CN104356299A - Method for synthesizing ultraviolet-writable fluorine-containing erbium-containing polymer waveguide amplifier material - Google Patents
Method for synthesizing ultraviolet-writable fluorine-containing erbium-containing polymer waveguide amplifier material Download PDFInfo
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Abstract
The invention relates to a method for synthesizing an ultraviolet-writable fluorine-containing erbium-containing polymer waveguide amplifier material and belongs to the field of synthesis of polymer near-infrared light-emitting materials. According to the method, a fluorine-containing active monomer containing an olefin double bond and an epoxy group, an erbium-containing complex and epoxypropyl methacrylate are subjected to ternary polymerization to prepare a fluorine-containing erbium-containing polymer near-infrared light-emitting material so that the compounding of an erbium ion and the polymer at the molecular level is achieved and the fluorescence quenching caused by uneven concentration of a rare earth complex due to phase separation generated by uneven doping is avoided. Polymer optical waveguide amplifier micro-patterns with stripe structures are prepared by carrying out lithography development on a polymer film obtained by a spin coating through a direct ultraviolet-writing technology, compared with the traditional process, copying processes such as evaporating a metal film layer and ion etching are not needed and thus the process steps are reduced and meanwhile, the cost is decreased and the method is an advantageous method for producing a polymer waveguide amplifier.
Description
Technical field
The present invention relates to a kind of synthesis can the fluorine-containing method containing erbium polymer waveguide amplifier material of U-V writing, belongs to polymkeric substance near-infrared light-emitting material synthesis field.
Background technology
Er-doped fiber material is the study hotspot of optical-fibre communications field in recent years always, this is because Er
3+after exciting by incident light, the fluorescent emission of communication windows wavelength 1550nm can be provided, and can react with beta-diketon class, fragrant lopps, heterocyclic, the large lopps of armed or multiamide type part, generate a series of novel structure, abundant species containing Erbium organic complex.And for the application of rare earth erbium organic coordination compound, be mostly at present and be doped in organic phase (as polymkeric substance), comprise the mode of physical doping and in-situ polymerization.But these methods can cause rare earth compounding disperse uneven or occur reuniting and causing the phenomenons such as quenching of fluorescence in the course of processing.In title complex, introduce active group, carry out copolymerization by active group and polymerisable monomer and form the high molecular polymer containing rare earth compounding group, feasible solves these difficult problems effectively.
Polymkeric substance is exactly will have low optical loss at communication window (1310,1550nm) as the most important condition of the body material of optical waveguides.Absorption loss and scatter loss are the main optical losss of polymer optical wave guide material, should reduce the impact of these factors when choosing matrix as far as possible.Vibration as intramolecular c h bond, O-H key and N-H key can cause light in the absorption loss of near infrared communication band (1000-1700nm).Therefore, although conventional synthetic glass and light-passing plastic are good polymeric optical materials in visible light wave range (400-750nm) scope, they are not also suitable for optical communication wave band.In order to address this problem, the method that present stage can adopt has: 1) replace hydrogen atom with halogen atom or heavy atom, because the stretching vibration wavelength ratio c h bond of C-D and C-F key larger (namely vibrational frequency is less), absorption can be made to move (namely occurring red shift) to long wave direction, the absorption loss of near infrared region can be reduced thus; 2) consider that the general frequency vibration of c h bond is the main cause occurring absorption loss, therefore the substituting group proportion of adjustable polymkeric substance long-chain reduces the general frequency vibration etc. of c h bond.Replace hydrogen atom at the multiplex fluorine atom of near-infrared band at present and reduce the absorb light loss of material at optical communication window, namely possess low light loss character.
Can direct ultraviolet Writing Technology be the most promising technology in polymer optical wave guide aspect epoxy resin being used for lithographic nano level pattern He there is particular geometric configuration.This technology was used for greatly micron, nano level lithography and manufactured opto-electronic device etc. present stage, and current research shows that this technology can also be used to make polymer optical waveguide device.This technology, compared with traditional technology, without the need to copy process such as evaporation metal rete and ion etchings, also reduces cost while reducing processing step, is the favorable method making polymer optical wave guide amplifier.Micro-pattern of the polymer optical wave guide made by this method, not only there is regular constitutional features, also possesses the advantage of polymer matrix material, as good thermostability, film-forming properties, near-infrared luminous characteristic, specific refractory power is adjustable, and wherein the optical waveguides pattern of bar shaped geometry has steep sidewall and lower surfaceness, the scattered light loss of material can be reduced, but fail to solve the problem in the larger absorb light loss of optical communication window (1310 and 1550nm place) existence.Epoxy resin can be cross-linked under ultraviolet light irradiation in open loop, because having, cure shrinkage is low, material interface adhesivity is good, dielectric properties are good, good stability of the dimension, thermostability are excellent, solvent resistance good, physical strength advantages of higher, and direct ultraviolet Writing Technology can be utilized the polymer optical wave guide material becoming to have particular geometric configuration containing erbium polymers manufacturing of band epoxide group.Containing the polymer optical wave guide material of erbium having concurrently on the basis containing the advantage of Erbium organic complex and epoxy resin, require there is low absorption loss at optical communication window place, wherein replacing hydrogen atom with heavy atom and halogen atom, is the effective ways reducing absorption loss.
Summary of the invention
For current polymer waveguide amplifier mainly based on physical doping and the present situation of device fabrication process complexity, the invention provides a kind of synthesis can the fluorine-containing method containing erbium polymer waveguide amplifier material of U-V writing, the method should adopt the fluorine-containing reactive monomer containing olefinic double bonds and epoxide group, by carrying out terpolymer prepare the fluorine-containing polymkeric substance near-infrared light-emitting material containing erbium with containing Er complex, glytidyl methacrylate.
The technical solution used in the present invention is: a kind of synthesis can the fluorine-containing method containing erbium polymer waveguide amplifier material of U-V writing comprise the following steps:
Step 1, there is the synthesis of the fluorochemical monomer (FA) of olefinic double bonds and epoxide group
Weigh the THF that 2-200g hexafluoro bisphenol-a is dissolved in about 20-2000mL, pour in the there-necked flask be placed in ice bath, add 0.65-65g triethylamine, after logical nitrogen gas stirring 20-60min, rare for 0.53-53g third acyl chlorides be dissolved in 10-1000mLTHF and be added drop-wise to rapidly in above-mentioned solution, reaction 1-2h recession, from ice bath, at room temperature continues reaction 12h; By underpressure distillation at reaction solution 95 DEG C, after the tetrahydrofuran (THF) in reaction system to be removed and triethylamine, add 20-200g epoxy chloropropane, be transferred in the there-necked flask of 50 DEG C of waters bath with thermostatic control, after logical nitrogen 30-60min, add NaOH every 0.5h, amount to 3-300g; Then be warming up to 60 DEG C, isothermal reaction 6-12h, to complete cyclization, obtains thick product, and underpressure distillation removes remaining epoxy chloropropane, 70-80 DEG C of vacuum-drying 12h; After being cooled to room temperature, with anhydrous alcohol solution, leave standstill 2-6h; With the salinity that organic membrane filtration is residual, normal pressure boils off ethanol, obtains the transparent thick liquid of tawny, in 40-50 DEG C of vacuum-drying 2 days, obtains step 1 product (FA);
Step 2, synthesis containing Erbium organic complex (EDPM)
The diphenylpropane-1,3-dione(DPPO) (DBM) of 0.002mol and the phenanthroline (Phen) of 0.001mol are joined in 30mL ethanolic soln, 50-70 DEG C of water bath with thermostatic control is heated to dissolve completely; Instill the methacrylic acid (HMA) of 0.0011mol in this solution, pour in the there-necked flask be placed in 25-35 DEG C of constant temperature oil bath, logical nitrogen also stirs, slowly drip with separating funnel the ethanolic soln 20mL that concentration is the Erbium trichloride of 0.05mol/L after 30-60min, and the aqueous sodium hydroxide solution adjust ph dripping 1mol/L is 7.0-8.0, continue constant temperature stirring reaction 12h; Reaction solution supercentrifuge is separated, and gained solid phase ethanol repeatedly washs, and 25-35 DEG C of vacuum-drying 12h obtains containing Er complex (EDPM); Step 3, the fluorine-containing synthesis containing erbium polymkeric substance
0.3394g (0.377mmol)-2.4924g (2.77mmol) EDPM that 0.04mol fluorochemical monomer step 1 obtained, step 2 obtain, 0.02mol glytidyl methacrylate (GMA), 50mL DMF joins in 100mL there-necked flask, after logical nitrogen gas stirring 30min, add 0.0342g Diisopropyl azodicarboxylate (AIBN), 75 DEG C of reaction 6h obtain transparent copolymer solution;
Step 4, the fluorine-containing purifying containing erbium polymkeric substance
Getting 100mL methyl alcohol pours in beaker, slowly drips the transparent copolymer solution that step 3 obtains under fast stirring, produces white flock precipitate, leave standstill deposition to be precipitated, suction filtration, 30 DEG C of vacuum-drying 12h; By the dissolution of solid of gained in THF, repeat above precipitation process, 30 DEG C of vacuum-dryings, gained solid is the fluorine-containing containing erbium polymkeric substance (PFA-EDPM-GMA) of purifying.
The invention has the beneficial effects as follows: this synthesis can the fluorine-containing method containing erbium polymer waveguide amplifier material of U-V writing by polymerization by luminescent material compound in the polymer and introduce can the epoxide group of U-V writing, obtain a kind of can the near-infrared luminous polymer materials of direct photoetching, this Material cladding avoids point mutual-assistance rare earth compounding density unevenness caused due to inequality of adulterating and causes quenching of fluorescence.Utilize direct ultraviolet Writing Technology, the mode that polymeric film adopts photoetching development is obtained to spin coating, has been made into the micro-pattern of polymer optical wave guide amplifier of strip structure.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of fluoropolymer monomer (FA).
Fig. 2 is the infrared spectrogram of fluorine-containing reactive monomer (FA).
Fig. 3 be fluorine-containing reactive monomer (FA) proton nmr spectra (
1h-NMR).
Fig. 4 be fluorine-containing reactive monomer (FA) Enantiomeric excess (
19f-NMR).
Fig. 5 is the synthetic route chart of title complex EDPM.
Fig. 6 is the infrared spectrum of title complex EDPM.
Fig. 7 is fluorine-containing containing erbium polymer P FA-EDPM-GMA synthetic route chart.
Fig. 8 is the fluorine-containing infrared spectrogram containing erbium polymer P FA-EDPM-GMA.
Fig. 9 is the fluorine-containing nuclear magnetic spectrogram containing erbium polymer P FA-EDPM-GMA.
Figure 10 is the fluorine-containing fluorescence spectrum figure containing erbium polymer P FA-EDPM-GMA (Er=0.5wt%).
Figure 11 is the stereoscan photograph of the fluorine-containing optical waveguides pattern containing erbium polymer P FA-EDPM-GMA.
Embodiment
Following embodiment can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
Weigh the THF that 2g (0.005952mol) hexafluoro bisphenol-a is dissolved in about 20mL, pour in the there-necked flask be placed in ice bath, add 0.65g (0.006436mol) triethylamine (Et
3the amount of N should than the HCl generated in reaction little over amount), after logical nitrogen gas stirring 30min, the rare acyl chlorides of 0.5383g (0.006223mol) third be dissolved in 10ml THF and be added drop-wise to rapidly in above-mentioned solution, reaction 1h recession is from ice bath, at room temperature continue reaction, spend the night.By reaction solution 95 DEG C of underpressure distillation in Rotary Evaporators, the tetrahydrofuran (THF) in removing reaction system and triethylamine; Add 20g (0.2162mol) epoxy chloropropane, be transferred in the there-necked flask of 50 DEG C of waters bath with thermostatic control, logical N
2after 30min, add 0.25g solid NaOH every 0.5h, add 12 times, amount to 3g; Be warming up to 60 DEG C, isothermal reaction 6h, to complete cyclization, obtains thick product, 80 DEG C of vacuum-dryings (spending the night); Underpressure distillation removes remaining epoxy chloropropane, after being cooled to room temperature, with the dissolve with ethanol of 100%, is put in stink cupboard and leaves standstill 2h.With the salinity that organic membrane filtration is residual, normal pressure boils off ethanol, obtains the transparent thick liquid of tawny, within 2 days, obtains fluorochemical monomer in 50 DEG C of vacuum-dryings.
Join in 30mL ethanolic soln by the diphenylpropane-1,3-dione(DPPO) (DBM) of 0.002mol and the phenanthroline (Phen) of 0.001mol, heating in 60 DEG C of waters bath with thermostatic control is until dissolve completely; Instill the methacrylic acid (HMA) of 0.0011mol little over amount in this solution, pour in the there-necked flask be placed in 35 DEG C of constant temperature oil baths, logical nitrogen also stirs, slowly drip the ethanolic soln of the Erbium trichloride of about 20mL 0.001mol with separating funnel after 30min, and the aqueous sodium hydroxide solution dripping 1mol/L regulates pH, this object is HMA to change into sodium salt, be beneficial to and rare-earth ion coordination, precipitation can be produced in this process, the pH scope keeping solution is 7.0-8.0, continues constant temperature stirring reaction and spends the night; Reaction solution supercentrifuge is separated, and gained solid phase ethanol repeatedly washs, and 35 DEG C of vacuum-dryings obtain Er (DBM)
2(Phen) (MA) (EDPM).
By be provided with agitator, nitrogen protection device, reflux condensing tube 100ml there-necked flask be positioned in the constant temperature oil bath of 75 DEG C; add 0.5719g (0.6354mmol) EDPM; 2.843g (0.02mol) GMA; 17.84g (0.04mol) fluorochemical monomer FA is dissolved in N; in dinethylformamide (DMF) (50ml); after logical nitrogen gas stirring 30min, add 0.0342g AIBN, isothermal reaction 6h obtains transparent copolymer solution.
Get 100ml methyl alcohol and pour 200ml beaker into, slowly drip the transparent copolymer solution that step 3 obtains under fast stirring, produce white flock precipitate, leave standstill deposition to be precipitated, suction filtration, 30 DEG C of dried in vacuo overnight; By the dissolution of solid of gained in THF, repeat above precipitation process, 30 DEG C of vacuum-dryings, it is the fluorine-containing containing erbium polymkeric substance of the purifying of 0.5wt% that gained solid is containing erbium amount.
Embodiment 2
The all reaction raw materials used and working method are with embodiment 1, and the add-on that difference is containing Er complex EDPM is that to obtain erbium content be that 0.3wt% is fluorine-containing containing erbium polymkeric substance to 0.3394g.
Embodiment 3
The all reaction raw materials used and working method are with embodiment 1, and the add-on that difference is containing Er complex EDPM is that to obtain erbium content be that 1wt% is fluorine-containing containing erbium polymkeric substance to 2.4934g.
Figure 1 shows that the synthetic route chart of fluoropolymer monomer (FA) prepared by embodiment 1.
Figure 2 shows that the infrared spectrogram of fluorine-containing reactive monomer (FA) prepared by embodiment 1.As seen from the figure: fluorine-containing dihydroxyphenyl propane and acrylate chloride react products therefrom at 1636cm
-1there is the characteristic peak of C=C double bond in place, and 928cm
-1place is the characteristic peak of epoxide group, and 3367cm
-1-OH the absorption peak at place disappears substantially, and this illustrates that the phenolic hydroxyl group at fluorine-containing dihydroxyphenyl propane two ends and acrylate chloride, epoxy chloropropane complete reaction substantially.2930cm
-1place is the characteristic peak of methylene radical, 1611cm
-1, 1515cm
-1place is the charateristic avsorption band of phenyl ring, 1132-1297cm
-1place is the charateristic avsorption band of C – F.
IR(KBr,cm
-1)：γ(epoxy group)＝928cm
-1，γ(Caromatic)＝1611-1515cm
-1，γ(C–F)＝1132-1297cm
-1。
Figure 3 shows that fluorine-containing reactive monomer (FA) prepared by embodiment 1 proton nmr spectra (
1h-NMR).
As seen from the figure: the benzene ring hydrogen of the corresponding fluorine-containing dihydroxyphenyl propane of the characteristic peak at chemical shift δ=7.33-6.89ppm place, the hydrogen in the corresponding acrylate chloride of characteristic peak at 6.47-5.88ppm place on C=C, the corresponding methylene radical-CH of characteristic peak at 4.31-3.98ppm place
2on hydrogen (in figure 8,9) ,-CH and-CH in the corresponding epoxide group of the characteristic peak at 3.42-2.73ppm place
2on hydrogen (in figure 10,11,12), can judge that acrylate chloride, fluorine-containing dihydroxyphenyl propane, epoxy chloropropane three kinds of monomers successfully react thus, synthesize fluorine-containing reactive monomer.
1H NMR(400MHz,CDCl
3,TMS):δ(ppm),7.33(m,2H,-Ph),7.29(m,2H,-Ph),6.93(m,2H,-Ph),6.89(m,2H,-Ph),6.47(s,H,＝CH2),6.18(s,H,＝CH),5.88(s,H,＝CH2),4.31-3.98(m,2H,
),3.42(m,H,
),2.87-2.73(m,2H,
).
Figure 4 shows that fluorine-containing reactive monomer (FA) prepared by embodiment 1 Enantiomeric excess (
19f-NMR).Can be found out by the fluorine spectrum of fluorine-containing reactive monomer, be the characteristic peak at-64.3ppm place in chemical shift, be-CF
3in fluorine, in conjunction with fluorine-containing reactive monomer hydrogen spectrum spectrogram, its structure can be determined.
Figure 5 shows that title complex Er (DBM) prepared by embodiment 1
2(Phen) synthetic route chart of (MA) (EDPM)
Figure 6 shows that title complex Er (DBM) prepared by embodiment 1
2(Phen) infrared spectrum of (MA) (EDPM)
Figure 7 shows that prepared by embodiment 1 fluorine-containing containing erbium polymer P FA-EDPM-GMA synthetic route chart
Figure 8 shows that the fluorine-containing infrared spectrogram containing erbium polymer P FA-EDPM-GMA prepared by embodiment 1.
As seen from the figure, there is the fluorine-containing reactive monomer (FA) of polymerization activity and EDPM, GMA after free-radical polymerized, 1636cm
-1the C=C double bond absorption peak at place disappears, 907cm
-1the characteristic peak of the epoxide group at place still exists; 1669 and 1453cm
-1it is the charateristic avsorption band of phenyl ring; 1378-1142cm
-1place is the C – F absorption peak in fluorochemical monomer.IR (KBr, cm
-1): γ (epoxy group)=907cm
-1, γ (Caromatic)=1669 and 1453cm
-1, γ (C – F)=1378-1142cm
-1.
Figure 9 shows that the fluorine-containing nuclear magnetic spectrogram containing erbium polymkeric substance prepared by embodiment 1
As seen from the figure: the fluorine-containing dihydroxyphenyl propane phenyl ring of characteristic peak correspondence at chemical shift δ=8.01-6.90ppm place obtains hydrogen ,-CH in the corresponding GMA of characteristic peak at 4.31-3.82ppm place
2on hydrogen (in figure 1,2), hydrogen (in figure 3,4,5) in the corresponding epoxide group of characteristic peak at 3.23 – 2.85ppm places, the characteristic peak at 2.62-1.91ppm place is to the hydrogen (in figure 6,7) on emergencing copolymer carbon carbon long-chain, and the characteristic peak at 1.25-0.91ppm place is to-CH in emergencing copolymer
3hydrogen.
1H NMR(400MHz,CDCl
3,TMS):δ(ppm),8.01(m,2H,-Ph),7.68(m,2H,-Ph),7.51(m,2H,-Ph),6.89(m,2H,-Ph),4.31-3.82(m,2H,
),2.62(s,1H,–CH),1.91(s,2H,–CH
2),3.23(m,H,
),2.96–2.85(m,2H,
),1.25-0.91(s,3H,CH
3).
Figure 10 shows that the fluorine-containing fluorescence spectrum figure containing erbium polymer P FA-EDPM-GMA (Er=0.5wt%) prepared by embodiment 1
Application examples 1
The fluorine-containing preparation carrying out slab waveguide containing erbium polymkeric substance embodiment 1 obtains: what embodiment 1 obtained is fluorine-containing containing erbium polymer dissolution, polymeric film (by concentration and rotating speed controlling diaphragm layer thickness) is obtained by the method for spin coating, film is put into dry (90 DEG C of baking oven, 30min) to remove desolventizing, choose the template of bar shaped geometry, at ultraviolet lamp (the UV lamp of 400W, maximum wavelength 365nm) under, at least 1min is exposed in image-wise exposure mode, in the baking oven of 120 DEG C, toast 1h again, thoroughly complete the photocuring reaction of epoxy; Select DMF solvent to be developing solution, complete for curing cross-linked is immersed 30s in developing solution containing erbium polymeric film, and in the baking oven of 120 DEG C, dry 30min is to remove DMF, obtains strip optical waveguide pattern.
Figure 11 shows that the stereoscan photograph of the fluorine-containing optical waveguides pattern containing erbium polymkeric substance prepared by application examples 1.
Claims (1)
1. synthesis can the fluorine-containing method containing erbium polymer waveguide amplifier material of U-V writing, it is characterized in that: comprise the following steps:
Step 1, there is the synthesis of the fluorochemical monomer (FA) of olefinic double bonds and epoxide group
Weigh the THF that 2-200g hexafluoro bisphenol-a is dissolved in about 20-2000mL, pour in the there-necked flask be placed in ice bath, add 0.65-65g triethylamine, after logical nitrogen gas stirring 20-60min, rare for 0.53-53g third acyl chlorides be dissolved in 10-1000mLTHF and be added drop-wise to rapidly in above-mentioned solution, reaction 1-2h recession, from ice bath, at room temperature continues reaction 12h; By underpressure distillation at reaction solution 95 DEG C, after the tetrahydrofuran (THF) in reaction system to be removed and triethylamine, add 20-200g epoxy chloropropane, be transferred in the there-necked flask of 50 DEG C of waters bath with thermostatic control, after logical nitrogen 30-60min, add NaOH every 0.5h, amount to 3-300g; Then be warming up to 60 DEG C, isothermal reaction 6-12h, to complete cyclization, obtains thick product, and underpressure distillation removes remaining epoxy chloropropane, 70-80 DEG C of vacuum-drying 12h; After being cooled to room temperature, with anhydrous alcohol solution, leave standstill 2-6h; With the salinity that organic membrane filtration is residual, normal pressure boils off ethanol, obtains the transparent thick liquid of tawny, in 40-50 DEG C of vacuum-drying 2 days, obtains step 1 product (FA);
Step 2, synthesis containing Erbium organic complex (EDPM)
The diphenylpropane-1,3-dione(DPPO) (DBM) of 0.002mol and the phenanthroline (Phen) of 0.001mol are joined in 30mL ethanolic soln, 50-70 DEG C of water bath with thermostatic control is heated to dissolve completely; Instill the methacrylic acid (HMA) of 0.0011mol in this solution, pour in the there-necked flask be placed in 25-35 DEG C of constant temperature oil bath, logical nitrogen also stirs, slowly drip with separating funnel the ethanolic soln 20mL that concentration is the Erbium trichloride of 0.05mol/L after 30-60min, and the aqueous sodium hydroxide solution adjust ph dripping 1mol/L is 7.0-8.0, continue constant temperature stirring reaction 12h; Reaction solution supercentrifuge is separated, and gained solid phase ethanol repeatedly washs, and 25-35 DEG C of vacuum-drying 12h obtains containing Er complex (EDPM);
Step 3, the fluorine-containing synthesis containing erbium polymkeric substance
0.3394g (0.377mmol)-2.4924g (2.77mmol) EDPM that 0.04mol fluorochemical monomer step 1 obtained, step 2 obtain, 0.02mol glytidyl methacrylate (GMA), 50mL DMF joins in 100mL there-necked flask, after logical nitrogen gas stirring 30min, add 0.0342g Diisopropyl azodicarboxylate (AIBN), 75 DEG C of reaction 6h obtain transparent copolymer solution;
Step 4, the fluorine-containing purifying containing erbium polymkeric substance
Getting 100mL methyl alcohol pours in beaker, slowly drips the transparent copolymer solution that step 3 obtains under fast stirring, produces white flock precipitate, leave standstill deposition to be precipitated, suction filtration, 30 DEG C of vacuum-drying 12h; By the dissolution of solid of gained in THF, repeat above precipitation process, 30 DEG C of vacuum-dryings, gained solid is the fluorine-containing containing erbium polymkeric substance (PFA-EDPM-GMA) of purifying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829639A (en) * | 2015-04-24 | 2015-08-12 | 嘉兴学院 | Hyperbranched polyester rare earth complex containing nitrogen heterocyclic terminal group, and preparation method and use thereof |
| CN105199114A (en) * | 2015-10-28 | 2015-12-30 | 大连工业大学 | Synthesis method of photoluminescence europium-containing polymer hydrogel material |
| CN110590710A (en) * | 2019-09-17 | 2019-12-20 | 西北工业大学 | Bisphenol AF type epoxy end group adamantane and preparation method thereof, and high-wave-transmittance resin matrix and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434994A (en) * | 2000-02-18 | 2003-08-06 | X光子公司 | Rare earth polymer optical amplifier or fiber |
| CN101459311A (en) * | 2008-12-30 | 2009-06-17 | 吉林大学 | Polymer organic optical waveguide amplifier material containing erbium/ytterbium rare earth ion |
| KR20140121171A (en) * | 2013-04-05 | 2014-10-15 | 재단법인대구경북과학기술원 | A core composition for an optical waveguide device |
-
2014
- 2014-11-20 CN CN201410668827.XA patent/CN104356299B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434994A (en) * | 2000-02-18 | 2003-08-06 | X光子公司 | Rare earth polymer optical amplifier or fiber |
| CN101459311A (en) * | 2008-12-30 | 2009-06-17 | 吉林大学 | Polymer organic optical waveguide amplifier material containing erbium/ytterbium rare earth ion |
| KR20140121171A (en) * | 2013-04-05 | 2014-10-15 | 재단법인대구경북과학기술원 | A core composition for an optical waveguide device |
Non-Patent Citations (3)
| Title |
|---|
| XU FEI,ET AL.: "Synthesis of UV-Writing Fluoinated Polymer for Organic Optical Waveguide", 《ADVANCED MATERIALS RESEARCH》 * |
| YING WAN,ET AL.: "Highly fluorinated low-molecular-weight photoresists for optical waveguides", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
| 张丹等: "有机光波导放大器最新进展", 《激光与红外》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829639A (en) * | 2015-04-24 | 2015-08-12 | 嘉兴学院 | Hyperbranched polyester rare earth complex containing nitrogen heterocyclic terminal group, and preparation method and use thereof |
| CN105199114A (en) * | 2015-10-28 | 2015-12-30 | 大连工业大学 | Synthesis method of photoluminescence europium-containing polymer hydrogel material |
| CN105199114B (en) * | 2015-10-28 | 2017-08-01 | 大连工业大学 | A kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light |
| CN110590710A (en) * | 2019-09-17 | 2019-12-20 | 西北工业大学 | Bisphenol AF type epoxy end group adamantane and preparation method thereof, and high-wave-transmittance resin matrix and preparation method thereof |
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