CN104744364B - A method of directly preparing luminescent material 8-hydroxyquinoline zinc - Google Patents
A method of directly preparing luminescent material 8-hydroxyquinoline zinc Download PDFInfo
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- CN104744364B CN104744364B CN201510167625.1A CN201510167625A CN104744364B CN 104744364 B CN104744364 B CN 104744364B CN 201510167625 A CN201510167625 A CN 201510167625A CN 104744364 B CN104744364 B CN 104744364B
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- Prior art keywords
- hydroxyquinoline
- reaction
- zinc
- raw materials
- luminescent material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
- C07D215/30—Metal salts; Chelates
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- Organic Chemistry (AREA)
Abstract
The present invention discloses a kind of method directly preparing 8 hydroxyquinoline zinc of luminescent material.Using anhydrous zn formate and 8 oxyquinolines as raw material, carrier band hot melt prepares 8 hydroxyquinoline zincs, specific process step：First, according to oxyquinoline=1 of molar ratio anhydrous zn formate/8:2, reaction raw materials are added in batch mixer, are uniformly mixed.Then, uniformly mixed reaction raw materials are transferred in reactor, after being filled with the air that nitrogen is driven away in reactor, and under the carrier band of nitrogen stream and protection, are warming up to 110 DEG C~130 DEG C, reaction 1 h~3 h；Reaction finishes, and is cooled to room temperature, discharging.Finally, 8 hydroxyquinoline zincs that purity is 97%~99% are obtained, yield is 98%~100%.The present invention has the advantages that raw material availability is high, flow is short, yield is high, low etc. without discharging of waste liquid, production cost.
Description
Technical field
The present invention relates to a kind of methods directly preparing luminescent material 8-hydroxyquinoline zinc, more particularly to one kind with formic acid
Zinc is primary raw material, the method that carrier band hot melt directly prepares 8-hydroxyquinoline zinc.The invention belongs to electroluminescent organic materials
Technical field.
Background technology
In existing electroluminescent organic material, 8-hydroxyquinoline metal complex with film forming characteristics, imitate by good, quantum
The advantages that rate is high, glass transition temperature is high, stability is good, therefore become the most ripe and most widely used organic electroluminescence of current techniques
Luminescent material.Wherein, the light emission luminance of 8-hydroxyquinoline zinc is up to 16200 cd/m2, luminescent properties are splendid and are concerned.No
It crosses, its purity is clearly required, only 8-hydroxyquinoline zinc of the purity higher than 95% is just suitable as luminescent material.
The existing method for preparing 8-hydroxyquinoline zinc mainly has two class of liquid-phase precipitation method and solid-phase sequencing.Currently, industrial
It is liquid-phase precipitation method that metaplasia, which produces preparation method used in 8-hydroxyquinoline zinc,.
Liquid-phase precipitation method is usually with 8-hydroxyquinoline and water-soluble zinc salt（For example, zinc chloride, zinc sulfate etc.）It is former for reaction
Material is that reaction motive force prepares 8-hydroxyquinoline zinc to promote precipitation reaction with alkali neutralization.The general process of preparation is：By 8-
Oxyquinoline is dissolved in organic solvent（For example, ethyl alcohol, acetone etc.）, zinc salt be dissolved in water or ethyl alcohol；At a certain temperature, by 8- hydroxyls
Quinoline solution is mixed with zinc solution, and alkaline matter is added（For example, triethylamine, sodium hydroxide etc.）Control the pH of reaction system
Value, reaction finish the precipitation that can obtain product 8-hydroxyquinoline zinc.Due under the collective effect of oxygen and water, 8- hydroxyl quinolines
The side reactions such as polymerization can all occur for quinoline zinc, even 8-hydroxyquinoline, cause the purity of reaction product 8-hydroxyquinoline zinc relatively low, must
Must take several times the technological measures such as crystallization-recrystallization, vacuum sublimation purified, wanting substantially for luminescent material could be met
It asks.In order to improve yield, precipitating reagent 8-hydroxyquinoline usually requires significantly excessive in liquid-phase precipitation method.
Solid-phase sequencing is usually using 8-hydroxyquinoline and zinc salt as reaction raw materials, in low temperature（For example, room temperature）Under ground
Mill prepares 8-hydroxyquinoline zinc so that mechanical force is reaction motive force.Currently, there are two types of the zinc salts selected, one is hydration vinegar
Sour zinc, the second is basic zinc carbonate.Although solid-phase sequencing need not use organic solvent during the reaction, reaction process
Green degree increases.But the 8-hydroxyquinoline zinc purity and yield of preparation are still relatively low.For example, hydration zinc acetate
For raw material when, need to be purified with ethyl alcohol or the continuous washing reaction product of acetone, yield only has 77%.Moreover, in industrialized production
When, if process parameter control is improper, the purity that the abrasion of abrasive material also leads to 8-hydroxyquinoline zinc further decreases.
Therefore, the preparation method of existing luminescent material 8-hydroxyquinoline zinc, generally existing reaction product purity is low, technique walks
Rapid length, low yield, the shortcomings of organic solvent consumption is big, production cost is high.
For this purpose, the present invention has developed solvent-free hot melt reaction system, reacted by providing heat content and pushing and strengthen, and
Nitrogen stream carries under the promotion of formic acid, makes the reaction raw materials 8-hydroxyquinoline of higher price need not be excessive, reduces and be produced into
This.Under the protection of nitrogen stream, the side reaction for preparing 8-hydroxyquinoline zinc in liquid-phase reaction system is avoided, improves 8- hydroxyls
The purity of quinoline zinc.Cumbersome purification step is eliminated, technological process is shortened.Without using organic solvent, no discharging of waste liquid, work
The green degree of skill is high.
Invention content
The purpose of the present invention is the method for existing preparation of industrialization luminescent material 8-hydroxyquinoline zinc there are low yield,
The shortcomings of step is long, of high cost, and propose a kind of yield is high, step is few, the period is short, without using organic solvent, at low cost straight
Connect the method for preparing luminescent material 8-hydroxyquinoline zinc.
The present invention reaction principle be：
Zn(HCOO)2+2C9H6NOH = Zn(C9H6NO)2 +2HCOOH↑
A kind of method directly preparing luminescent material 8-hydroxyquinoline zinc of the present invention, using solvent-free hot melt reactant
System, using anhydrous zn formate and 8-hydroxyquinoline as reaction raw materials, directly prepares in the case where nitrogen stream carries and protects and is used as the material that shines
The 8-hydroxyquinoline zinc of material.It is realized especially by following steps：
1）Batch mixing
It is 1 according to the molar ratio of anhydrous zn formate and 8-hydroxyquinoline:2, reaction raw materials are added in batch mixer, mixing is equal
It is even.
2）Carrier band hot melt reaction
Uniformly mixed reaction raw materials are transferred in reactor, after being filled with the air that nitrogen is driven away in reactor, and
In the case where the L/min nitrogen streams of 10 L/min~30 carry and protect, 110 DEG C~130 DEG C are warming up to, reaction 1 h~3 h；Reaction
It finishes, is cooled to room temperature, discharge.The 8-hydroxyquinoline zinc that purity is 97%~99% is obtained, yield is 98%~100%.
It is an advantage of the invention that：Without using organic solvent, no discharging of waste liquid, green degree height；8-hydroxyquinoline is not required to
Excessive, raw material availability is high；The purity of product 8-hydroxyquinoline zinc is high, yield is high；Without purifying technique step, technological process
It is short, consuming little energy；Production cost is low；Formic acid can be recycled in hot melt reaction process, which can be used for preparing zinc formate
To which formation process recycles.
Specific implementation mode
With reference to specific embodiment to a kind of side directly preparing luminescent material 8-hydroxyquinoline zinc of the present invention
Method is further described.
Embodiment 1：
1）Batch mixing
According to molar ratio anhydrous zn formate/8-hydroxyquinoline=1:2, by 174.34 kg anhydrous zn formates of reaction raw materials and
325.66 kg 8-hydroxyquinolines sequentially add in batch mixer, are uniformly mixed.
2）Carrier band hot melt reaction
500 uniformly mixed kg reaction raw materials are transferred in 1000 L reactors, nitrogen is filled with and drives away in reactor
After air, and in the case where 20 L/min nitrogen streams carry and protect, 120 DEG C are warming up to, reacts 2 h；Reaction finishes, and is cooled to room
Temperature, discharging.Obtain the 8-hydroxyquinoline zinc that purity is 98%, yield 99%.The first generated in condensation method recycling hot melt reaction
Acid.
Embodiment 2：
1）Batch mixing
According to molar ratio anhydrous zn formate/8-hydroxyquinoline=1:2, by 174.34 kg anhydrous zn formates of reaction raw materials and
325.66 kg 8-hydroxyquinolines sequentially add in batch mixer, are uniformly mixed.
2）Carrier band hot melt reaction
500 uniformly mixed kg reaction raw materials are transferred in 1000 L reactors, nitrogen is filled with and drives away in reactor
After air, and in the case where 10 L/min nitrogen streams carry and protect, 110 DEG C are warming up to, reacts 3 h；Reaction finishes, and is cooled to room
Temperature, discharging.Obtain the 8-hydroxyquinoline zinc that purity is 99%, yield 98%.The first generated in condensation method recycling hot melt reaction
Acid.
Embodiment 3：
1）Batch mixing
According to molar ratio anhydrous zn formate/8-hydroxyquinoline=1:2, by 174.34 kg anhydrous zn formates of reaction raw materials and
325.66 kg 8-hydroxyquinolines sequentially add in batch mixer, are uniformly mixed.
2）Carrier band hot melt reaction
500 uniformly mixed kg reaction raw materials are transferred in 1000 L reactors, nitrogen is filled with and drives away in reactor
After air, and in the case where 30 L/min nitrogen streams carry and protect, 130 DEG C are warming up to, reacts 1 h；Reaction finishes, and is cooled to room
Temperature, discharging.Obtain the 8-hydroxyquinoline zinc that purity is 97%, yield 100%.The first generated in condensation method recycling hot melt reaction
Acid.
Claims (1)
1. a kind of method directly preparing luminescent material 8-hydroxyquinoline zinc, it is characterised in that：The method is using solvent-free
Hot melt reaction system, nitrogen stream carry and protect under, using anhydrous zn formate and 8-hydroxyquinoline as reaction raw materials, directly system
The spare 8-hydroxyquinoline zinc for making luminescent material；
It is realized especially by following steps：
1）Batch mixing
It is 1 according to the molar ratio of anhydrous zn formate and 8-hydroxyquinoline:2, reaction raw materials are added in batch mixer, are uniformly mixed；
2）Carrier band hot melt reaction
Uniformly mixed reaction raw materials are transferred in reactor, after being filled with the air that nitrogen is driven away in reactor, and 10
Under the L/min nitrogen streams of L/min~30 are carried and protected, 110 DEG C~130 DEG C are warming up to, reaction 1 h~3 h；Reaction finishes,
It is cooled to room temperature, discharges；The 8-hydroxyquinoline zinc that purity is 97%~99% is obtained, yield is 98%~100%.
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| CN201510167625.1A CN104744364B (en) | 2015-04-10 | 2015-04-10 | A method of directly preparing luminescent material 8-hydroxyquinoline zinc |
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| CN201510167625.1A CN104744364B (en) | 2015-04-10 | 2015-04-10 | A method of directly preparing luminescent material 8-hydroxyquinoline zinc |
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| CN104744364B true CN104744364B (en) | 2018-10-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237475B (en) * | 2015-11-23 | 2018-01-16 | 南昌航空大学 | A kind of green synthesis method of 8 oxyquinoline strontium |
| CN105348191B (en) * | 2015-11-30 | 2018-01-16 | 南昌航空大学 | A kind of method for directly preparing pure 8 oxyquinoline calcium |
| CN105622504B (en) * | 2015-12-26 | 2018-04-06 | 南昌航空大学 | A kind of green method for preparing the oxyquinoline barium of luminescent material 8 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857568A (en) * | 2010-06-03 | 2010-10-13 | 安徽大学 | Preparation method of 8-hydroxyquinoline zinc with shape of octahedron |
| CN104151238A (en) * | 2014-07-30 | 2014-11-19 | 南昌航空大学 | Method for directly preparing pure tris-(8-hydroxyquinoline)aluminum |
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2015
- 2015-04-10 CN CN201510167625.1A patent/CN104744364B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857568A (en) * | 2010-06-03 | 2010-10-13 | 安徽大学 | Preparation method of 8-hydroxyquinoline zinc with shape of octahedron |
| CN104151238A (en) * | 2014-07-30 | 2014-11-19 | 南昌航空大学 | Method for directly preparing pure tris-(8-hydroxyquinoline)aluminum |
Non-Patent Citations (3)
| Title |
|---|
| 8-羟基喹啉金属配合物的制备与提纯;卫芳芳，等;《人工晶体学报》;20090630;第38卷(第3期);全文 * |
| Ultrasonication solid state chemical reaction synthesis and characterization of nanocrystalline Zn(Oxin)2·2H2O(zinc 8-quinolinolate);李道华;《Transactions of Nonferrous Metals Society of China》;20061231;第16卷(第1期);实验部分 * |
| 一步法室温（准室温）固相化学反应合成8-羟基喹啉的Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物;贾殿赠,等;《化学学报》;19931231;第51卷;实验 * |
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