CN104356299B - 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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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 44
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 12
- -1 erbium ion Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 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 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 3
- 244000144992 flock Species 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- AHVIPVIHHYMXPY-UHFFFAOYSA-N phenanthrene quinoline Chemical group N1=CC=CC2=CC=CC=C12.C1=CC=CC=2C3=CC=CC=C3C=CC12 AHVIPVIHHYMXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000992 sputter etching Methods 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
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- 239000001257 hydrogen Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
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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 U-V writing fluorine-containing polymer waveguide containing erbium amplifier material method, belong to poly-
Compound near-infrared light-emitting material synthesizes field.
Background technology
The study hotspot of Er-doped fiber material always optical-fibre communications field in recent years, this is because Er3+By incident light
After exciting, using the teaching of the invention it is possible to provide the fluorescent emission of communication windows wavelength 1550nm, and can with beta-diketon class, aromatic rings class, heterocyclic,
Armed big ring class or multiamide type part react, generate a series of structures novel, abundant species containing Erbium organic complex.
And the application for rare earth Erbium organic complex, it is mostly at present and is doped in organic phase (as polymer), including physics
Doping and the mode of in-situ polymerization.But these methods can cause rare earth compounding dispersion uneven or occur in process reuniting
And lead to the phenomenons such as fluorescent quenching.Introduce active group in complex, copolymerization is carried out by active group and polymerisable monomer
Form the high molecular polymer containing rare earth compounding group, feasible efficiently solves these difficult problems.
Polymer as the matrix material of fiber waveguide the most important condition be exactly to have in communication window (1310,1550nm) low
Light loss.Absorption loss and scattering loss are the main light loss of polymer optical wave guide material, should try one's best when choosing matrix
Reduce the impact of these factors.Vibration as intramolecular c h bond, O-H key and N-H key can cause light in near-infrared communication band
(1000-1700nm) absorption loss.Therefore although conventional lucite and light-passing plastic are in visible light wave range (400-
It is good polymeric optical material in the range of 750nm), but they are not particularly suited for optical communication wave band.Ask to solve this
Topic, the method that can adopt at this stage has：1) halogen atom or heavy atom is used to replace hydrogen atom, because the flexible of C-D and C-F key shakes
Dynamic wavelength ratio c h bond is bigger (i.e. vibration frequency is less), absorption can be made mobile (red shift) to long wave direction, thus can subtract
The absorption loss of few near infrared region；2) the general frequency vibration in view of c h bond is main cause absorption loss, therefore adjustable poly-
The substituent proportion of compound long-chain is reducing general frequency vibration of c h bond etc..Replace hydrogen in the multiplex fluorine atom of near infrared band at present
Atom to reduce the absorption light loss in optical communication window for the material, that is, possesses low light loss property.
Can direct ultraviolet Writing Technology be epoxy resin to be used for lithographic nano level pattern and there is particular geometric configuration
The most promising technology of polymer optical wave guide aspect.This technology is mostly used for micron, nanoscale lithographic printing and manufacture at this stage
Opto-electronic device etc., recent studies have shown that this technology can also be used to make polymer optical waveguide device.This technology and traditional work
Skill is compared, and without copy process such as evaporation metal film layer and ion etchings, also reduces cost, be while reducing processing step
Make the favorable method of polymer optical wave guide amplifier.Micro- pattern of the polymer optical wave guide making of the method, not only has
Regular architectural feature, the advantage being also equipped with polymeric matrix material, such as good heat endurance, film forming, near-infrared luminous
Characteristic, refractive index is adjustable etc., the fiber waveguide pattern of wherein bar shaped geometry has steep side wall and relatively low rough surface
Degree, can reduce the scattering light loss of material, but fails to solve there is larger absorption in optical communication window (at 1310 and 1550nm)
The problem of light loss.Epoxy resin under ultraviolet light irradiation can open loop crosslinked, because having, cure shrinkage is low, material interface adheres to
Property good, dielectric properties are good, good stability of the dimension, heat endurance are excellent, solvent resistance is good, high mechanical strength the advantages of, can be utilized
Direct ultraviolet Writing Technology will become have the polymer optical wave guide of particular geometric configuration with epoxide group polymers manufacturing containing erbium
Material.Polymer optical wave guide material containing erbium on the basis of having the advantage containing Erbium organic complex and epoxy resin concurrently it is desirable to
There is low absorption loss at optical communication window, wherein use heavy atom and halogen atom to replace hydrogen atom, be to reduce absorption loss
Effective ways.
Content of the invention
For current polymer waveguide amplifier mainly based on physical doping and the complicated present situation of device fabrication process,
The present invention provide a kind of synthesis can U-V writing fluorine-containing polymer waveguide containing erbium amplifier material method, the method should be using containing
There is the fluorine-containing activated monomer of olefinic double bonds and epoxide group, by carrying out three with containing Er complex, GMA
The fluorine-containing polymer near-infrared light-emitting material containing erbium is prepared in first copolymerization.
The technical solution used in the present invention is：A kind of synthesis can U-V writing fluorine-containing polymer waveguide containing erbium amplifier material
Method comprise the following steps：
Step 1, have olefinic double bonds and epoxide group fluorochemical monomer (FA) synthesis
Weigh the THF that 2-200g hexafluoro bisphenol-a is dissolved in 20-2000mL, pour in the there-necked flask being placed in ice bath, add
Plus 0.65-65g triethylamine, after logical nitrogen gas stirring 20-60min, 0.53-53g propylene acyl chlorides is dissolved in 10-1000mLTHF fast
Speed is added drop-wise in above-mentioned solution, and reaction 1-2h drops back from ice bath, continues reaction 12h at room temperature；To reduce pressure at 95 DEG C of reactant liquor
Distillation, after the oxolane in reaction system to be removed and triethylamine, adds 20-200g epoxychloropropane, is transferred to 50 DEG C of perseverances
In the there-necked flask of tepidarium, after logical nitrogen 30-60min, add NaOH, 3-300g altogether every 0.5h；Then heat to 60
DEG C, isothermal reaction 6-12h, to complete cyclization, obtains crude product, and vacuum distillation removes remaining epoxychloropropane, 70-80
DEG C vacuum drying 12h；After being cooled to room temperature, with anhydrous alcohol solution, stand 2-6h；The salinity being remained with organic membrane filtration,
Normal pressure boils off ethanol, obtains yellowish-brown transparent viscous liquid, is vacuum dried 2 days in 40-50 DEG C, obtains step 1 product (FA)；
Step 2, the synthesis containing Erbium organic complex (EDPM)
Adjacent phenanthrene quinoline (Phen) of the dibenzoyl methane (DBM) of 0.002mol and 0.001mol is added to 30mL ethanol
In solution, dissolving is heated on 50-70 DEG C of water bath with thermostatic control completely；Instill the methacrylic acid of 0.0011mol in this solution
(MAA), pour in the there-necked flask being placed in 25-35 DEG C of constant temperature oil bath, logical nitrogen simultaneously stirs, with a point liquid leakage after 30-60min
Bucket is slowly added dropwise the ethanol solution 20mL of the erbium chloride that concentration is 0.05mol/L, and drips the sodium hydrate aqueous solution of 1mol/L
Regulation pH value is 7.0-8.0, continues constant temperature stirring reaction 12h；Reactant liquor is separated with supercentrifuge, and gained solid phase ethanol is many
Secondary washing, 25-35 DEG C of vacuum drying 12h obtains containing Er complex (EDPM)；
Step 3, the fluorine-containing synthesis containing erbium polymer
0.3394g (the 0.377mmol) -2.4924g that 0.04mol fluorochemical monomer that step 1 is obtained, step 2 obtain
(2.77mmol) EDPM, 0.02mol GMA (GMA), 50mL DMF is added in 100mL there-necked flask,
After logical nitrogen gas stirring 30min, add 0.0342g azodiisobutyronitrile (AIBN), to obtain transparent copolymer molten for 75 DEG C of reaction 6h
Liquid；
Step 4, the fluorine-containing purifying containing erbium polymer
100mL methyl alcohol is taken to pour in beaker, the transparent copolymer being slowly added dropwise that step 3 obtains under fast stirring is molten
Liquid, produces white flock precipitate, stands deposition to be precipitated, suction filtration, 30 DEG C of vacuum drying 12h；By the solid dissolving of gained in THF
In, repeat above precipitation process, 30 DEG C of vacuum drying, gained solid is the fluorine-containing (PFA-EDPM- of polymer containing erbium purifying
GMA).
The invention has the beneficial effects as follows：This synthesis can U-V writing fluorine-containing polymer waveguide containing erbium amplifier material side
Method pass through polymerization by luminescent material be combined in the polymer and introduce can U-V writing epoxide group, obtaining one kind can be direct
The near-infrared luminous polymeric material of photoetching, this Material cladding avoids makes rare earth coordinate due to the split-phase that doping inequality causes
Thing density unevenness causes fluorescent quenching.Using direct ultraviolet Writing Technology, thin polymer film is obtained to spin coating and adopts photoetching development
Mode, be fabricated to the micro- pattern of polymer optical wave guide amplifier of strip structure.
Brief description
Fig. 1 is the synthetic route chart of fluoropolymer monomer (FA).
Fig. 2 is the infrared spectrogram of fluorine-containing activated monomer (FA).
Fig. 3 be fluorine-containing activated monomer (FA) proton nmr spectra (1H-NMR).
Fig. 4 be fluorine-containing activated monomer (FA) Enantiomeric excess (19F-NMR).
Fig. 5 is the synthetic route chart of complex EDPM.
Fig. 6 is the infrared spectrum of complex EDPM.
Fig. 7 is the fluorine-containing FA-EDPM-GMA synthetic route chart of polymer P containing erbium.
Fig. 8 is the infrared spectrogram of the fluorine-containing FA-EDPM-GMA of polymer P containing erbium.
Fig. 9 is the nuclear magnetic spectrogram of the fluorine-containing FA-EDPM-GMA of polymer P containing erbium.
Figure 10 is the fluorescence spectra of the fluorine-containing FA-EDPM-GMA of polymer P containing erbium (Er=0.5wt%).
Figure 11 is the stereoscan photograph of the fiber waveguide pattern of the fluorine-containing FA-EDPM-GMA of polymer P containing erbium.
Specific embodiment
Following embodiments can make those of ordinary skill in the art that the present invention is more fully understood, but never in any form
Limit the present invention.
Embodiment 1
Weigh the THF that 2g (0.005952mol) hexafluoro bisphenol-a is dissolved in about 20mL, pour three mouthfuls of burnings being placed in ice bath into
In bottle, add 0.65g (0.006436mol) triethylamine (Et3The amount of N should be more slightly excessive than the HCl generating in reaction), logical nitrogen stirs
After mixing 30min, 0.5383g (0.006223mol) propylene acyl chlorides is dissolved in 10ml THF and is added drop-wise to rapidly in above-mentioned solution, instead
Answer 1h to drop back from ice bath, continue reaction at room temperature, overnight.95 DEG C of vacuum distillations, the removing in Rotary Evaporators by reactant liquor
Oxolane in reaction system and triethylamine；Add 20g (0.2162mol) epoxychloropropane, be transferred to 50 DEG C of waters bath with thermostatic control
There-necked flask in, logical N2After 30min, add 0.25g solid NaOH every 0.5h, add 12 times, 3g altogether；It is warming up to 60
DEG C, isothermal reaction 6h, to complete cyclization, obtains crude product, 80 DEG C of vacuum drying (overnight)；Vacuum distillation removes remaining
Epoxychloropropane, after being cooled to room temperature, with 100% ethanol dissolving, is put in standing 2h in fume hood.Residual with organic membrane filtration
The salinity staying, normal pressure boils off ethanol, obtains yellowish-brown transparent viscous liquid, obtains fluorochemical monomer within 2 days in 50 DEG C of vacuum drying.
Adjacent phenanthrene quinoline (Phen) of the dibenzoyl methane (DBM) of 0.002mol and 0.001mol is added to 30mL ethanol
In solution, heating in 60 DEG C of waters bath with thermostatic control is until dissolving is complete；Instill the slightly excessive methyl-prop of 0.0011mol in this solution
Olefin(e) acid (MAA), pours in the there-necked flask being placed in 35 DEG C of constant temperature oil baths, and logical nitrogen simultaneously stirs, and uses separatory funnel after 30min
It is slowly added dropwise the ethanol solution of the erbium chloride of about 20mL 0.001mol, and drips the sodium hydrate aqueous solution of 1mol/L and adjust pH,
This purpose is for MAA to change into sodium salt, beneficial to rare-earth ion coordination, can produce precipitation during this, keep solution
PH scope is 7.0-8.0, continues constant temperature stirring reaction overnight；Reactant liquor is separated with supercentrifuge, and gained solid phase ethanol is many
Secondary washing, 35 DEG C of vacuum drying obtain Er (DBM)2(Phen)(MA)(EDPM).
By be provided with agitator, nitrogen protection device, reflux condensing tube 100ml there-necked flask be positioned over 75 DEG C of constant temperature
In oil bath, add 0.5719g (0.6354mmol) EDPM, 2.843g (0.02mol) GMA, 17.84g (0.04mol) fluorochemical monomer
FA is dissolved in DMF (DMF) (50ml), after logical nitrogen gas stirring 30min, adds 0.0342g AIBN, constant temperature is anti-
6h is answered to obtain transparent copolymer solution.
Take 100ml methyl alcohol to pour 200ml beaker into, be slowly added dropwise the transparent copolymer that step 3 obtains under fast stirring
Solution, produces white flock precipitate, stands deposition to be precipitated, suction filtration, 30 DEG C of dried in vacuum overnight；By the solid dissolving of gained in
In THF, repeat above precipitation process, 30 DEG C of vacuum drying, gained solid is the fluorine-containing of purifying that amount containing erbium is 0.5wt% and contains
Erbium polymer.
Embodiment 2
, with embodiment 1, difference is adding containing Er complex EDPM for all reaction raw materials using and method of operating
Enter amount to obtain erbium content for 0.3394g is the fluorine-containing polymer containing erbium of 0.3wt%.
Embodiment 3
, with embodiment 1, difference is adding containing Er complex EDPM for all reaction raw materials using and method of operating
Enter amount to obtain erbium content for 2.4934g is the fluorine-containing polymer containing erbium of 1wt%.
Fig. 1 show the synthetic route chart of the fluoropolymer monomer (FA) of embodiment 1 preparation.
Fig. 2 show the infrared spectrogram of the fluorine-containing activated monomer (FA) of embodiment 1 preparation.As seen from the figure：Fluorine-containing bisphenol-A
React products therefrom with acryloyl chloride in 1636cm-1Place occurs in that the characteristic peak of C=C double bond, and 928cm-1Locate as epoxide group
Characteristic peak, and 3367cm-1- OH the absworption peak at place disappears substantially, and this illustrates the phenolic hydroxyl group at fluorine-containing bisphenol-A two ends and acryloyl
Chlorine, epoxychloropropane are basically completed reaction.2930cm-1Locate the characteristic peak for methylene, 1611cm-1、1515cm-1Locate as phenyl ring
Characteristic absorption peak, 1132-1297cm-1Locate the characteristic absorption peak for C F.
IR(KBr,cm-1)：γ (epoxy group)=928cm-1, γ (Caromatic)=1611-1515cm-1, γ
(C F)=1132-1297cm-1.
Fig. 3 show embodiment 1 preparation fluorine-containing activated monomer (FA) proton nmr spectra (1H-NMR).Can by figure
Know：The benzene ring hydrogen of the corresponding fluorine-containing bisphenol-A of the characteristic peak at chemical shift δ=7.33-6.89ppm, 6.47-5.88ppm
Hydrogen on C=C in the corresponding acryloyl chloride of the characteristic peak at place, the characteristic peak at 4.31-3.98ppm corresponds to methylene-CH2On hydrogen
(in figure 8,9) ,-CH and-CH in the corresponding epoxide group of the characteristic peak at 3.42-2.73ppm2On hydrogen (in figure 10,11,12),
Thus can determine whether that acryloyl chloride, fluorine-containing bisphenol-A, three kinds of monomers of epoxychloropropane successfully react, synthesized fluorine-containing activated monomer
.1H NMR(400MHz,CDCl3,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,).
Fig. 4 show embodiment 1 preparation fluorine-containing activated monomer (FA) Enantiomeric excess (19F-NMR).By fluorine-containing
The fluorine of activated monomer is composed as can be seen that being the characteristic peak at -64.3ppm in chemical shift, as-CF3In fluorine, in conjunction with fluorine-containing
The hydrogen spectrum spectrogram of activated monomer is it may be determined that its structure.
Fig. 5 show the complex Er (DBM) of embodiment 1 preparation2(Phen) synthetic route chart of (MA) (EDPM)
Fig. 6 show the complex Er (DBM) of embodiment 1 preparation2(Phen) infrared spectrum of (MA) (EDPM)
Fig. 7 show the fluorine-containing FA-EDPM-GMA synthetic route chart of polymer P containing erbium of embodiment 1 preparation
Fig. 8 show the infrared spectrogram of the fluorine-containing FA-EDPM-GMA of polymer P containing erbium of embodiment 1 preparation.
As seen from the figure, there is fluorine-containing activated monomer (FA) and the EDPM of polymerization activity, 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-1
It is the characteristic absorption peak of phenyl ring；1378-1142cm-1Locate as the C F absworption 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.
Fig. 9 show the fluorine-containing nuclear magnetic spectrogram containing erbium polymer of embodiment 1 preparation
As seen from the figure：The corresponding fluorine-containing bisphenol-A phenyl ring of characteristic peak at chemical shift δ=8.01-6.90ppm obtains hydrogen,
- CH in the corresponding GMA of characteristic peak at 4.31-3.82ppm2On hydrogen (in figure 1,2), characteristic peak at 3.23 2.85ppm corresponds to
Hydrogen (in figure 3,4,5) in epoxide group, the characteristic peak at 2.62-1.91ppm is to the hydrogen (in figure on emergencing copolymer carbon carbon long-chain
6th, 7), the characteristic peak at 1.25-0.91ppm is to-CH in emergencing copolymer3Hydrogen.
1H NMR(400MHz,CDCl3,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,–
CH2),3.23(m,H,),2.96–2.85(m,2H,),1.25-0.91(s,3H,CH3).
Figure 10 show the fluorescence of the fluorine-containing FA-EDPM-GMA of the polymer P containing erbium (Er=0.5wt%) of embodiment 1 preparation
Spectrogram
Application examples 1
The fluorine-containing polymer containing erbium that embodiment 1 is obtained carries out the preparation of slab waveguide：Fluorine-containing contain what embodiment 1 obtained
Erbium polymer dissolves, and thin polymer film (by concentration and rotating speed control thicknesses of layers) is obtained by the method for spin coating, by film
Put into and (90 DEG C, 30min) are dried in baking oven to remove solvent, choose the template of bar shaped geometry, in the uviol lamp (UV of 400W
Lamp, maximum wavelength 365nm) under, at least 1min is exposed in image-wise exposure mode, then toasts 1h in 120 DEG C of baking oven, thoroughly
Complete the photocuring reaction of epoxy；It is developer solution from DMF solvent, the immersion of thin polymer film containing erbium that solidification crosslinking is finished is aobvious
30s in shadow liquid, is dried 30min in 120 DEG C of baking oven to remove DMF, obtains strip optical waveguide pattern.
Figure 11 show the stereoscan photograph of the fluorine-containing fiber waveguide pattern containing erbium polymer of application examples 1 preparation.
Claims (1)
1. a kind of synthesis can U-V writing fluorine-containing polymer waveguide containing erbium amplifier material method it is characterised in that：Including with
Lower step：
Step 1, have olefinic double bonds and epoxide group fluorochemical monomer (FA) synthesis
Weigh the THF that 2-200g hexafluoro bisphenol-a is dissolved in 20-2000mL, pour in the there-necked flask being placed in ice bath, add
0.65-65g triethylamine, after logical nitrogen gas stirring 20-60min, 0.53-53g propylene acyl chlorides is dissolved in 10-1000mLTHF simultaneously rapid
It is added drop-wise in above-mentioned solution, reaction 1-2h drops back from ice bath, continue reaction 12h at room temperature；Decompression at 95 DEG C of reactant liquor is steamed
Evaporate, after the oxolane in reaction system to be removed and triethylamine, add 20-200g epoxychloropropane, be transferred to 50 DEG C of constant temperature
In the there-necked flask of water-bath, after logical nitrogen 30-60min, add NaOH, 3-300g altogether every 0.5h；Then heat to 60 DEG C,
Isothermal reaction 6-12h, to complete cyclization, obtains crude product, and vacuum distillation removes remaining epoxychloropropane, and 70-80 DEG C true
Sky is dried 12h；After being cooled to room temperature, with anhydrous alcohol solution, stand 2-6h；With the salinity of organic membrane filtration residual, normal pressure
Boil off ethanol, obtain yellowish-brown transparent viscous liquid, be vacuum dried 2 days in 40-50 DEG C, obtain step 1 product (FA)；
Step 2, the synthesis containing Erbium organic complex (EDPM)
Adjacent phenanthrene quinoline (Phen) of the dibenzoyl methane (DBM) of 0.002mol and 0.001mol is added to 30mL ethanol solution
In, dissolving is heated on 50-70 DEG C of water bath with thermostatic control completely；Instill the methacrylic acid of 0.0011mol in this solution
(MAA), pour in the there-necked flask being placed in 25-35 DEG C of constant temperature oil bath, logical nitrogen simultaneously stirs, with a point liquid leakage after 30-60min
Bucket is slowly added dropwise the ethanol solution 20mL of the erbium chloride that concentration is 0.05mol/L, and drips the sodium hydrate aqueous solution of 1mol/L
Regulation pH value is 7.0-8.0, continues constant temperature stirring reaction 12h；Reactant liquor is separated with supercentrifuge, and gained solid phase ethanol is many
Secondary washing, 25-35 DEG C of vacuum drying 12h obtains containing Er complex (EDPM)；
Step 3, the fluorine-containing synthesis containing erbium polymer
0.3394g (the 0.377mmol) -2.4924g that 0.04mol fluorochemical monomer that step 1 is obtained, step 2 obtain
(2.77mmol) EDPM, 0.02mol GMA (GMA), 50mL DMF is added in 100mL there-necked flask,
After logical nitrogen gas stirring 30min, add 0.0342g azodiisobutyronitrile (AIBN), to obtain transparent copolymer molten for 75 DEG C of reaction 6h
Liquid；
Step 4, the fluorine-containing purifying containing erbium polymer
Take 100mL methyl alcohol to pour in beaker, be slowly added dropwise the transparent copolymer solution that step 3 obtains under fast stirring, produce
Raw white flock precipitate, stands deposition to be precipitated, suction filtration, 30 DEG C of vacuum drying 12h；By the solid dissolving of gained in THF, weight
Multiple above precipitation process, 30 DEG C of vacuum drying, gained solid is the fluorine-containing polymer containing erbium (PFA-EDPM-GMA) purifying.
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