CN108083998A - LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method - Google Patents
LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method Download PDFInfo
- Publication number
- CN108083998A CN108083998A CN201711411177.0A CN201711411177A CN108083998A CN 108083998 A CN108083998 A CN 108083998A CN 201711411177 A CN201711411177 A CN 201711411177A CN 108083998 A CN108083998 A CN 108083998A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- dione compounds
- led light
- aryl
- led
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of aryl diketone photoinitiator, the absorbing wavelength of such compound is 395nm.The compound of the present invention may be used as the LED light initiator of the light polymerization of unsaturated allyl compound or the mixture containing the compound.It is compared with traditional initiator, such initiator can make unsaturated allyl compound that quick polymerisation occur under LED lamplight irradiation.Aryl alkyl ketone is used as raw material, is reacted under the action of hydrogen chloride with nitrous ether (ethyl nitrite), generates aryl alkyl ketoxime, further hydrolysis obtains 1 aryl, 1,2 dione compounds in formalin in acid condition.Application of 1 aryl, 1,2 dione compounds in LED is coating material solidified is investigated.The influence of the lower hydrolysis of hydrochloric acid effect has been investigated, has provided 1 aryl 1 of synthesis easy to operate, economical and practical, the new process of 2 dione compounds.
Description
Technical field
Scope and 1- aryl -1,2- dione compounds the invention belongs to LED light initiator is in LED light polymeric material
Application.
Background technology
UV photocuring technologies are the new techniques of 20th century mid-term appearance, it is that (wavelength is in 200- using ultraviolet light
It is 400nm) energy, triggers with the process that chemical reactivity liquid fast transition is solid.With traditional heat cure
Technology is compared, it has the advantages that fast curing rate, high efficiency, pollution is small, it is low with expense to have excellent performance, and is a kind of fast development
" green " new technology.UV photocurings product is made of three parts material, i.e. light-cured resin, diluent and photoinitiator.
In recent years, with stringent control of the country to VOC emission, UV photocuring technologies become more and more important, it will by
Traditional heat cure and bi-component is gradually substituted to cure so that UV photocuring technologies more quickly develop.Toy for children oil at present
Ink, food and Key works Drug packing ink cause a large amount of VOC emissions usually using solvent-based ink in work progress, serious to pollute
Environment, this just needs the photo-curing material for developing environment-friendly type that UV photocuring technologies are introduced into these fields.With 3D printing
The fast development of technology, following target are 3D human organ printing techniques, this just needs the photocuring material for developing high effect nontoxic
Material is particularly nontoxic photoinitiator to meet the needs of marketing industries.1- phenyl -1,2- propanedione is a kind of milk fragrance
Food additives, can make an addition to pudding, in cold drink and candy, No. FEMA:3226, additive amount is no more than 10mg/Kg.1- benzene
For base -1,2- propanedione as a kind of food-grade LED light initiator of new and effective low toxicity, industrialized application prospect is very wide
It is general, it can be widely applied to LED (light emitting diode) photocuring toy for children ink, food and Key works Drug packing ink and 3D people
On body Organ printing material.
Light emitting diode (LED) is a kind of electronic device of semiconductor, and LED device can convert electrical energy into optical radiation.
LED has been used widely as radiation device in the fields such as radiation curing and photopolymerization reaction.Compared with traditional UV light sources,
LED light source has the characteristics that following:(1) monochromatic light can be almost sent, spectral line width is very narrow (5-20nm);(2)
Luminous output quantity is almost 100%;(3) low energy consumption;(4) ozone is not generated;(5) without ultraviolet radioactive;(6) heat generated is low;
(7) operation cost is low;(8) service life is long;(9) safe operation is simple;(10) it is compact to design, it is convenient for carrying.Make in the industry
It can ensure personnel safety with the LED light source that low energy consumption and security performance is high but also cut down expenses.In view of its advanced, economy
And the features such as environmental-friendly, LED have good development prospect, it can be as a kind of complementation of ultraviolet photo-curing, applied to one
A little potential frontiers.
There are many wavelength species of LED light source, and the most commonly used is 395-405nm, 395nm is that UV-LED cures common wavelengths.
However it is most of reported or the absorbing wavelength of commercialized photoinitiator in more than 365nm to absorb luminous energy poor, in LED light source
Irradiation under, the initiation performance of these photoinitiators is not fine.Efficiently trigger under LED light source irradiation so under background various
The photopolymerization reaction of type is a huge challenge.In order to preferably promote development of the LED light curing technology in photopolymerization,
The photoinitiator of longer wavelength must be developed to meet the cured needs of LED light source.1- aryl -1,2- dione compounds into
Work(development, it will promote the cured fast development of LED light, realize the cured leap from ultraviolet photo-curing to LED light.
The content of the invention
It is an object of the invention to provide a kind of LED light initiator, absorbing wavelength can be applied to LED light and consolidate in 395nm
Change in coating, a kind of production technology of synthesis 1- aryl -1,2- dione compounds more practical, cost is lower is also provided.
The present invention solves its technical problem and following technical scheme is taken to realize:
A kind of food-grade LED light initiator 1- phenyl -1,2- dione compounds, the general formula of the compound are as follows:
Wherein the absorbing wavelength of the compound is in 395nm, R1And R2It can be in any combination.
Preferably, R is worked as2For isopropyl when, the compound be 1- phenyl -3- methyl-1s, 2- diacetyl, LED cure effect
Fruit is best.
A kind of application of food-grade LED light initiator 1- phenyl -1,2- dione compounds in LED light is coating material solidified.
A kind of synthetic method of food-grade LED light initiator 1- phenyl -1,2- dione compounds, using aryl alkyl ketoxime
For raw material, formalin hydrolysis, obtains 1- phenyl -1,2- dione compounds, reaction temperature is room temperature, instead in acid condition
When being 8-12 small between seasonable.
Preferably, in the synthesis of intermediate aryl alkyl ketoxime, aryl alkyl ketone is used as raw material, in the effect of hydrogen chloride
Lower and nitrous ether (ethyl nitrite) reacts, and generates aryl alkyl ketoxime, and reaction temperature is room temperature, when the reaction time is 2 small.
The advantages and positive effects of the present invention are:
1st, the invention discloses a kind of LED light initiator 1- aryl -1,2- dione compounds, absorbing wavelength 395nm,
It can be applied in LED light polymeric material compare with traditional initiator, such initiator can make unsaturated allyl compound exist
LED lamplight irradiation is lower to occur quick polymerisation.
2nd, the present invention optimizes reaction condition, provides a simple and direct and warp by the change to reaction raw materials and condition
The production technology of Ji material benefit.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
The synthesis chemical formula that the present invention prepares 1- phenyl -1,2- dione compounds is as follows:
Embodiment 1
(1) in 2000 liters of reaction kettle, 800kg ethyl alcohol and 400kg propiophenones are added in, being passed through 78kg under ice water cooling does
Dry hydrogen chloride gas is maintained at 30-35 DEG C and is passed through 242kg nitrous ether (ethyl nitrite)s, continues after having led to when this thermotonus 2 is small,
Stop reaction, decompression steams ethyl alcohol, obtains crude product.700kg re crystallization from toluene is added in, obtains 1- phenyl 1,2- propanedione -2-
Oxime 310kg, yield 63.8%.
(2) in 1000 liters of reaction kettle, 200kg concentrated hydrochloric acids, 200kg30% formalins and 200kg ethyl alcohol are added in,
200kg1- phenyl 1 is added portionwise below 15 DEG C in the lower cooling of ice water cooling, and 2- propanedione -2- oximes are stirred at room temperature anti-after adding
Answer 8 it is small when, with 400kg dichloromethane extract, then respectively washed once with saturated sodium bicarbonate solution and water, remove dichloromethane
Crude product is obtained, vacuum distillation obtains yellow liquid 1- phenyl -1,2- propanedione 133.5kg, yield 73.5%.
Embodiment 2
(1) in 1000 milliliters of reaction bulb, 300g ethyl alcohol and 148g isobutyrophenones is added in, 40g is passed through under ice water cooling
Dry hydrogen chloride gas is maintained at 30-35 DEG C and is passed through 120g nitrous ether (ethyl nitrite)s, continues after having led to when this thermotonus 2 is small,
Stop reaction, decompression steams ethyl alcohol, adds in 300kg toluene, respectively with 100g washings twice, removes toluene, obtains 1- phenyl -3-
Methyl-1,2- diacetyl -2- oxime 139g, yield 78.5%.It is directly entered and reacts in next step.
(2) in 1000 milliliters of reaction bulb, 150g concentrated hydrochloric acids, 150g30% formalins and 200kg ethyl alcohol are added in,
139g1- phenyl -3- methyl-1s are added portionwise in the lower cooling of ice water cooling below 15 DEG C, and 2- diacetyl -2- oximes add rear room temperature
Be stirred to react 12 it is small when, with 200g dichloromethane extract, then respectively washed once with saturated sodium bicarbonate solution and water, removing two
Chloromethanes obtains crude product, and vacuum distillation obtains yellow liquid 1- phenyl -3- methyl-1s, 2- diacetyl 120g, and yield is
94.3%.
Embodiment 3
(1) in 1000 milliliters of reaction bulb, the third methyl ketone of 300g ethyl alcohol and 160g benzyl rings is added in, under ice water cooling
The hydrogen chloride gas of 40g dryings is passed through, 30-35 DEG C is maintained at and is passed through 120g nitrous ether (ethyl nitrite)s, is continued after having led to anti-in this temperature
Answer 2 it is small when, stop reaction, decompression steams ethyl alcohol, adds in 300kg toluene, respectively with 100g washings twice, removes toluene, obtains
1- phenyl -2- cyclopropyl -1,2- propanedione -2- oxime 148g, yield 78.3%.It is directly entered and reacts in next step.
(2) in 1000 milliliters of reaction bulb, it is cold that 150g hydrochloric acid, 150g formalins and 150g ethyl alcohol, ice water are added in
148g1- phenyl -2- cyclopropyl -1,2- propanedione -2- oximes are added portionwise in lower cooling below 15 DEG C, are stirred at room temperature after adding
React 2 it is small when, with 300g dichloromethane extract, then respectively washed once with saturated sodium bicarbonate solution and water, remove dichloromethane
Alkane obtains crude product, and vacuum distillation obtains yellow liquid 1- phenyl -2- cyclopropyl -1,2- propanedione 158g, yield 90.8%.
Embodiment 4
(1) in 1000 milliliters of reaction bulb, 300g ethyl alcohol and 190g phenyl hexamethylene methyl ketones are added in, under ice water cooling
The hydrogen chloride gas of 40g dryings is passed through, 30-35 DEG C is maintained at and is passed through 120g nitrous ether (ethyl nitrite)s, is continued after having led to anti-in this temperature
Answer 2 it is small when, stop reaction, decompression steams ethyl alcohol, adds in 300kg toluene, respectively with 100g washings twice, removes toluene, obtains
1- phenyl -2- cyclopropyl -1,2- propanedione -2- oxime 170g, yield 77.6%.It is directly entered and reacts in next step.
(2) in 1000 milliliters of reaction bulb, it is cold that 200g hydrochloric acid, 200g formalins and 200kg ethyl alcohol, ice water are added in
170g1- phenyl -2- cyclohexyl -1,2- propanedione -2- oximes are added portionwise in lower cooling below 15 DEG C, are stirred at room temperature after adding
React 12 it is small when, with 300g dichloromethane extract, then respectively washed once with saturated sodium bicarbonate solution and water, remove dichloromethane
Alkane obtains crude product, and vacuum distillation obtains yellow liquid 1- phenyl -2- cyclohexyl -1,2- propanedione 185g, yield 90.7%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention god.
Claims (5)
1.LED photoinitiator 1- phenyl -1,2- dione compounds, it is characterised in that:The general formula of the compound is as follows:
Wherein the absorbing wavelength of the compound is in 395nm, R1For C1-6Alkyl, R2For C1-6Alkyl, cyclopropyl, cyclohexyl or
Isopropyl, R1And R2It can be in any combination.
2. LED light initiator 1- phenyl -1,2- dione compounds according to claim 1, it is characterised in that:Work as R2To be different
During propyl, which is 1- phenyl -3- methyl-1s, and 2- diacetyl, LED solidification effects are best.
3. LED light initiator 1- phenyl -1,2- dione compounds described in a kind of claim 1 or 2 are in LED light is coating material solidified
Application.
4. a kind of synthetic method of LED light initiator 1- phenyl -1,2- dione compounds described in claim 1 or 2, feature
It is:Aryl alkyl ketoxime is used as raw material, formalin hydrolyzes in acid condition, and it is diketonate to obtain 1- phenyl -1,2-
Object is closed, reaction temperature is room temperature, when the reaction time is 8-12 small.
5. synthetic method according to claim 4, it is characterised in that:In the synthesis of intermediate aryl alkyl ketoxime, use
Aryl alkyl ketone is raw material, is reacted under the action of hydrogen chloride with nitrous ether (ethyl nitrite), generates aryl alkyl ketoxime, and reaction temperature is
Room temperature, when the reaction time is 2 small.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711411177.0A CN108083998A (en) | 2017-12-23 | 2017-12-23 | LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711411177.0A CN108083998A (en) | 2017-12-23 | 2017-12-23 | LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108083998A true CN108083998A (en) | 2018-05-29 |
Family
ID=62178653
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711411177.0A Pending CN108083998A (en) | 2017-12-23 | 2017-12-23 | LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108083998A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101233113A (en) * | 2005-07-29 | 2008-07-30 | 惠氏公司 | Cycloalkyl amino-hydantoin compounds and use thereof for beta-secretase modulation |
CN106883109A (en) * | 2017-02-21 | 2017-06-23 | 怀化金鑫新材料有限公司 | The synthetic method of the propanedione of 1 phenyl of novel photoinitiator 1,2 |
-
2017
- 2017-12-23 CN CN201711411177.0A patent/CN108083998A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101233113A (en) * | 2005-07-29 | 2008-07-30 | 惠氏公司 | Cycloalkyl amino-hydantoin compounds and use thereof for beta-secretase modulation |
CN106883109A (en) * | 2017-02-21 | 2017-06-23 | 怀化金鑫新材料有限公司 | The synthetic method of the propanedione of 1 phenyl of novel photoinitiator 1,2 |
Non-Patent Citations (3)
Title |
---|
CHUN KEUN JANG等: "Red-emitting materials derived from 2,3-dicyanopyrazine for organic light emitting devices", 《JOURNAL OF CHEMICAL RESEARCH》 * |
R. BISHO等: "Photochemical Formation of Hydroxycyclopentenones from Unsaturated 1,2-diketones", 《CHEMICAL COMMUNICATIONS》 * |
STEFANO SANTORO等: "Oxidation of Alkynes in Aqueous Media Catalyzed by Diphenyl Diselenide", 《LETTER》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Maul et al. | Benzotrifluoride and derivatives: useful solvents for organic synthesis and fluorous synthesis | |
White et al. | The ortho-Claisen Rearrangement. IV. The Rearrangement of X-Cinnamyl p-Tolyl Ethers1 | |
US4388450A (en) | Aromatic polyvinyl ethers and heat curable molding compositions obtained therefrom | |
CN105170018B (en) | A kind of fluorine-containing surfactant without perfluoro caprylic acid and preparation method thereof and process system | |
Dumur | Recent advances on iron-based photoinitiators of polymerization | |
AU2003285305A1 (en) | Continuous process for producing pseudoionones and ionones | |
CN109369406B (en) | Photocatalytic synthesis method and application of 1-hydroxycyclohexyl phenyl ketone compound | |
CN108083998A (en) | LED light initiator 1- phenyl -1,2- dione compounds and its synthetic method | |
US4518788A (en) | Aromatic polyvinyl ethers and heat curable molding compositions obtained therefrom | |
US4705887A (en) | Aromatic polyvinyl ethers and heat curable molding compositions obtained therefrom | |
CN101550203B (en) | Photoinitiator for ultraviolet light radiation solidification, aromatic ketone compound and method of manufacturing the same | |
CN102503774A (en) | Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis | |
CN108358871B (en) | Synthetic method of 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone | |
CN107759450B (en) | Method for synthesizing alpha, beta-unsaturated ketone compound from dimethyl sulfoxide and ketone compound | |
CN109897063B (en) | Preparation method of macromolecular low-migration phosphine oxide UV-LED photoinitiator | |
CN107793378A (en) | A kind of novel method for synthesizing of glycerin triglycidyl ether | |
CN111116339B (en) | Method for artificially synthesizing curcumin and derivatives thereof | |
CN109400530B (en) | Naphthalimide aryl thioether type photoinitiator suitable for UV-LED photocuring, and preparation method and application thereof | |
CN106883109A (en) | The synthetic method of the propanedione of 1 phenyl of novel photoinitiator 1,2 | |
CN108101763A (en) | Double [4 '-(the 2,2- dialkoxies acetyl) phenyl] methane of photoinitiator and its synthetic method | |
CN106905127B (en) | Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone | |
CN110976751A (en) | Precoated sand | |
CN108047359A (en) | (the 2,2- dialkoxies acetyl) biphenyl of photoinitiator 4,4 '-two and its synthetic method | |
Ye et al. | Synthesis and characterization of oligomers containing the α‐aminoalkylphenone chromophore as oligomeric photoinitiator | |
CN103980392A (en) | Star-like visible light initiator having conjugated structure and containing benzophenone fragments as well as synthesis and application of visible light initiator |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180529 |