CN102503962A - Preparation method of composite ligand barium precursor salt - Google Patents
Preparation method of composite ligand barium precursor salt Download PDFInfo
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- CN102503962A CN102503962A CN2011103080697A CN201110308069A CN102503962A CN 102503962 A CN102503962 A CN 102503962A CN 2011103080697 A CN2011103080697 A CN 2011103080697A CN 201110308069 A CN201110308069 A CN 201110308069A CN 102503962 A CN102503962 A CN 102503962A
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- barium
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- tmhd
- forerunner
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Abstract
The invention relates to a preparation method of a composite ligand barium precursor salt, which comprises the following steps: preparing anhydrous beta-diketone barium precursor salt (Ba(tmhd)2) from metal barium and 2,2,6,6-tetramethyl-3,5-heptanedione as raw materials, and then directly adding tetraethylenepentamine (C8H23N5) or pentaethylenehexamine (C10H28N6) as an auxiliary ligand into a reaction system to prepare the composite ligand barium precursor salt Ba(tmhd)2(L) together with the produced Ba(tmhd)2 under nitrogen gas protection. The composite ligand barium salt prepared with the method disclosed by the invention has high volatility.
Description
Technical field
The present invention relates to a kind of high temperature superconducting materia Preparation Method, be specifically related to a kind of preparation method of compound part barium forerunner salt.
Background technology
In recent years, the effective way that is considered to the long band of macro preparation two generations high-temperature superconductor with the long band technology of metal organic salt chemical Vapor deposition process (MOCVD) preparation yttrium barium copper oxide (YBCO) high-temperature superconductor.Except that MOCVD equipment and the thin film deposition processes, the performance of metal organic precursor salt, quality (purity, volatility, stability etc.) and cost also are one of decision gained YBCO superconducting thin film performance and key in application factor.At present both at home and abroad preparation YBCO superconducting thin film mainly adopts with 2,2,6,6-tetramethyl--3, and (beta-diketon is that the high volatile volatile yttrium, copper, barium metal organic salt of part is (like Y (tmhd) tmhd) to the 5-heptadione
3, Cu (tmhd)
2, Ba (tmhd)
2XH
2O).Yet compare with the organic salt of beta-diketon metallic yttrium and copper, because the atomic radius of barium is big, surface charge is low, cause the beta diketone of barium metal in receiving thermal process, to be easy to reunite, volatility reduces; Especially prepared barium metal organic salt Ba (tmhd) in alcohol/water mixed solvent
2XH
2Contain crystal water among the O; Be prone to cause the volatilization poor repeatability of barium salt and then influence yttrium, copper, barium metal composition and system film properties (Otway D J, Rees Jr W S, the Coordination Chemistry Reviews in the YBCO superconducting thin film; 2000,210:279-328).Therefore, preparation has temperature that high-volatile, anhydrous beta-diketon barium salt not only can reduce the MOCVD technological process, for the preparation high-quality thin film provides forerunner's salt of stable in properties, can also further reduce the preparation cost of YBCO superconducting thin film.At present with barium metal directly and the anhydrous beta-diketon barium salt of tmhd prepared in reaction mainly according to bibliographical information; But the volatile weight loss of gained barium salt under 270 ℃ of normal pressures (MOCVD technological temperature) only accounts for 3～5% (Drozdov AA of total volatile weight loss; Troyanov S I, Polyhedron, 1992; 11,2877; Drake S R, Hursthouse M B, Abdul-Malik K M, Otway D J, J.Chem.Soc.Dalton Trans.1993,2883; Turnipseed S B, Barkley R M, Sievers R E, Inorg Chem, 1991,30:1164).The organic cpds that contains aerobic, nitrogen-atoms has lone-pair electron, can be used as assistant ligand is coated on Ba (tmhd)
2Prevent ion aggregation around the barium ion of center, be expected to further improve Ba (tmhd)
2The volatility of forerunner's salt and solvability.Containing the imido grpup compound of polyether chain, single-ended amido imide based compound and end alkyl imido grpup compound like the employing described in the USP 6338873B1 is that assistant ligand prepares barium metal forerunner salt; But gained salt through the thermogravimetric analysis test chart reveal multistage weightlessness, thermostability is relatively poor, and the volatile weight loss rate of gained salt when 270 ℃ of MOCVD technological temperatures is less than 5%; Factor all can cause the center barium ion not protected fully, be easy to reunite to show that the polyether chain unit that contains Sauerstoffatom and barium metal ionic binding ability are weak, number of nitrogen atoms length few, the ligand compound molecular chain is short in the ligand compound etc.; And then causing gained forerunner salt poor heat stability, volatility is poor.In addition, prepare compound part barium forerunner salt at present mostly and all adopt following route: at first prepare Ba (tmhd)
2Pressed powder carries out secondary reaction with assistant ligand again and prepares compound part barium forerunner salt; In this route because Ba (tmhd)
2Poor stability forms hypoploid and then causes the salt volatility to reduce even under the cryogenic vacuum condition, preserve also can progressively take place to assemble.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art for preparing gained barium metal forerunner's salt volatility and poor heat stability, propose a kind of preparation method of compound part barium forerunner salt.The present invention is at preparation Ba (tmhd)
2Directly adopt in the process of forerunner's salt have double-end amino, long-chain imido grpup compound is assistant ligand, utilizes it to have strong interaction and barium ion is realized effective isolated characteristics with the central metal barium ion, not only can suppress Ba (tmhd)
2Forerunner's salt is assembled the formation hypoploid, can also be simplified the preparation technology who closes part barium forerunner salt greatly in last handling process.
The present invention at first adopts barium metal and 2,2,6,6-tetramethyl--3,5-heptadione (beta-diketon, tmhd) preparation anhydrous beta diketone barium forerunner salt Ba (tmhd)
2, be that assistant ligand directly adds the described compound part barium forerunner salt of preparation in the reaction system subsequently with the organic compounds containing nitrogen, described preparing method's synthesis technique step is following:
(1) at first, with barium metal and 2,2,6,6-tetramethyl--3, (beta-diketon is a reaction solvent for raw material, dry Skellysolve A or normal hexane tmhd) to the 5-heptadione.At first, barium metal and normal hexane are restrained in about 1: 100 milliliters ratio joins in the glass there-necked flask that prolong, drying tube and nitrogen air-intake duct are housed, and logical nitrogen is after 20 minutes; With 2,2,6; 6-tetramethyl--3,5-heptadione and normal hexane restrain by 1: 10 milliliters mixed is even, slowly is added dropwise to described mixing solutions in the there-necked flask through the normal pressure tap funnel then; Under 0～60 ℃ of temperature, reacting under the air tight condition of anhydrous and oxygen-free, until the barium metal completely dissolve;
(2) subsequently, with waiting organic compounds containing nitrogen assistant ligand L with the barium molar mass to be dissolved among the exsiccant organic solvent S, the volume ratio of described organic compounds containing nitrogen assistant ligand L and organic solvent S is 1 gram: 10 milliliters.Subsequently in the glass there-necked flask that prolong, drying tube and nitrogen air-intake duct are housed; The organic solvent S solution that under the air tight condition of anhydrous and oxygen-free, will contain organic compounds containing nitrogen assistant ligand L slowly is added dropwise in the glass there-necked flask; Under 0～60 ℃ of temperature, mix stirring reaction after 0.5～24 hour; Successively through the rotatory evaporator underpressure distillation desolventize, 60 ℃ of vacuum-dryings of vacuum drying oven, obtain the thick compound part barium forerunner salt of water white transparency, its chemical structural formula is Ba (tmhd)
2(L), wherein L is the organic compounds containing nitrogen assistant ligand, and yield is greater than 95%.
Organic compounds containing nitrogen assistant ligand L used in the above-mentioned technology is TEPA (C
8H
23N
5) or five ethene hexamine (C
10H
28N
6) in a kind of; Used dry organic solvent S is a kind of in normal hexane, Skellysolve A, chloroform or the THF.
Compared with prior art, advantage of the present invention is: with the barium metal raw material and 2,2,6, and 6-tetramethyl--3, the anhydrous beta-diketon barium of 5-heptadione prepared in reaction forerunner salt (Ba (tmhd)
2) after, directly be that assistant ligand L directly adds in the barium salt reaction system and can directly make the thick compound part barium forerunner salt Ba of water white transparency (tmhd) with the organic compounds containing nitrogen
2(L), this technology can suppress Ba (tmhd)
2Forerunner's salt is assembled formation hypoploid, while and is simplified the preparation technology who closes part barium forerunner salt greatly in last handling process; Reaction yield is greater than 95%, and gained barium salt steady quality, volatility are higher than Ba (tmhd)
2Forerunner's salt.Compare Ba (tmhd) through thermogravimetric analysis experiment (TGA)
2With assistant ligand protection Ba (tmhd)
2(L) TGA curve is visible: through the compound ligand metal barium salt Ba (tmhd) through organic compounds containing nitrogen assistant ligand L protection
2(L) not only volatile quantity significantly improves (bringing up to 88% from 78%), and volatilization temperature significantly reduces, and single stage method has significantly suppressed Ba (tmhd)
2The gathering of forerunner's salt, improved its volatility.
Description of drawings
Fig. 1 is compound part barium forerunner salt Ba (tmhd)
2(C
10H
28N
6) ir spectra;
Fig. 2 is compound part barium forerunner salt Ba (tmhd)
2(C
10H
28N
6) nuclear magnetic resonance spectrum (
1H-NMR with
13C-NMR);
Fig. 3 is anhydrous beta-diketon barium forerunner salt Ba (tmhd)
2With compound part barium forerunner salt Ba (tmhd)
2(C
10H
28N
6) TGA curve (10 ℃ of nitrogen protections, temperature rise rate/min).
Embodiment
Embodiment 1:
, 1500 milliliters of there-necked flasks of prolong, drying tube and nitrogen air-intake duct add 6.85 gram metal granellae and 700 milliliters of exsiccant Skellysolve As in being housed successively; Logical nitrogen restrained 2 with 18.4 after 20 minutes; 2; 6,6-tetramethyl--3 is after 5-heptadione (beta-diketon, tmhd) and 184 milliliters of Skellysolve As mix; Through the normal pressure tap funnel above-mentioned mixing solutions slowly is added dropwise in the there-necked flask, under the air tight condition of anhydrous and oxygen-free in 30 ℃ of following high degree of agitation reactions, until the completely dissolve of metal granellae; Subsequently; 120 milliliters of chloroformic solutions that contain 11.6 grams, five ethene hexamines slowly are added dropwise in the glass there-necked flask, under the air tight condition of anhydrous and oxygen-free, mixed stirring reaction 12 hours in 60 ℃; Successively through the rotatory evaporator underpressure distillation desolventize, 60 ℃ of vacuum-dryings of vacuum drying oven, obtain the thick compound part barium forerunner salt Ba (tmhd) of water white transparency
2(C
10H
28N
6), yield 98%.As shown in Figure 1, through IR spectroscopy (IR, cm
-1) sign compound part barium forerunner salt Ba (tmhd)
2(C
10H
28N
6) chemical structure: γ (NH
2), 3447; γ (NH), 3250; γ (CH
3, CH
2), 2955,2874; δ (NH
2), 1602; γ (C-O), 1591,1574; γ (C-C), 1550; γ (C-O)+γ (C-C)+γ (C-H): 1507; γ (C-C)+γ (C-H): 1438; γ (Ba-O)+γ (C-O): 1389; γ [C-(CH
3)
3]+δ (C-C): 1289,1262,1215; γ [C-(CH
3)
3]+δ (C-H): 1200; γ [C-(CH
3)
3]+γ (C-O): 1044,970,931; γ [C-(CH
3)
3]+γ (C-C-O)+γ (Ba-O): 817,794,780,739; γ (Ba-O): 595,478.As shown in Figure 2, through nuclear magnetic resonance spectrum (
1H-NMR with
13C-NMR) characterize compound part barium forerunner salt Ba (tmhd)
2(C
10H
28N
6) chemical structure: 1H NMR (CDCl
3Ppm): 1.12 (18H ,-CH
3); 5.7 (H ,-CH-); 2.87 (NH
2-CH
2-C
H 2-NH-); 2.57 (NH
2-C
H 2-); 2.48 (NH-C
H 2-C
H 2-NH-); 13C NMR (CDCl
3Ppm): 196.6 (C=O), 86.1 (CH), 41.2 (ipso C), 28.77 (CH
3); 41.6 (NH
2-
CH
2-); 49.6 (NH-C
H 2-C
H 2-NH-); 51.7～53.1 (NH
2-CH
2-C
H 2-NH-); As shown in Figure 3, compare Ba (tmhd) through thermogravimetric analysis experiment (TGA)
2With assistant ligand protection Ba (tmhd)
2(L) TGA curve is visible: through the compound ligand metal barium salt Ba (tmhd) through organic compounds containing nitrogen assistant ligand L protection
2(L) not only volatile quantity significantly improves: bring up to 88% from 78%, and volatilization temperature reduces significantly, single stage method has significantly suppressed Ba (tmhd)
2The gathering of forerunner's salt, improved its volatility.
Embodiment 2:
, 250 milliliters of there-necked flasks of prolong, drying tube and nitrogen air-intake duct add 1.37 gram metal granellae and 150 milliliters of exsiccant Skellysolve As in being housed successively; Logical nitrogen restrained 2,2,6 with 3.68 after 20 minutes; 6-tetramethyl--3; 5-heptadione (beta-diketon, tmhd) and 40 milliliters of Skellysolve As mix the back and through the normal pressure tap funnel above-mentioned mixing solutions slowly are added dropwise in the there-necked flask, under the air tight condition of anhydrous and oxygen-free, react in 0 ℃ of high degree of agitation, until the completely dissolve of metal granellae; Subsequently; 25 milliliters of dry Skellysolve A solution that contain 2.32 gram TEPAs slowly are added dropwise in the there-necked flask, under the air tight condition of anhydrous and oxygen-free, reacted 12 hours in 30 ℃; Successively through the rotatory evaporator underpressure distillation desolventize, 60 ℃ of vacuum-dryings of vacuum drying oven, obtain water white transparency thick, the compound part barium of high volatile volatile forerunner salt Ba (tmhd)
2(C
8H
23N
5), yield 97%.The compound ligand metal barium salt of gained Ba (tmhd)
2(C
8H
23N
5) results of IR and thermogravimetric analysis effect relatively (TGA) with embodiment 1.
Embodiment 3:
, 500 milliliters of there-necked flasks of prolong, drying tube and nitrogen air-intake duct restrain metal granellae and 350 milliliters of exsiccant normal hexanes with 3.425 successively in being housed; Logical nitrogen restrained 2,2,6 with 9.2 after 20 minutes; 6-tetramethyl--3; 5-heptadione (beta-diketon, tmhd) and 40 ml n-hexanes mix the back and through the normal pressure tap funnel described mixing solutions slowly are added dropwise in the there-necked flask, under the air tight condition of anhydrous and oxygen-free, react in 60 ℃ of high degree of agitation, until the completely dissolve of metal granellae; Subsequently; 60 milliliters of dry hexane solutions that contain 5.8 gram TEPAs slowly are added dropwise in the there-necked flask, under the air tight condition of anhydrous and oxygen-free, reacted 24 hours in 0 ℃; Successively through the rotatory evaporator underpressure distillation desolventize, 60 ℃ of vacuum-dryings of vacuum drying oven, obtain water white transparency thick, the compound part barium of high volatile volatile forerunner salt Ba (tmhd)
2(C
8H
23N
5), yield 97%.
The compound ligand metal barium salt of gained Ba (tmhd)
2(C
8H
23N
5) results of IR and thermogravimetric analysis effect relatively (TGA) with embodiment 1.
Embodiment 4:
In 2500 milliliters of there-necked flasks of prolong, drying tube and nitrogen air-intake duct are housed successively with 13.7 the gram metal granellaes and and 1400 milliliters of exsiccant normal hexanes; Logical nitrogen restrained 2 with 36.8 after 20 minutes; 2; 6,6-tetramethyl--3,5-heptadione (beta-diketon, tmhd) and 400 milliliters of exsiccant normal hexanes mix the back and slowly are added dropwise to described mixing solutions in the there-necked flask through the normal pressure tap funnel; Under the air tight condition of anhydrous and oxygen-free, react, until the completely dissolve of metal granellae in 50 ℃ of high degree of agitation; Subsequently; 250 milliliters of tetrahydrofuran solutions that contain 23.2 grams, five ethene hexamines slowly are added dropwise in the there-necked flask, under 25 ℃ of nitrogen protections, were reacting 0.5 hour under the air tight condition of anhydrous and oxygen-free; Successively through the rotatory evaporator underpressure distillation desolventize, 60 ℃ of vacuum-dryings of vacuum drying oven, obtain water white transparency thick, the compound part barium of high volatile volatile forerunner salt Ba (tmhd)
2(C
10H
28N
6), yield 96%.
The compound ligand metal barium salt of gained Ba (tmhd)
2(C
10H
28N
6) results of IR and thermogravimetric analysis effect relatively (TGA) with embodiment 1.
Claims (3)
1. the preparation method of a compound part barium forerunner salt is characterized in that at first adopting barium metal and 2,2,6,6-tetramethyl--3,5-heptadione (beta-diketon, tmhd) preparation anhydrous beta diketone barium forerunner salt Ba (tmhd)
2, be that assistant ligand directly adds in the reaction system the described compound part barium forerunner salt of preparation subsequently with the organic compounds containing nitrogen, described preparing method's synthesis step order as follows:
At first, barium metal and normal hexane are restrained in 1: 100 milliliters ratio joins in the glass there-necked flask that prolong, drying tube and nitrogen air-intake duct are housed, and logical nitrogen is after 20 minutes; With 2,2,6; 6-tetramethyl--3,5-heptadione and normal hexane restrain by 1: 10 milliliters mixed is even, slowly is added dropwise to described mixing solutions in the there-necked flask through the normal pressure tap funnel afterwards; Under 0～60 ℃ of temperature, reacting under the air tight condition of anhydrous and oxygen-free, until the barium metal completely dissolve; Subsequently, will be dissolved among the exsiccant organic solvent S with the organic compounds containing nitrogen assistant ligand L of molar mass such as barium, the volume ratio of described organic compounds containing nitrogen assistant ligand L and organic solvent S is 1 gram: 10 milliliters; The organic solvent S solution that under the air tight condition of anhydrous and oxygen-free, will contain organic compounds containing nitrogen assistant ligand L slowly is added dropwise in the glass there-necked flask; Under 0～60 ℃ of temperature, mix stirring reaction after 0.5～24 hour; Desolventize through the rotatory evaporator underpressure distillation successively; 60 ℃ of vacuum-dryings of vacuum drying oven obtain described compound part barium forerunner salt Ba (tmhd)
2(L).
2. the preparation method of compound part barium forerunner salt according to claim 1 is characterized in that described organic compounds containing nitrogen assistant ligand L is TEPA (C
8H
23N
5) or five ethene hexamine (C
10H
28N
6).
3. the preparation method of compound part barium forerunner salt according to claim 1 is characterized in that described dry organic solvent S is a kind of in normal hexane, Skellysolve A, chloroform or the THF.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707159A (en) * | 2018-05-29 | 2018-10-26 | 北京交通大学 | A kind of preparation method and application of high volatile composite ligand barium precursor salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023635A1 (en) * | 1998-10-21 | 2000-04-27 | The President And Fellows Of Harvard College | Liquid compounds for formation of materials containing alkaline earth metals |
| CN102153568A (en) * | 2011-02-10 | 2011-08-17 | 中国科学院电工研究所 | Preparation method of composite ligand barium precursor salt |
-
2011
- 2011-10-11 CN CN2011103080697A patent/CN102503962A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023635A1 (en) * | 1998-10-21 | 2000-04-27 | The President And Fellows Of Harvard College | Liquid compounds for formation of materials containing alkaline earth metals |
| CN102153568A (en) * | 2011-02-10 | 2011-08-17 | 中国科学院电工研究所 | Preparation method of composite ligand barium precursor salt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707159A (en) * | 2018-05-29 | 2018-10-26 | 北京交通大学 | A kind of preparation method and application of high volatile composite ligand barium precursor salt |
| CN108707159B (en) * | 2018-05-29 | 2019-11-05 | 北京交通大学 | A kind of preparation method and application of high volatile composite ligand barium precursor salt |
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