CN103059052B - A kind of rare earth compound and synthesis technique thereof - Google Patents
A kind of rare earth compound and synthesis technique thereof Download PDFInfo
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- CN103059052B CN103059052B CN201210211935.5A CN201210211935A CN103059052B CN 103059052 B CN103059052 B CN 103059052B CN 201210211935 A CN201210211935 A CN 201210211935A CN 103059052 B CN103059052 B CN 103059052B
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- -1 rare earth compound Chemical class 0.000 title claims abstract description 106
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 47
- MFSHNFBQNVGXJX-UHFFFAOYSA-N 2-oxo-1,2-dihydroquinoline-4-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(=O)NC2=C1 MFSHNFBQNVGXJX-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 229910052693 Europium Inorganic materials 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 23
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 16
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 15
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 7
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 15
- 150000002910 rare earth metals Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- MDFCXYVJUZMYCJ-UHFFFAOYSA-N europium gadolinium Chemical compound [Eu][Gd] MDFCXYVJUZMYCJ-UHFFFAOYSA-N 0.000 description 9
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000005594 diketone group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000002178 europium compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021644 lanthanide ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000000176 photostabilization Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- RGZSQWQPBWRIAQ-HUUCEWRRSA-N (2r)-6-methyl-2-[(1s)-4-methylcyclohex-3-en-1-yl]hept-5-en-2-ol Chemical compound CC(C)=CCC[C@@](C)(O)[C@H]1CCC(C)=CC1 RGZSQWQPBWRIAQ-HUUCEWRRSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of rare earth compound and synthesis technique thereof, the chemical general formula of described rare earth compound is as follows:
Description
Technical field
The invention belongs to rare earth metal field, be specifically related to a kind of rare earth compound and synthesis technique thereof.
Background technology
Rare earth compound is the compound that rare earth metal and other substance reactions generate.Thulium is the general name of scandium, yttrium, group of the lanthanides 17 kinds of elements in the periodic table of chemical element III B race, conventional R or Re represents, their title and chemical symbol are scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) respectively.An important use of rare earth compound uses as fluorescent material, is mainly used in the marker field of data carrier and file goods.
In rare-earth luminescent material, the major ingredient of the red fluorescence material in earlier technique is diketone rare earth metal europium complex or europium Carboxylates.With the UV rayed diketone rare earth metal europium complex of wavelength 365nm or 254nm, diketone rare earth metal europium complex can be made to excite, thus launch strong red fluorescence, but the shortcoming of diketone rare earth metal europium complex is that light stability and thermostability are poor; Compared with diketone rare earth metal europium complex, europium Carboxylates has higher thermostability, but europium Carboxylates only just can send stronger fluorescence at the shorter UV light of use as during 254nmUV rayed, and the fluorescence sent under 365nmUV rayed is very weak.
In order to solve the defect that above-mentioned red fluorescence material exists, Chinese patent literature CN1608072A discloses a kind of rare earth compound, described rare earth compound is at least one rare earth metal and the synthetics being carboxylic acid monomer with 2-hydroxyquinoline-4-carboxylic acid, and corresponding chemical general formula is:
Wherein A and B is the different rare earth metals being selected from europium, terbium, gadolinium, yttrium, neodymium, lanthanum and cerium, and C is the alkaline-earth metal from calcium, strontium and barium, L
1-L
5represent a kind of substituting group or H, 1>x+y>0, N=x+y+2 independently of each other.This compound can launch the fluorescence of high strength under the UV rayed of 365nm, also has excellent thermostability and photostabilization simultaneously.
Although above-mentioned rare earth compound improves the fluorescence intensity under the thermostability of red fluorescence material, photostabilization and long wave UV rayed, but the resistance to acid solution of above-mentioned rare earth compound and resistance to alkali lye poor, the phenomenon that generation burn into comes off is easy to when running into the pollutent of acidity or alkalescence by the printing that it is made, cause fluorescence to disappear, thus limit the widespread use of this fluorescent material.In addition, the solubleness of above-mentioned rare earth compound powder in organic dissolution is extremely low, dispersiveness in ketone, ester class and alcohols material is poor, when reality uses, the surface of goods is transferred to again after normally being mixed with above-mentioned ketone, ester class and alcohols material by rare earth compound powder, and the bad dispersibility of above-mentioned rare earth compound powder just causes it that phenomenon of reuniting easily occurs in use, cannot be dispersed, have impact on giving full play to of fluorescence property.
Summary of the invention
The technical problem that the present invention solves be in prior art for the resistance to acid solution of the rare earth compound of red fluorescence material and resistance to alkali lye poor, be easy to when running into the pollutent of acidity or alkalescence by the printing that it is made that corrosion occurs and cause fluorescence extinction tests and the poor problem of dispersiveness in ketone, ester class and alcohols material.And then provide a kind of acid resistance and alkali resistance is excellent, the good rare earth compound of dispersing property, present invention also offers the synthesis technique of this rare earth compound.
The technical scheme of the rare earth compound described in the present invention and synthesis technique thereof is:
A kind of rare earth compound, is characterized in that, described compound corresponds to general formula:
Wherein, x > 0, y >=0; M > 0, n > 0, m+n=3 (x+y); Z=x+y; Re is any one in the thulium except Eu.
Re is any one in Gd, Y, La, Tb.
The synthesis technique of described rare earth compound, comprises following steps:
(1) 2-hydroxyquinoline-4-carboxylic acid, Whitfield's ointment dibasic acid esters and alkaline matter is utilized to carry out reacting the carboxylate salt both generating in water or alcohol or water-ol mixed solvent;
Or utilize 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters in water or alcohol or water-ol mixed solvent, to carry out reacting the carboxylate salt both generating respectively with alkaline matter respectively;
The mol ratio of described 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters is 3:7 ~ 7:3, and the pH value of the carboxylic acid salt solution that reaction generates controls 6 ~ 8;
(2) 2-hydroxyquinoline-4-carboxylic acid step (1) generated and the metal-salt of the carboxylate salt of Whitfield's ointment dibasic acid esters and the metal-salt of Eu or Eu react with the mixing solutions of other rare earth metal salt, temperature of reaction is 20 ~ 80 DEG C, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) reacted with 1,10-phenanthroline in alcoholic solvent by described filter cake, temperature of reaction is 50 ~ 80 DEG C, filters, washs, dries, namely obtain described rare earth compound to the throw out that reaction generates.
In described step (1), the mol ratio of 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters is 3:7 ~ 7:3.
Alcohol in described step (1) and step (3) is ethanol or Virahol.
Described alkaline matter is one or more mixtures in sodium hydroxide, potassium hydroxide and organic amine.
In described step (2), in described carboxylate salt and metal-salt, the mol ratio of metal ion is 3:1.
Metal-salt or other rare earth metal salt of the middle Eu of described step (2) are hydrochloride or nitrate.
Bake out temperature in described step (3) is 60 ~ 105 DEG C.
Filter cake is 0.5 ~ 3 hour with the reaction times of 1,10-phenanthroline in alcoholic solvent in described step (3).
Described rare earth compound is used as the purposes of red high-visibility pigment.
The synthesis technique of rare earth compound of the present invention, step (1) utilizes 2-hydroxyquinoline-4-carboxylic acid, Whitfield's ointment dibasic acid esters and alkaline matter to carry out reaction in water or alcohol or water-ol mixed solvent and generates carboxylate salt, the mol ratio of described 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters is 3:7 ~ 7:3, and the pH value of the carboxylic acid salt solution that reaction generates controls 6 ~ 8; The mol ratio that the present invention limits described 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters is 3:7 ~ 7:3, and more preferably 1:1, reason is, the red high-visibility pigment synthesized in this ratio range is acidproof, alkaline resistance properties is optimum; In addition, the present invention also controls the pH value of the carboxylic acid salt solution of reaction generation 6 ~ 8, is that technique described in the present invention has higher productive rate because under partial neutral pH value condition.
The metal-salt of described carboxylate salt and Eu or the metal-salt of Eu and the mixture of other rare earth metal salt react by step (2), and temperature of reaction is 20 ~ 80 DEG C, filters and washs, obtain filter cake to the precipitation that reaction generates; Here arranging temperature of reaction is 20 ~ 80 DEG C, and reason is that this temperature range is conducive to sedimentary generation, too high or too low productive rate and the purity that all can reduce target product.
Described filter cake reacts with 1,10-phenanthroline by step (3) in alcoholic solvent, and temperature of reaction is 50 ~ 80 DEG C, and arranging temperature of reaction is here 50 ~ 80 DEG C, and this temperature is provided with the removing being beneficial to water molecules in compound.It is 0.5 ~ 3 hour that the present invention goes back the defined reaction time, reason is, it is too short that reaction times is arranged, then reaction cannot fully be carried out, thus the productive rate of impact reaction, and reaction times setting is long, in actual applications, can affect again the efficiency of production, the present invention is 0.5 ~ 3 hour by the defined reaction time, effectively prevent above-mentioned two situations.
The advantage of the rare earth compound described in the present invention is:
(1) rare earth compound of the present invention is visual lower colourless, the red fluorescence of high strength can be launched under the UV rayed of 365nm, there is good acid resistance and alkali resistance, the phenomenon that burn into comes off and fluorescence disappears can not be there is when running into the pollutent of acidity or alkalescence by the printing that it is made, thus be conducive to widespread use and the popularization of this fluorescent material; Simultaneously, rare earth compound of the present invention, dispersiveness in ketone, ester class and alcohols material is better, with the ink that the powder of described rare earth compound is made, powder is uniformly dispersed, the phenomenon of reuniting can not be there is, the fluorescence property of rare earth compound can be not fully exerted.
(2) rare earth compound of the present invention, also restriction Re is preferably any one in Gd, Y, La, Tb further, and the advantage arranged like this is: there are some researches show, add non-fluorescence inert lanthanide ions (as La in luminescent rare earth complexes system
3+, Gd
3+, Y
3+deng), form different dinuclear complex, luminous intensity can be made to improve.Inert lanthanide ions
5d
0the triplet energy level of a little higher than part of energy level, thus part energy can not pass to coexisting ion, inert ion rare earth compounding and rare earth ion complex molecule spacing very near, the energy that inert ion part is absorbed likely is transferred to rare earth ion adjacent with it, thus greatly improves rare earth ion fluorescence intensity.The effect that this energy is concentrated to a core, is called " dense poly-effect "; In addition, as the Eu ion of rare earth compound luminescence center of the present invention, cost is higher, in design and synthesize in rare earth compound of the present invention and suitably add non-fluorescence inert lanthanide ions, effectively can also reduce the preparation cost of rare earth compound.
Embodiment
More being convenient to make content of the present invention understand, below in conjunction with embodiment, technical solutions according to the invention being further elaborated.
Embodiment 1
A kind of europium compound, its chemical formula is:
The synthesis technique of this europium compound is as follows:
(1) be dissolved in the solution of the 600ml water containing 6.00 grams of (0.15mol) sodium hydroxide by 14.20 grams of (0.075mol) 2-hydroxyquinoline-4-carboxylic acids, 19.35 grams of (0.075mol) Whitfield's ointment dibasic acid esters, the pH value of the carboxylic acid salt solution that reaction generates is 7.
(2) 8.8 grams of europium sesquioxides (0.025mol) be dissolved in a certain amount of 37% hydrochloric acid, be made into the aqueous solution of 150 milliliters, regulator solution pH value is 6, prepares the hydrochloride of Eu; In 30 minutes, the hydrochloride of the described Eu of preparation is added drop-wise in described carboxylic acid salt solution, constantly stir in dropping and reaction process, controlling temperature of reaction is 30 DEG C, and reaction is incubated half an hour, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) filter cake obtained is placed in 500ml ethanol system, by 9.90 grams of (0.05mol) 1 under the state constantly stirred, 10-phenanthroline added in described ethanol system in 10 minutes, controlling temperature of reaction is 50 DEG C, reaction times is 0.5h, filter the precipitation obtained, wash, dry, controlling bake out temperature is 80 DEG C, namely obtains the rare earth compound described in the present embodiment 43.58 grams (productive rate is 87.14%).
The Theoretical molecular formula of the europium compound in the present embodiment is C
48h
30.5o
12n
3.5eu.Measure the rare earth compound that the present embodiment prepares, wherein C, H, N element content are obtained by ultimate analysis, and calculated value is: C, and 57.63; H, 3.08; N, 4.90.Measured value is: C, 57.14; H, 2.92; N, 4.67.Rare earth metal content measures by high temperature (about 800 DEG C) burning rare earth compound, and products of combustion hydrochloric acid dissolves, and then carries out titration.Result shows that rare earth compound actual measurement molecular formula is C
48h
30.5o
12n
3.5eu, conforms to Theoretical molecular formula.
Embodiment 2
A kind of europium-gadolinium compound, its chemical formula is:
The synthesis technique of this europium-gadolinium compound is as follows:
(1) be dissolved in the solution of the 600ml water containing 6.00 grams of (0.15mol) sodium hydroxide by the 2-hydroxyquinoline-4-carboxylic acid of 14.20 grams (0.075mol), 19.35 grams of (0.075mol) Whitfield's ointment dibasic acid esters, the pH value of the carboxylic acid salt solution that reaction generates is 7.
(2) be dissolved in a certain amount of 37% hydrochloric acid by the lucium of 3.52 grams of (0.01mol) europium sesquioxides and 5.43 grams of (0.015mol) gadolinium sesquioxides, be made into the aqueous solution of 150 milliliters, regulator solution pH value is 6, prepares the hydrochloride of Eu and Gd; In 30 minutes, the hydrochloride of described Eu and Gd of preparation is added drop-wise in described carboxylic acid salt solution, constantly stir in dropping and reaction process, controlling temperature of reaction is 70 DEG C, and reaction is incubated half an hour, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) filter cake obtained is placed in 500ml ethanol system, by being stirred in 9.90 grams of (0.05mol) 1 in 10 minutes, 10-phenanthroline adds in described ethanol system, controlling temperature of reaction is 60 DEG C, reaction times is 3h, filter the precipitation obtained, wash, dry, controlling bake out temperature is 60 DEG C, namely obtains the rare earth compound described in the present embodiment 45.56 grams (productive rate is 90.87%).
The Theoretical molecular formula of the europium-gadolinium compound in the present embodiment is C
48h
30.5o
12n
3.5eu
0.4gd
0.6.Measure the rare earth compound that the present embodiment prepares, wherein C, H, N element content are obtained by ultimate analysis, and constituent content calculated value is: C, and 57.45; H, 3.07; N, 4.89.Measured value is: C, 57.10; H, 2.89; N, 4.69.Rare earth metal content measures by high temperature (about 800 DEG C) burning rare earth compound, and products of combustion hydrochloric acid dissolves, and then carries out titration.Result shows that rare earth compound actual measurement molecular formula is C
48h
30.5o
12n
3.5eu
0.4gd
0.6, conform to Theoretical molecular formula.
Experimental example 3
A kind of europium-gadolinium compound, its chemical formula is:
The synthesis technique of this europium-gadolinium compound is as follows:
(1) be dissolved in the 600ml 1:1 ethanol-water solution containing 6.00 grams of (0.15mol) sodium hydroxide by the Whitfield's ointment dibasic acid esters of the 2-hydroxyquinoline-4-carboxylic acid of 8.52 grams (0.045mol), 27.09 grams (0.105mol), the pH value of the carboxylic acid salt solution that reaction generates is 8
(2) be dissolved in a certain amount of nitric acid by the lucium of 3.52 grams of (0.01mol) europium sesquioxides and 5.43 grams of (0.015mol) gadolinium sesquioxides, be made into the aqueous solution of 150 milliliters, regulator solution pH value is 6, prepares the nitrate of europium and gadolinium; In 30 minutes, the described europium of preparation and the nitrate of gadolinium are added drop-wise in described carboxylic acid salt solution, constantly stir in dropping and reaction process, controlling temperature of reaction is 50 DEG C, and reaction is incubated half an hour, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) filter cake obtained is placed in 500ml Isopropanol Solvent, by being stirred in 9.90 grams of (0.05mol) 1 in 10 minutes, 10-phenanthroline adds in described ethanol system, controlling temperature of reaction is 65 DEG C, reaction times is 2h, filter the precipitation obtained, wash, dry, controlling bake out temperature is 90 DEG C, namely obtains the rare earth compound described in the present embodiment 44.47 grams (productive rate is 85.12%).
The Theoretical molecular formula of the europium-gadolinium compound in the present embodiment is C
50.4h
32.3o
13.2n
2.9eu
0.4gd
0.6.Measure the rare earth compound that the present embodiment prepares, wherein C, H, N element content are obtained by ultimate analysis, and constituent content calculated value is: C, and 57.93; H, 3.12; N, 3.89.Measured value is: C, 57.49; H, 2.98; N, 3.68.Rare earth metal content measures by high temperature (about 800 DEG C) burning rare earth compound, and products of combustion hydrochloric acid dissolves, and then carries out titration.Result shows that rare earth compound actual measurement molecular formula is C
50.4h
32.3o
13.2n
2.9eu
0.4gd
0.6, conform to Theoretical molecular formula.
Embodiment 4
A kind of europium-gadolinium compound, its chemical formula is:
The synthesis technique of this europium-gadolinium compound is as follows:
(1) be dissolved in by the Whitfield's ointment dibasic acid esters of the 2-hydroxyquinoline-4-carboxylic acid of 19.88 grams (0.105mol), 11.61 grams (0.045mol) in the solution of the 600ml 1:1 isopropanol-water containing 6.00 grams of (0.15mol) sodium hydroxide, the pH value of the carboxylic acid salt solution that reaction generates is 6.
(2) be dissolved in 37% hydrochloric acid by the lucium of 3.52 grams of (0.01mol) europium sesquioxides and 5.43 grams of (0.015mol) gadolinium sesquioxides, be made into the aqueous solution of 150 milliliters, regulator solution pH value is 6, prepares the hydrochloride of europium and gadolinium; In 40 minutes, the described carboxylic acid salt solution of preparation is added drop-wise in the hydrochloride of described europium and gadolinium, constantly stir in dropping and reaction process, controlling temperature of reaction is 50 DEG C, and reaction is incubated half an hour, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) filter cake obtained is placed in 500ml ethanol system, by being stirred in 9.90 grams of (0.05mol) 1 in 10 minutes, 10-phenanthroline adds in described ethanol system, controlling temperature of reaction is 75 DEG C, reaction times is 2h, filter the precipitation obtained, wash, dry, controlling bake out temperature is 105 DEG C, namely obtains the rare earth compound described in the present embodiment 41.87 grams (productive rate 87.05%).
The Theoretical molecular formula of the europium-gadolinium compound in the present embodiment is C
47.6h
28.7o
10.8n
4.1eu
0.4gd
0.6.Measure the rare earth compound that the present embodiment prepares, wherein C, H, N element content are obtained by ultimate analysis, and constituent content calculated value is: C, and 56.93; H, 3.01; N, 5.97, measured value is: C, 56.68; H, 2.88; N, 5.64.Rare earth metal content measures by high temperature (about 800 DEG C) burning rare earth compound, and products of combustion hydrochloric acid dissolves, and then carries out titration.Result shows that rare earth compound actual measurement molecular formula is C
47.6h
28.7o
10.8n
4.1eu
0.4gd
0.6, conform to Theoretical molecular formula.
In above-described embodiment 2-4, described rare earth compound Re is Gd, and as selectable embodiment, described Re can also select the one in other arbitrary rare earth element;
In above-described embodiment, step (1) utilizes 2-hydroxyquinoline-4-carboxylic acid, Whitfield's ointment dibasic acid esters and alkaline matter in water or alcohol, carry out reacting the carboxylate salt both generating; As selectable embodiment, 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters also can be utilized in water or alcohol or water-ol mixed solvent, to carry out reaction with alkaline matter respectively and to generate carboxylate salt, then the carboxylate salt of the two is mixed; The alkaline matter adopted in above-described embodiment is sodium hydroxide, and as selectable embodiment, described alkaline matter can also select other single or mixed-alkali materials such as such as potassium hydroxide or organic amine etc.
In addition, in the step (2) of above-described embodiment, have employed and under whipped state, the metal-salt of Eu or the metal-salt of Eu and the mixing solutions of other rare earth metal salt are added drop-wise in described carboxylic acid salt solution to improve speed of reaction, as selectable embodiment, also carboxylic acid salt solution can be added drop-wise in the metal-salt of Eu or the metal-salt of Eu and the mixing solutions of other rare earth metal salt, and, when carboxylic acid salt solution is added drop-wise in the metal-salt of Eu or the metal-salt of Eu and the mixing solutions of other rare earth metal salt, 2-hydroxyquinoline-4-carboxylate salt, Whitfield's ointment dibasic acid esters salt can drip respectively or mix rear dropping.
In addition, in the above-described embodiments, in order to improve raw material availability, in carboxylate salt described in step (2) and metal-salt, the mol ratio of metal ion is 3:1, as selectable embodiment, also can be set as other any mol ratios.
Comparative example
In order to confirm technique effect of the present invention further, the present invention is also provided with comparative example, specific as follows:
Comparative example 1
Make gram (0.075mol) 2-hydroxyquinoline-4-carboxylic acid of 14.20 in embodiment 1,19.35 grams of (0.075mol) Whitfield's ointment dibasic acid esters into 28.40 grams of (0.15mol) 2-hydroxyquinoline-4-carboxylic acids, all the other process portion are identical, and the chemical formula of the rare earth compound finally obtained is:
Comparative example 2
By 1 in embodiment 1,10-phenanthroline is removed, and all the other process portion are identical.The chemical formula of the rare earth compound finally obtained is:
Comparative example 3
Comparative example 3 adopts the rare earth compound in background technology, and chemical formula is:
The present invention can test with following methods respectively to the luminous intensity of the various rare earth compounds in embodiment and comparative example, acidproof and alkaline resistance properties, powder dispersity:
The detection method of rare earth compound luminous intensity is: be dispersed in 5wt% rare earth compound containing in polyurethane or acryloid cement, be then coated on non-blooming paper, tests the fluorescence intensity when wavelength is the UV rayed of 365nm.
The testing method that is acidproof, alkaline resistance properties of rare earth compound is: the unstressed configuration paper being coated with rare earth compound (5wt%) is cut into 5 × 5cm square and is placed in 3% hydrochloric acid and 3% sodium hydroxide solution half an hour, the fluorescence intensity of range estimation when wavelength is the UV rayed of 365nm after taking out.
The detection method of the dispersing property of rare earth compound is: in 150ml beaker, evenly spreads in 100ml ethyl acetate by 3 grams of rare earth compounds, estimates the number of beaker bottom accumulation of solids after 1 hour.
In embodiment 1 ~ 4, comparative example 1 ~ 3, the test result of the rare earth compound properties of synthesis is as shown in table 1:
Table 1: the test result of rare earth compound properties
| Rare earth compound | Luminous intensity | Acid resistance | Alkali resistance | Dispersed |
| Embodiment 1 | +++ | +++ | +++ | ++++ |
| Embodiment 2 | ++++ | ++++ | ++++ | ++++ |
| Embodiment 3 | ++ | +++ | +++ | ++++ |
| Embodiment 4 | +++ | ++ | ++ | ++++ |
| Comparative example 1 | ++ | + | + | +++ |
| Comparative example 2 | + | + | + | ++ |
| Comparative example 3 | +++ | —— | —— | + |
Note: the implication of each symbology is:---nothing ,+very low, ++ it is slightly good, +++ relatively good, ++++very good.
According to above-mentioned experimental result, the acid resistance of rare earth compound of the present invention, alkali resistance and dispersing property, the rare earth compound being all better than in comparative example, technical solutions according to the invention have significant progress compared to the technical scheme in comparative example.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments, and thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (9)
1. a rare earth compound, is characterized in that, described compound corresponds to general formula:
Wherein, x > 0, y >=0; M > 0, n > 0, m+n=3 (x+y); Z=x+y; Re is any one in the thulium except Eu.
2. rare earth compound according to claim 1, is characterized in that, Re is any one in Gd, Y, La, Tb.
3. the synthesis technique of the rare earth compound described in claim 1-2 any one, comprises following steps:
(1) 2-hydroxyquinoline-4-carboxylic acid, Whitfield's ointment dibasic acid esters and alkaline matter is utilized to carry out reacting the carboxylate salt both generating in water or alcohol or water-ol mixed solvent;
Or utilize 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters in water or alcohol or water-ol mixed solvent, to carry out reacting the carboxylate salt both generating respectively with alkaline matter respectively;
Described alkaline matter is sodium hydroxide; The mol ratio of described 2-hydroxyquinoline-4-carboxylic acid and Whitfield's ointment dibasic acid esters is 3:7 ~ 7:3, and the pH value of the carboxylic acid salt solution that reaction generates controls 6 ~ 8;
(2) 2-hydroxyquinoline-4-carboxylic acid step (1) generated and the metal-salt of the carboxylate salt of Whitfield's ointment dibasic acid esters and the metal-salt of Eu or Eu react with the mixing solutions of other rare earth metal salt, temperature of reaction is 20 ~ 80 DEG C, the precipitation that reaction generates is filtered and washed, obtains filter cake;
(3) reacted with 1,10-phenanthroline in alcoholic solvent by described filter cake, temperature of reaction is 50 ~ 80 DEG C, filters, washs, dries, namely obtain described rare earth compound to the throw out that reaction generates.
4. the synthesis technique of rare earth compound according to claim 3, is characterized in that, the alcohol in described step (1) and step (3) is ethanol or Virahol.
5. the synthesis technique of the rare earth compound according to claim 3 or 4, is characterized in that, in described step (2), in described carboxylate salt and metal-salt, the mol ratio of metal ion is 3:1.
6. the synthesis technique of the rare earth compound according to claim 3 or 4, is characterized in that, metal-salt or other rare earth metal salt of the middle Eu of described step (2) are hydrochloride or nitrate.
7. the synthesis technique of rare earth compound according to claim 6, is characterized in that, the bake out temperature in described step (3) is 60 ~ 105 DEG C.
8. the synthesis technique of the rare earth compound according to claim 3 or 4 or 7, is characterized in that, filter cake is 0.5 ~ 3 hour with the reaction times of 1,10-phenanthroline in alcoholic solvent in described step (3).
9. the rare earth compound described in claim 1-2 any one is used as the purposes of red high-visibility pigment.
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