CN109836047B - Organosilicon-rare earth derivative, synthesis method thereof and application of organosilicon-rare earth derivative in preparation of rare earth doped optical fiber - Google Patents
Organosilicon-rare earth derivative, synthesis method thereof and application of organosilicon-rare earth derivative in preparation of rare earth doped optical fiber Download PDFInfo
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Abstract
The invention discloses a raw material for preparing a rare earth doped optical fiber preform, which is an organic silicon-rare earth derivative with a chemical structural general formula shown as formula 1-1 or formula 1-2, wherein M represents trivalent rare earth metal ions, X represents monovalent anions, R represents monovalent anions1‑R7Including but not limited to one or more of methoxy, ethoxy, methyl, ethyl, phenyl, vinyl, allyl, siloxane, vinylsiloxy, and the like. The rare earth doped optical fiber perform produced by taking the derivative as a raw material has high utilization rate of rare earth ions, the rare earth ions are uniformly distributed in the optical fiber perform longitudinally, and the refractive index fluctuation is small.
Description
Technical Field
The invention relates to an organic silicon-rare earth derivative, a synthesis method thereof and application of the organic silicon-rare earth derivative as a raw material to preparation of a rare earth doped optical fiber, belonging to the field of optical fiber manufacturing.
Technical Field
The rare earth doped optical fiber prefabricated rod is a key material for producing optical fiber amplifiers and optical fiber lasers. Compared with the traditional semiconductor laser amplifier, the optical fiber amplifier can directly amplify signals in all light without complex processes such as photoelectric conversion, electro-optical conversion, signal regeneration and the like, has the characteristics of high gain, large bandwidth, low noise, polarization insensitive gain and low lead-in loss within the working wavelength range, has good transparency, and is particularly suitable for relay amplification of long-distance optical communication. The optical fiber amplifier lays an important technical foundation for realizing high-capacity and all-optical communication. Rare earth doped fibers are an important component of high power fiber lasers and are the main factors determining the performance of the high power fiber lasers.
At present, the rare earth doped optical fiber preform is produced mainly based on three traditional optical fiber preform production methods: melting method, in tubesThe method, the outside of tubes method, carries out physical doping in the production process, and introduces rare earth elements, such as: the method adopts a 'hydrolysis-melting combined' method to produce a mixture of rare earth oxide and silicon dioxide, and the mixture is smelted at high temperature to prepare a rare earth doped quartz glass rod (CN 102351414A); soaking a nano-porous quartz glass rod or quartz powder into a mixed solution containing doped ions, and sintering the soaked nano-porous quartz glass rod or quartz powder into a compact and transparent quartz glass core rod (CN102503113A, CN 105837025A); SiO nano-pore2Adding the powder into a suspension of a rare earth inorganic salt solution, drying, dehydrating and granulating to form ion-adsorbed SiO2Sintering the particles to form a rare earth doped silicon oxide core rod (CN 102992613B); depositing an inner cladding and a loose soot core layer in sequence in a deposition tube, injecting a solution containing rare earth elements into the deposition tube, and fusing the deposition tube, the inner cladding and the loose soot core layer to form a solid preform (CN102515501B, CN1500069, US 5711782A and US 5262365A); depositing a soot core layer of the rare earth element doped optical fiber preform by VAD method, soaking the core layer soot in a solution containing rare earth element, and vitrifying the soaked core layer soot in a high temperature furnace to obtain the core layer (CN102108008B) of the rare earth element doped optical fiber preform.
The doping process has two main disadvantages: 1. no matter the powder, the porous glass rod or the silicon dioxide particles are doped, the steps of soaking and adsorbing by using a rare earth solution are carried out, and closed device equipment is required to be separated among the working procedures of deposition, soaking, drying and the like, so that impurities are easily introduced to influence the performance of the rare earth doped optical fiber preform; 2. the pure physical doping mode among the raw materials is difficult to overcome the problems that the doping of the prefabricated rod is uneven and the doping content is difficult to quantitatively control, so that the longitudinal absorption coefficient of the rare earth doped optical fiber prefabricated rod is different, and the control of the nonlinear effect of the optical fiber after drawing is not facilitated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel organic silicon-rare earth derivative aiming at the defects in the prior art, and the rare earth doped optical fiber preform produced by taking the derivative as a raw material has high utilization rate of rare earth ions, uniform longitudinal distribution of the rare earth ions in the optical fiber preform and small refractive index fluctuation.
The technical scheme adopted by the invention for solving the problems is as follows:
a novel organosilicon-rare earth derivative has a chemical structural general formula shown as formula 1-1 or formula 1-2, wherein M represents trivalent rare earth metal ion, and X represents monovalent anion; r in the formula 1-11-R3And R in the formula 1-21-R7Represent the same or different functional groups and are respectively selected from one or more of methoxyl, ethoxyl, methyl, ethyl, phenyl, vinyl, allyl, siloxane group, vinyl siloxane group and the like.
According to the scheme, the trivalent rare earth metal ions are selected from ions of rare earth metals such as Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
According to the above scheme, the monovalent anion includes, but is not limited to chloride, nitrate, benzene sulfonate, tert-pentoxy, triflate, methylsulfonate, caprylate or perfluorocaprylate, etc.
The preparation method of the organic silicon-rare earth derivative comprises the following synthetic steps:
(1) dissolving rare earth salt in an anhydrous organic solvent to prepare a rare earth salt solution;
(2) taking organic silicon with the same molar weight as the rare earth salt, dripping the rare earth salt solution into the organic silicon in an anhydrous and oxygen-free environment, and then continuously stirring fully to ensure that the reaction is fully carried out; after the reaction is finished, the organic solvent is removed by rotary evaporation, and the organic silicon-rare earth derivative shown as the formula 1 is obtained.
According to the scheme, the chemical structural general formula of the rare earth salt can be MX3Wherein M, X has the same meaning as in formula 1-1 or formula 1-2.
According to the above scheme, the anhydrous organic solvent includes but is not limited to DMF, cyclohexane, dioxane, carbon tetrachloride, nitrobenzene, etc., preferably Cyclohexane (CYH).
According to the scheme, the general formula of the chemical structure of the organic silicon is shown as a formula 2-1 or a formula 2-2, and R in the formula 2-11-R3And R in the formula 2-21-R7Represent the same or different functional groups and are respectively selected from one or more of methoxyl, ethoxyl, methyl, ethyl, phenyl, vinyl, allyl, siloxane group, vinyl siloxane group and the like. The organosilicon includes one or more of tetramethyltetravinylcyclotetrasiloxane, 1,3,5,7 tetravinyl-1, 3,5,7 tetramethylcyclotetrasiloxane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethyldivinyldisiloxane, methyl-vinylsiloxane, allyltriphenylsilane, etc.
According to the scheme, in the step (1), the molar concentration of the rare earth salt solution is between 5 and 20 percent, and the preferred molar concentration is 10 percent.
According to the scheme, in the step (2), the rare earth salt solution is dripped into the organic silicon for 0.5-1.5 hours, preferably 1 hour; controlling the reaction temperature between 30 ℃ and 70 ℃, preferably 50 ℃; after the completion of the dropwise addition, the stirring is continued sufficiently for 1 to 3.5 hours, preferably for 2.5 hours.
In the synthesis process of the organic silicon-rare earth derivative, a chemical reaction equation mainly involved is shown as a formula 3-1 or a formula 3-2.
On the premise of not changing the structure of the existing preform production equipment, the rare earth doped optical fiber preform can be prepared by replacing the silicon-containing raw material with the organic silicon-rare earth derivative.
Compared with the prior art, the invention has the beneficial effects that:
1. the raw material organosilicon-rare earth derivative for preparing the rare earth doped optical fiber preform is a silicon source (silicon-containing raw material) and a rare earth raw material, and the derivative ensures uniform distribution between silicon elements and rare earth elements from the aspect of molecular structure, so that the problems of uneven doping and difficult quantitative control in the conventional doped optical fiber preform production are avoided from the source;
2. the rare earth doped optical fiber preform produced by taking the organic silicon-rare earth derivative as the raw material has the advantages of high utilization rate of rare earth ions, uniform longitudinal distribution of the rare earth ions in the optical fiber preform, small refractive index fluctuation and high slope efficiency of optical fiber laser obtained by drawing.
3. When the organic silicon-rare earth derivative is used for preparing the rare earth doped optical fiber preform, a new procedure is not needed to be added in the production process of the preform, only the raw materials are changed, the production equipment and the process route can utilize the existing mature technology, the universality and the adaptability are strong, the utilization rate of rare earth ions can reach more than 50 percent, and the preparation method is an environment-friendly and resource-saving production mode.
Drawings
FIG. 1 is a graph showing the laser slope efficiency of an erbium-doped fiber drawn from a solid preform obtained in example 3.
FIG. 2 is a graph showing the laser slope efficiency of ytterbium doped fiber drawn from the solid preform obtained in example 4.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
The embodiment provides an organosilicon-rare earth derivative, the general formula of the chemical structure is shown as formula 4, the organosilicon-rare earth derivative is prepared by reacting vinyl triethoxysilane with erbium chloride, and the chemical reaction formula is shown as formula 5.
The specific preparation process of the organic silicon-rare earth derivative comprises the following steps:
(1) taking a dry 500ml single-mouth ground flask, and adding tetrafluoro stirring slurry; adding 0.2mol and 54.75g of erbium chloride and 2mol and 168g of cyclohexane solvent into the flask, and fully stirring and dissolving to obtain an erbium chloride solution with the molar concentration of 10%;
(2) pre-drying, and N2Fully replaced 1000ml three-necked bottle in N2Adding 0.2mol and 38g of vinyltriethoxysilane under protection, and heating to 50 ℃; and (2) dropwise adding the erbium chloride solution obtained in the step (1) into the three-necked bottle, finishing the addition within about 1 hour, continuously reacting for 2.5 hours, performing rotary evaporation, and purifying to obtain 88.1g of the organic silicon rare earth derivative with the chemical structure shown as the formula 4.
Through tests, the organosilicon rare earth derivative obtained in the embodiment has a molecular ion peak MS (ES +) on a mass spectrometer of m/e 463.5; elemental analysis, calculated: c20.71, H3.88, O10.36, test values: c20.73, H3.85, O10.34.
Example 2
The embodiment provides an organosilicon-rare earth derivative, the general formula of the chemical structure is shown as formula 6, the organosilicon-rare earth derivative is prepared by reacting tetramethyl tetravinylcyclotetrasiloxane and ytterbium octoate, and the chemical reaction equation is shown as formula 7.
The specific preparation process of the organic silicon-rare earth derivative comprises the following steps:
(1) taking a dry 500ml single-mouth ground flask, and adding tetrafluoro stirring slurry; adding 0.2mol and 120.4g of ytterbium octoate and 2mol and 168g of cyclohexane solvent into the flask, and fully stirring and dissolving to obtain a ytterbium octoate solution with the molar concentration of 10%;
(2) pre-drying, and N2Fully-replaced 1000ml three-mouth bottleIn N2Adding 0.2mol and 68.8g of tetramethyltetravinylcyclotetrasiloxane under protection, and heating to 50 ℃; and (2) dropwise adding the ytterbium caprylate solution obtained in the step (1) into the three-necked bottle, finishing the addition within about 1 hour, continuously reacting for 2.5 hours, performing rotary evaporation, and purifying to obtain 168.2g of the organic silicon rare earth derivative with the chemical structure shown in the formula 6.
Through tests, the organosilicon rare earth derivative obtained in the embodiment has a molecular ion peak MS (ES +) on a mass spectrometer, wherein m/e 946; elemental analysis, calculated: c45.67, H7.29, O16.91, test value: c45.63, H7.31, O16.88.
Example 3
The erbium-doped optical fiber preform is produced by using an organic silicon-rare earth derivative with a chemical structure as formula 4 as a raw material (both a silicon source and a rare earth raw material) and using a conventional MCVD (modified chemical vapor deposition) process, and the production process comprises the following steps:
preparing a 1200mm quartz liner tube, flame polishing at 1900-2100 deg.C to eliminate the scratches, impurities, bubbles and other defects on the inner wall of the liner tube, and depositing 10-15 SiO-containing layers on the inner wall of the liner tube at 1850-1950 deg.C2-P2O5The inner cladding of-F adopts reverse deposition at 1530-1580 ℃, organic silicon-rare earth derivative gas with the chemical structure as formula 4 is introduced to deposit a loose core layer, and He and O are introduced at 1150-1200 DEG C2，Cl2Dehydrating the loose core layer, and finally fusing and shrinking the quartz tube into a solid prefabricated rod at 2220-2300 ℃.
Testing by an electronic probe to obtain the core Er of the solid preform2O3The content of (b) is 0.5 wt%, and the laser slope efficiency of the drawn fiber reaches 75.2% (as shown in FIG. 1). Through measurement and calculation, the utilization rate of the organic silicon-rare earth derivative as a rare earth raw material is 53.8%, the longitudinal refractive index distribution of the organic silicon-rare earth derivative is shown in a table 1 through testing, and the erbium-doped optical fiber preform prepared by adopting the organic silicon-rare earth derivative with the chemical structure shown in the formula 4 as the raw material has better longitudinal uniformity.
TABLE 1
Example 4
The organic silicon-rare earth derivative with the chemical structure as formula 6 is used as a silicon-containing raw material and a rare earth raw material, and a conventional MCVD process is used for producing the ytterbium-doped optical fiber preform, wherein the production process comprises the following steps:
preparing a 1200mm quartz liner tube, flame polishing at 1900-2100 deg.C to eliminate the scratches, impurities, bubbles and other defects on the inner wall of the liner tube, and depositing 10-15 SiO-containing layers on the inner wall of the liner tube at 1850-1950 deg.C2-P2O5The inner cladding of-F adopts reverse deposition at 1530-1580 ℃, organic silicon-rare earth derivative gas with the chemical structure shown as formula 6 is introduced to deposit a loose core layer, and He and O are introduced at 1150-1200 DEG C2，Cl2Dehydrating the loose core layer, and finally fusing and shrinking the quartz tube into a solid prefabricated rod at 2220-2300 ℃.
Testing with an electronic probe to obtain core Yb of solid preform2O3The content of (A) is 0.7 wt%, and the laser slope efficiency of the drawn fiber reaches 72.8% (as shown in FIG. 1). Through measurement and calculation, the utilization rate of the organic silicon-rare earth derivative as a rare earth raw material is 51.3%, the longitudinal refractive index distribution of the organic silicon-rare earth derivative is shown in a table 2 by testing, and the ytterbium-doped optical fiber preform prepared by adopting the organic silicon-rare earth derivative with the chemical structure shown in the formula 6 as the raw material has better longitudinal uniformity.
TABLE 2
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (9)
1. An organosilicon-rare earth derivative for preparing a rare earth doped optical fiber preform is characterized in that the general formula of the chemical structure of the organosilicon-rare earth derivative is shown as formula 1-1 or formula 1-2, wherein M represents trivalent rare earth metal ions, and X represents univalent anions;
r in the formula 1-11-R3And R in the formula 1-21-R7Represents the same or different functional groups and respectively comprises one or more of methoxyl, ethoxyl, methyl, ethyl, phenyl, vinyl, allyl, siloxane group and vinyl siloxane group.
2. The organo-rare earth derivative for preparing a rare earth doped optical fiber preform according to claim 1, characterized in that the trivalent rare earth metal ion is selected from ions of rare earth metals Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; the monovalent anion includes one of chloride, nitrate, benzene sulfonic acid group, tert-pentyloxy group, trifluoro sulfonic acid group, methylsulfonic acid group, caprylic acid group or perfluorocaprylic acid group.
3. The process for preparing organosilicon-rare earth derivatives according to claim 1, characterized by the following synthesis steps:
(1) dissolving rare earth salt in an anhydrous organic solvent to prepare a rare earth salt solution;
(2) taking organic silicon with the same molar weight as the rare earth salt, dripping the rare earth salt solution into the organic silicon in an anhydrous and oxygen-free environment, and then continuously stirring fully to ensure that the reaction is fully carried out; after the reaction is finished, the organic solvent is removed by rotary evaporation to obtain the organic silicon-rare earth derivative shown as the formula 1-1 or the formula 1-2.
4. The method according to claim 3, wherein the rare earth salt has a chemical structure represented by the general formula MX3Wherein M represents a trivalent rare earth metal ion and X represents a monovalent anion;
the general formula of the chemical structure of the organic silicon is shown as a formula 2-1 or a formula 2-2, and R in the formula 2-11-R3And R in the formula 2-21-R7Represents the same or different functional groups and respectively comprises one or more of methoxyl, ethoxyl, methyl, ethyl, phenyl, vinyl, allyl, siloxane group and vinyl siloxane group.
5. The method according to claim 3, wherein the anhydrous organic solvent comprises DMF, cyclohexane, dioxane, carbon tetrachloride, nitrobenzene.
6. The method according to claim 3, wherein the silicone comprises tetramethyltetravinylcyclotetrasiloxane, 1,3,5,7 tetravinyl-1, 3,5,7 tetramethylcyclotetrasiloxane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethyldivinyldisiloxane, methyl-vinylsiloxane, allyltriphenylsilane.
7. The process according to claim 3, wherein in step (1), the rare earth salt solution has a molar concentration of between 5% and 20%.
8. The production method according to claim 3, characterized in that in the step (2), the rare earth salt solution is added dropwise to the silicone for 0.5 to 1.5 hours; controlling the reaction temperature between 30 ℃ and 70 ℃; after the dropwise addition is completed, the mixture is continuously and fully stirred for 1 to 3.5 hours.
9. A rare earth doped optical fiber preform prepared by using the organosilicon-rare earth derivative according to claim 1.
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| US4826288A (en) * | 1987-04-09 | 1989-05-02 | Polaroid Corporation, Patent Department | Method for fabricating optical fibers having cores with high rare earth content |
| US6620748B1 (en) * | 1998-10-20 | 2003-09-16 | Asahi Glass Co Ltd | Light-amplifying glass, light-amplifying medium and resin-coated light-amplifying medium |
| CN1693416A (en) * | 2005-05-25 | 2005-11-09 | 浙江大学 | Temp. sensitive sensing luminescent material mixed with double rare earth organic complex and preparation process thereof |
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