparing a polymer optical fiber doped with fluorescent dye and light stabilizer simultaneously according to claim 1, wherein the treatment time is 18-20h.
8. A polymer optical fiber doped with a fluorescent dye and a light stabilizer simultaneously, prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310198470.2A CN116084174A (en) | 2023-03-03 | 2023-03-03 | Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310198470.2A CN116084174A (en) | 2023-03-03 | 2023-03-03 | Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116084174A true CN116084174A (en) | 2023-05-09 |
Family
ID=86200856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310198470.2A Pending CN116084174A (en) | 2023-03-03 | 2023-03-03 | Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116084174A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605761A (en) * | 1994-11-28 | 1997-02-25 | Minnesota Mining And Manufacturing Company | Articles exhibiting durable color containing a polycarbonate, a fluorescent dye and an amine light stabilizer |
| WO1997008756A1 (en) * | 1995-08-28 | 1997-03-06 | Minnesota Mining And Manufacturing Company | Durable fluorescent solar collectors |
| CN1278841A (en) * | 1997-10-23 | 2001-01-03 | 美国3M公司 | Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers |
| JP2006124868A (en) * | 2004-10-28 | 2006-05-18 | Pilot Ink Co Ltd | Photochromic fiber |
| US20080023646A1 (en) * | 2004-07-08 | 2008-01-31 | International University Bremen Gmbh | Photostabilisation of Fluorescent Dyes |
| CN106133038A (en) * | 2014-04-15 | 2016-11-16 | 艾尼股份公司 | The method of impregnated polymer substrate |
| US20190284320A1 (en) * | 2016-09-30 | 2019-09-19 | Sekisui Plastics Co., Ltd. | Fluorescent resin particles and use thereof |
| CN113047045A (en) * | 2021-03-29 | 2021-06-29 | 中国科学院深圳先进技术研究院 | Flexible optical fiber and preparation method and application thereof |
| KR20210117755A (en) * | 2020-03-20 | 2021-09-29 | 동우 화인켐 주식회사 | A self emission type photosensitive resin composition, and a color conversion layer, a color conversion filter and a display device manufactured by using thereof |
-
2023
- 2023-03-03 CN CN202310198470.2A patent/CN116084174A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605761A (en) * | 1994-11-28 | 1997-02-25 | Minnesota Mining And Manufacturing Company | Articles exhibiting durable color containing a polycarbonate, a fluorescent dye and an amine light stabilizer |
| WO1997008756A1 (en) * | 1995-08-28 | 1997-03-06 | Minnesota Mining And Manufacturing Company | Durable fluorescent solar collectors |
| CN1278841A (en) * | 1997-10-23 | 2001-01-03 | 美国3M公司 | Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers |
| US20080023646A1 (en) * | 2004-07-08 | 2008-01-31 | International University Bremen Gmbh | Photostabilisation of Fluorescent Dyes |
| JP2006124868A (en) * | 2004-10-28 | 2006-05-18 | Pilot Ink Co Ltd | Photochromic fiber |
| CN106133038A (en) * | 2014-04-15 | 2016-11-16 | 艾尼股份公司 | The method of impregnated polymer substrate |
| US20190284320A1 (en) * | 2016-09-30 | 2019-09-19 | Sekisui Plastics Co., Ltd. | Fluorescent resin particles and use thereof |
| KR20210117755A (en) * | 2020-03-20 | 2021-09-29 | 동우 화인켐 주식회사 | A self emission type photosensitive resin composition, and a color conversion layer, a color conversion filter and a display device manufactured by using thereof |
| CN113047045A (en) * | 2021-03-29 | 2021-06-29 | 中国科学院深圳先进技术研究院 | Flexible optical fiber and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵川等: "二氧化碳流体体系中聚合物光纤内吡咯甲川染料的注入", 《纺织学报》, vol. 34, no. 2, pages 115 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102191023B (en) | Temporary plugging agent for medium/high-temperature oil-gas reservoir | |
| Huang et al. | Study on a polymerizable visible light initiator for fabrication of biosafety materials | |
| Yang et al. | Lutetium (iii) porphyrinoids as effective triplet photosensitizers for photon upconversion based on triplet–triplet annihilation (TTA) | |
| Charlot et al. | Photopolymerization of methyl methacrylate: effects of photochemical and photonic parameters on the chain length | |
| Peng et al. | Visible light controlled aqueous RAFT continuous flow polymerization with oxygen tolerance | |
| CN116084174A (en) | Polymer optical fiber simultaneously doped with fluorescent dye and light stabilizer and preparation method thereof | |
| Sakr et al. | Photophysical, photochemical and laser behavior of some diolefinic laser dyes in sol–gel and methyl methacrylate/2-hydroxyethyl methacrylate copolymer matrices | |
| Wu et al. | Photo‐RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light‐Regulated Healable Hydrogels under NIR Irradiation | |
| CN105199114A (en) | Synthesis method of photoluminescence europium-containing polymer hydrogel material | |
| CN108219084A (en) | A kind of cell ultra-violet protecting agent of 3,4- dihydrogen phosphorothioates pyrimid-2-one copolymer structure and preparation method and application | |
| Jing et al. | A novel high-strength polymer hydrogel with identifiability prepared via a one-pot method | |
| CN113462380B (en) | Organic gel for realizing triplet annihilation photon up-conversion in air state and preparation method and application thereof | |
| Lacôte et al. | NHC-boranes: air-and water-tolerant coinitiators for type II photopolymerizations | |
| CN101275040A (en) | Preparation for high-performance solid dye laser medium | |
| Chen et al. | 5, 12‐Dihydroindolo [3, 2‐a] Carbazole Derivatives‐Based Water Soluble Photoinitiators for 3D Antibacterial Hydrogels Preparation | |
| CN110387593A (en) | A kind of preparation method of nanoscale bonding type Fluorescent falsification-preventing fiber | |
| Sun et al. | Conjugated/nonconjugated alternating copolymers for enhanced NIR-II fluorescence imaging and NIR-II photothermal-ferrotherapy | |
| JP5332569B2 (en) | Medical materials | |
| US5136005A (en) | Composition and method of preparation of solid state dye laser rods | |
| CN104910040A (en) | Methacrylate containing ortho-tetrafluoroazobenzene structure, polymer thereof, and preparation method and application thereof | |
| Hill et al. | The effects of γ-radiation on polyacrylonitrile | |
| Liang et al. | Fabrication and amplified spontaneous emission of Eu (DBM) 3 Phen doped step-index polymer optical fiber | |
| CN109651567A (en) | A kind of high intensity hydrogel system and preparation method thereof of free radical polymerization kinetics regulation | |
| Kobayashi et al. | High-power polymer optical fiber lasers and amplifiers | |
| Gkogkos et al. | Synthesis of PEG-PPG-PEG templated polydopamine nanoparticles under intensified conditions: Kinetics investigation, continuous process design and demonstration for photothermal application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |