CN101659605B - Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound - Google Patents
Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound Download PDFInfo
- Publication number
- CN101659605B CN101659605B CN 200910192488 CN200910192488A CN101659605B CN 101659605 B CN101659605 B CN 101659605B CN 200910192488 CN200910192488 CN 200910192488 CN 200910192488 A CN200910192488 A CN 200910192488A CN 101659605 B CN101659605 B CN 101659605B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- hydroxyl
- diphenyl ketone
- reaction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing an o-hydroxy benzophenone-rare earth coordination compound. The synthesis method comprises the following steps: firstly, mixing o-hydroxy benzophenone, water soluble rare earth salt, alkali and water used as a reaction medium according to the stoichiometric ratio at a temperature below the melting point of the o-hydroxy benzophenone, then stirring, regulating the temperature, reacting, completing the reaction and obtaining a product of the o-hydroxy benzophenone-rare earth coordination compound by filtering, washing, dewatering and drying the obtained product. The invention realizes that the water is used as the reaction medium for synthesizing the o-hydroxy benzophenone-rare earth coordination compound by a one-step reaction; compared with the prior art requiring taking an organic solvent as the reaction medium, the operation is greatly simplified, the yield, the production efficiency, the environmental protection and the safety are obviously enhanced, and the production cost is correspondingly lowered.
Description
Technical field
The present invention relates to a kind of method of synthetic O-hydroxyl-diphenyl ketone-rare earth complex, more specifically, the present invention relates to a kind of with water the method for the synthetic O-hydroxyl-diphenyl ketone-rare earth complex of reaction medium single step reaction.
Background technology
O-hydroxyl-diphenyl ketone is one type of organic cpds that mother nucleus structure is shown below:
Because they can strong absorption can cause the solar ultraviolet of macromolecular material degraded; And self have the height photostabilization; Therefore, be widely used as macromolecular material UVA formulation photostabilizer (Gen Hete R, Miller H. plastics additive handbook. Cheng Guoxiang; Yao Kangde etc. translate. Beijing: Chemical Industry Press, 2000).
Recently, patent documentation (CN1730454) report, the O-hydroxyl-diphenyl ketone UV light absorber not only can make its photo-stability efficiency to macromolecular material be significantly improved, but also have the following advantages through forming suitable rare earth compounding:
(1) thermotolerance is apparently higher than UV light absorber commonly used and hindered amine as light stabilizer, and is higher than its HMW kind;
(2) tendency of generation bloom phenomenon is minimum;
(3) not with sulfur-containing additive generation antagonistic action.
According to CN1730454; By O-hydroxyl-diphenyl ketone, soluble rare-earth salt and the neutralizing agent stirring reaction in lower alcohol or lower alcohol-water medium of stoichiometric ratio, the deposition that reaction generates can be synthesized through filtration, washing and drying and obtained O-hydroxyl-diphenyl ketone-rare earth complex.It's a pity, adopt the synthetic O-hydroxyl-diphenyl ketone-rare earth complex of this method to require with an organic solvent lower alcohol to make reaction medium, therefore in industrial production, use and have following distinct disadvantage:
(1) because the solubleness of O-hydroxyl-diphenyl ketone-rare earth complex in organic solvent is bigger, so productive rate is on the low side;
(2) because must the organic solvent recovering system of configuration, so investment of production equipment and production energy consumption be higher;
(3) because organic solvent is poisonous, inflammable and explosive, so environmental protection and security risk are bigger;
(4) because productive rate is lower, production is invested and production energy consumption is higher, also need invest and solve environmental protection and security risk, so production cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of O-hydroxyl-diphenyl ketone-rare earth complex compound method that can effectively overcome the existing shortcoming of background technology.O-hydroxyl-diphenyl ketone-rare earth complex compound method of the present invention is following:
At first under the temperature that is lower than the O-hydroxyl-diphenyl ketone fusing point, the O-hydroxyl-diphenyl ketone of stoichiometric proportion (being the ratio that mol ratio equals stoichiometric number), water-solubility rare-earth salt, alkali are mixed with water as reaction medium; Stirring, regulate temperature then reacts; Reaction finishes, the gained product after filtration, washing, dehydration and dry O-hydroxyl-diphenyl ketone-rare earth complex product;
The structure of said O-hydroxyl-diphenyl ketone is suc as formula shown in (I):
Wherein, R is that hydrogen or carbonatoms are 1～12 alkyl;
The structure of said O-hydroxyl-diphenyl ketone-rare earth complex is suc as formula shown in (II):
Wherein, R is that hydrogen or carbonatoms are 1～12 alkyl; RE represents REE, comprises the lanthanon except scandium, yttrium and the promethium; N=1～3.
When synthesizing O-hydroxyl-diphenyl ketone-rare earth complex with the inventive method, water-solubility rare-earth salt is selected from rare earth chloride, rare earth nitrate, acetic acid rare earth, sulfuric acid rare earth or its mixture, and wherein, rare earth comprises the lanthanon except scandium, yttrium and the promethium.
The alkali that can be used for O-hydroxyl-diphenyl ketone-rare earth complex compound method of the present invention comprises sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, ammonia or its mixture;
With the synthetic O-hydroxyl-diphenyl ketone-rare earth complex of the inventive method, water-solubility rare-earth salt and alkali feed intake with this material itself or its aqueous solution form, for the purpose of accurately, preferably feed intake with the aqueous solution form through concentration calibration; The feed ratio of WATER AS FLOW MEDIUM and O-hydroxyl-diphenyl ketone (mass ratio) is 2: 1～10: 1, is preferably 3: 1～6: 1.
With the synthetic O-hydroxyl-diphenyl ketone-rare earth complex of method of the present invention, temperature of reaction is different because of O-hydroxyl-diphenyl ketone: during Synthetic 2-hydroxyl-4-methoxy benzophenone-rare earth compounding, temperature of reaction is room temperature～100 ℃; During Synthetic 2-hydroxyl-4-oxy-octyl benzophenone-rare earth compounding, temperature of reaction is 60～100 ℃.
The present invention has realized with water being the synthetic O-hydroxyl-diphenyl ketone-rare earth complex of reaction medium single step reaction, compares with background technology to have following tangible advantage:
(1) operation is greatly simplified;
(2) because the solubleness of O-hydroxyl-diphenyl ketone-rare earth complex in water is very little, productive rate significantly improves;
(3) owing to need not dispose solvent recovering system, investment of production equipment and production energy consumption reduce;
(4) since WATER AS FLOW MEDIUM nontoxic, do not fire not quick-friedly, environmental protection and security improve greatly;
(5) because the reaction times obviously shortens, productive rate significantly improves, production unit, environmental protection and security capital and production energy consumption reduce, production cost obviously descends.
Embodiment
Below through concrete but non-restrictive example the present invention is further described.
Embodiment 1
Under the room temperature, in reactor drum, add 224.2g 2-hydroxyl-4-methoxy benzophenone (HMBP, 1mol), contain LaCl
381.8g lanthanum chloride solution (0.333mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1000g of total mass of solution, stir then, heat temperature raising to 40 ℃, control isothermal reaction 10min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow powdered product in 105 ℃ of constant pressure and dries, productive rate is 99.3%.Through assay determination, the fusing point of product:＞300 ℃; La, C, H content are respectively 16.77%, 61.49% and 4.68%, with chemical formula La (MBP)
3(La, C, H cubage value are respectively 16.92%, 61.40%, 4.75%) conforms to.
Embodiment 2
Under the room temperature, in reactor drum, add 224.2g 2-hydroxyl-4-methoxy benzophenone (HMBP, 1mol), contain LaCl
3122.7g lanthanum chloride solution (0.5mol) and the aqueous sodium hydroxide solution that contains NaOH 60.0g (1.5mol); Add water to the about 1000g of total mass of solution, stir then, heat temperature raising to 40 ℃, control isothermal reaction 10min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow powdered product in 105 ℃ of constant pressure and dries, productive rate is 99.5%.Through assay determination, the fusing point of product:＞300 ℃; La, C, H content are respectively 23.27%, 22.59% and 4.07%, with chemical formula La (MBP)
2(OH) (La, C, H cubage value are respectively 23.06%, 55.79%, 3.98%) conforms to.
Embodiment 3
Under the room temperature, in reactor drum, add 224.2g 2-hydroxyl-4-methoxy benzophenone (HMBP, 1mol), contain LaCl
3245.4g lanthanum chloride solution (1mol) and the aqueous sodium hydroxide solution that contains NaOH 120.0g (3mol); Add water to the about 1000g of total mass of solution, stir then, heat temperature raising to 40 ℃, control isothermal reaction 10min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow powdered product in 105 ℃ of constant pressure and dries, productive rate is 99.1%.Through assay determination, the fusing point of product:＞300 ℃; La, C, H content are respectively 34.95%, 42.49% and 3.15%, with chemical formula La (MBP) (OH)
2(La, C, H cubage value are respectively 35.07%, 42.41%, 3.03%) conforms to.
Embodiment 4
Under the room temperature, in reactor drum, add 224.2g 2-hydroxyl-4-methoxy benzophenone (HMBP, 1mol), contain SmCl
385.6g the samarium trichloride aqueous solution (0.33mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1000g of total mass of solution; Stir then, heat temperature raising to 40 ℃; Control isothermal reaction 10min, resultant of reaction is through filtration, washing and dry yellow powdered product, and productive rate is 99.2%.Through assay determination, the fusing point of product:＞300 ℃; Sm, C, H content are respectively 17.97%, 60.69% and 4.66%, with chemical formula Sm (MBP)
3(Sm, C, H cubage value are respectively 18.06%, 60.55%, 4.68%) conforms to.
Embodiment 5
Under the room temperature, in reactor drum, add 224.2g 2-hydroxyl-4-methoxy benzophenone (HMBP, 1mol), contain TmCl
391.8g the thulium chloride aqueous solution (0.333mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1000g of total mass of solution, stir then, heat temperature raising to 40 ℃, control isothermal reaction 10min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow powdered product in 105 ℃ of constant pressure and dries, productive rate is 99.3%.Through assay determination, the fusing point of product:＞300 ℃; Tm, C, H content are respectively 19.77%, 59.15% and 4.68%, with chemical formula Tm (MBP)
3(Tm, C, H cubage value are respectively 19.85%, 59.23%, 4.58%) conforms to.
Embodiment 6
Under the room temperature, in reactor drum, add the 326.0g UV-531 (HOBP, 1mol), contain LaCl
381.8g lanthanum chloride solution (0.333mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1500g of total mass of solution, stir then, heat temperature raising to 70 ℃, control isothermal reaction 90min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow wax shape product in 50 ℃ of constant pressure and dries, productive rate is 99.0%.Through assay determination, La, C, H content are respectively 12.53%, 67.99% and 6.88%, with chemical formula La (OBP)
3(La, C, H cubage value are respectively 12.47%, 67.87%, 7.00%) conforms to.
Embodiment 7
Under the room temperature, in reactor drum, add the 326.0g UV-531 (HOBP, 1mol), contain LaCl
3122.7g lanthanum chloride solution (0.5mol) and the aqueous sodium hydroxide solution that contains NaOH 60.0g (1.5mol); Add water to the about 1500g of total mass of solution, stir then, heat temperature raising to 70 ℃, control isothermal reaction 90min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow wax shape product in 50 ℃ of constant pressure and dries, productive rate is 99.0%.Through assay determination, La, C, H content are respectively 17.37%, 62.49% and 6.48%, with chemical formula La (OBP)
2(OH) (La, C, H cubage value are respectively 17.24%, 62.54%, 6.45%) conforms to.
Embodiment 8
Under the room temperature, in reactor drum, add the 326.0g UV-531 (HOBP, 1mol), contain LaCl
3245.4g lanthanum chloride solution (1mol) and the aqueous sodium hydroxide solution that contains NaOH 120.0g (3mol); Add water to the about 1500g of total mass of solution, stir then, heat temperature raising to 70 ℃, control isothermal reaction 90min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow wax shape product in 50 ℃ of constant pressure and dries, productive rate is 99.0%.Through assay determination, La, C, H content are respectively 27.77%, 50.49% and 5.30%, with chemical formula La (OBP) (OH)
2(La, C, H cubage value are respectively 27.90%, 50.61%, 5.22%) conforms to.
Embodiment 9
Under the room temperature, in reactor drum, add the 326.0g UV-531 (HOBP, 1mol), contain SmCl
385.6g the samarium trichloride aqueous solution (0.33mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1500g of total mass of solution, stir then, heat temperature raising to 70 ℃, control isothermal reaction 90min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow wax shape product in 50 ℃ of constant pressure and dries, productive rate is 99.3%.Through assay determination, Sm, C, H content are respectively 13.27%, 67.30% and 6.86%, with chemical formula Sm (OBP)
3(Sm, C, H cubage value are respectively 13.36%, 67.18%, 6.93%) conforms to.
Embodiment 10
Under the room temperature, in reactor drum, add the 326.0g UV-531 (HOBP, 1mol), contain TmCl
391.8g the thulium chloride aqueous solution (0.333mol) and the aqueous sodium hydroxide solution that contains NaOH 40.0g (1mol); Add water to the about 1500g of total mass of solution, stir then, heat temperature raising to 70 ℃, control isothermal reaction 90min; Resultant of reaction is after filtration, washing and dehydration; To constant weight, get yellow wax shape product in 50 ℃ of constant pressure and dries, productive rate is 99.4%.Through assay determination, Tm, C, H content are respectively 14.63%, 66.25% and 6.88%, with chemical formula Tm (OBP)
3(Tm, C, H cubage value are respectively 14.77%, 66.09%, 6.82%) conforms to.
Claims (5)
1. the compound method of an O-hydroxyl-diphenyl ketone rare earth compounding; It is characterized in that: at first under the temperature that is lower than the O-hydroxyl-diphenyl ketone fusing point, the O-hydroxyl-diphenyl ketone of stoichiometric ratio, water-solubility rare-earth salt, alkali are mixed with water as reaction medium; Stirring, attemperation react then; Reaction finishes, and the gained resultant is through filtration, washing, dehydration and the dry O-hydroxyl-diphenyl ketone rare earth compounding product that gets;
The structure of said O-hydroxyl-diphenyl ketone is suc as formula shown in (I):
Wherein, R is that carbonatoms is 1～12 alkyl;
The structure of said O-hydroxyl-diphenyl ketone rare earth compounding is suc as formula shown in (II):
Wherein, R is that carbonatoms is 1～12 alkyl; RE is the lanthanon except scandium, yttrium and the promethium; N=1～3;
Above-mentioned stoichiometric ratio is meant that mol ratio equals the ratio of stoichiometric number.
2. the compound method of the rare earth compounding of O-hydroxyl-diphenyl ketone according to claim 1; It is characterized in that: said water-solubility rare-earth salt is rare earth chloride, rare earth nitrate, acetic acid rare earth, sulfuric acid rare earth or its mixture; Wherein, rare earth is the lanthanon except scandium, yttrium and the promethium.
3. the compound method of the rare earth compounding of O-hydroxyl-diphenyl ketone according to claim 1, it is characterized in that: described alkali is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, ammonia or its mixture.
4. the compound method of the rare earth compounding of O-hydroxyl-diphenyl ketone according to claim 1, it is characterized in that: said O-hydroxyl-diphenyl ketone is 2-hydroxyl-4-methoxy benzophenone, synthesis reaction temperature is room temperature～100 ℃.
5. the compound method of the rare earth compounding of O-hydroxyl-diphenyl ketone according to claim 1, it is characterized in that: said O-hydroxyl-diphenyl ketone is a UV-531, synthesis reaction temperature is 60～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910192488 CN101659605B (en) | 2009-09-18 | 2009-09-18 | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910192488 CN101659605B (en) | 2009-09-18 | 2009-09-18 | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101659605A CN101659605A (en) | 2010-03-03 |
| CN101659605B true CN101659605B (en) | 2012-12-26 |
Family
ID=41787886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910192488 Expired - Fee Related CN101659605B (en) | 2009-09-18 | 2009-09-18 | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101659605B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330514A (en) * | 2019-05-09 | 2019-10-15 | 包头稀土研究院 | Rare earth ion-fragrance ketone complex, stabilizer and its preparation method and application |
| CN110330686A (en) * | 2019-05-09 | 2019-10-15 | 包头稀土研究院 | Rare earth composite stabilizer and its preparation method and application |
| CN114874242A (en) * | 2022-04-20 | 2022-08-09 | 江西永通科技股份有限公司 | Preparation method of modified benzophenone ultraviolet absorbent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517447A (en) * | 2003-01-22 | 2004-08-04 | 田中贵金属工业株式会社 | Raw material composition for CVD and its manufacturing method and chemical gas-phase evaporation plating method of iridium or iridium compound film |
| CN1730454A (en) * | 2005-08-16 | 2006-02-08 | 广东工业大学 | O-hydroxyl-diphenyl ketone- rare earth complex and its preparation method and uses |
-
2009
- 2009-09-18 CN CN 200910192488 patent/CN101659605B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517447A (en) * | 2003-01-22 | 2004-08-04 | 田中贵金属工业株式会社 | Raw material composition for CVD and its manufacturing method and chemical gas-phase evaporation plating method of iridium or iridium compound film |
| CN1730454A (en) * | 2005-08-16 | 2006-02-08 | 广东工业大学 | O-hydroxyl-diphenyl ketone- rare earth complex and its preparation method and uses |
Non-Patent Citations (1)
| Title |
|---|
| 张祖华.稀土-紫外线吸收剂配合物对聚合物光稳定作用研究.《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》.2004,(第3期),第8页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101659605A (en) | 2010-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103282344A (en) | Method for preparation of ketoxime compound and method for preparation of alkoxy-mine hydrochloride | |
| CN103467306B (en) | Synthetic method of iodo-aniline derivatives | |
| CN101659605B (en) | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound | |
| CN101565364B (en) | Synthetic method of Beta-diketone metal salt | |
| CN102516139A (en) | Synthesis method of phenyl sulfide compound | |
| CN102275958A (en) | Method for preparing magnesium hydroxide utilizing magnesium sulfate as raw material | |
| CN105017028A (en) | Improved synthetic method for preparing o-phenylenediamine by reducing o-nitroaniline | |
| CN102309986A (en) | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method | |
| CN102442972B (en) | Industrial preparation method for pramipexole and its dihydrochloride monohydrate | |
| CN109529880A (en) | A kind of regeneration method of catalyst | |
| CN105732543A (en) | Improved synthetic method of alpha-amino-gamma-butyrolactone hydrochloride | |
| CN109896942A (en) | A kind of preparation method of alpha-alcohol ketone photoinitiator | |
| CN104910032A (en) | Preparation method of anilino-acetate | |
| CN102174023B (en) | Preparation method of hydroxyl pyridine compound | |
| CN103896843B (en) | A kind of preparation method of imidazophenylurea | |
| CN104557970B (en) | A kind of preparation method of ticlopidine hydrochloride | |
| CN112608229B (en) | Preparation method of zinc p-tert-butylbenzoate | |
| CN105968278A (en) | Sulfonated acetone-formaldehyde-amine fluorescent polymer as well as preparation method and application thereof | |
| CN102849789B (en) | Preparation method for stannic chloride pentahydrate | |
| CN113307729A (en) | Preparation method of high-performance aluminum acetylacetonate | |
| CN107344921A (en) | A kind of intermediate DAS of paratonere 177 preparation method | |
| CN101367762B (en) | Preparation method of midbody 7-chloroquinaldine | |
| CN103058884B (en) | Method for synthesizing 1-hydroxymethyl cyclopropyl acetonitrile | |
| CN101942033B (en) | High-methoxyl content methyl starch as well as preparation method and application thereof | |
| CN105732375A (en) | Method for synthesizing methyl 3,4,5-trimethoxybenzoate from gallic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121226 Termination date: 20150918 |
|
| EXPY | Termination of patent right or utility model |