CN104628540A - Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method - Google Patents
Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method Download PDFInfo
- Publication number
- CN104628540A CN104628540A CN201310553758.3A CN201310553758A CN104628540A CN 104628540 A CN104628540 A CN 104628540A CN 201310553758 A CN201310553758 A CN 201310553758A CN 104628540 A CN104628540 A CN 104628540A
- Authority
- CN
- China
- Prior art keywords
- pungent
- preparation
- benzene
- alkoxyl phenyl
- reaction
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
Abstract
The present invention relates to a cation photoinitiator (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate preparation method. According to the preparation method, in a solvent, iodobenzene diacetate and 4-octyloxy benzene are subjected to a one-step reaction in the presence of p-toluene sulfonic acid, wherein the reaction temperature is a room temperature, and the reaction time is 4-24 h; concentration is performed after completing the reaction so as to remove the solvent; petroleum ether is added to crystallize to obtain (4-octyloxyphenyl)phenyliodonium p-toluene sulfonate; and finally the(4-octyloxyphenyl)phenyliodonium p-toluene sulfonate and sodium hexafluoroantimonate are subjected to ion exchange to obtain the product. Compared with the technology in the prior art, the preparation method of the present invention has characteristics of reasonable process, simple operation, and safe production, is suitable for industrial mass production, and provides favorable conditions for industrial production of the (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate.
Description
Technical field
The present invention relates to the preparation method of the asymmetric two aromatic hydrocarbon salt compounded of iodine of cation light initiator, particularly relate to the preparation method of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate.
Background technology
Radiation curing is that a kind of to realize chemical formulation (coating, ink and tackiness agent) by liquid conversion by means of energy exposure be the solid-state course of processing.What radiation curing was the most frequently used is ultraviolet (UV) photocuring, and light trigger is one of important component in photocuring system, and it plays decisive role to solidification rate.Light trigger is by after UV-irradiation, and light absorbing energy, splits into 2 living radicals, causes photosensitive resin and reactive thinner generation chain reaction polymerization, makes sizing agent crosslinking curing, is characterized in fast, environmental protection, energy-conservation.Light trigger is divided into radical polymerization light trigger and the large class of Cationic photoinitiator two by photo-degradation mechanism.Cation photocuring system have solidification process volumetric shrinkage little, base material strong adhesion, Light Curing not easily do not stopped by oxygen inhibition, curing reaction and be suitable for the advantages such as thick film photocuring, have very wide application prospect in fields such as coating, ink, tackiness agent and polymer matrix composites, cation photocuring material just progressively replaces solvent-borne type, thermoset material in some field.Cation light initiator mainly comprises: diphenyl iodnium, triphenyl sulfosalt, luxuriant iron class etc., the synthesis of diphenyl iodnium of our primary study, due to the diphenyl iodnium poor solubility Application comparison difficulty of symmetric form, what current industrial value was higher is asymmetric diphenyl iodnium, but its synthesis relative difficulty some.The UV Acure1600 of as profound in U.S. Allnex new (former CYTEC cyanogen is special) company, chemistry is by name: (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, can be used for UV curing inks, tackiness agent, and timber, metal, plastics and other linking agents etc. used on the surface.
Formula one: UV Acure1600 structural formula
Have the pungent alkoxy benzene of 4-and toluene two to have different substituents to roll into a ball the salt compounded of iodine formed between phenyl ring in the structure of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, its synthesis mainly contains following two kinds of methods:
1.Beringer synthesis method
R1, R2: methyl, ethyl, sec.-propyl;
X: chlorion, hexafluorophosphoricacid acid ions, hexafluoro-antimonic acid radical ion;
By at Potassium Persulphate, generate iodine compound under vitriol oil effect and then carry out ion-exchange.
2.Widdowson synthesis method
To be survived under trifluoromethanesulfonic acid effect iodine compound by iodobenzene diacetate and phenylo boric acid compound.
Method 1Beringer synthesis method reaction product is more assorted, and separation and purification has certain difficulty, and method 2Widdowson synthesis method uses phenylo boric acid compound, and price comparison is expensive, and trifluoromethanesulfonic acid corrodibility is stronger, and operational danger is high.We are studied the synthesis of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate by experiment, adopting with trifluoroethanol is solvent, single stage method is done from iodobenzene diacetate and is reacted with the pungent alkoxy benzene of 4-tosic acid exists, make reaction product purer, condition is gentleer, simple to operate, and raw material sources also compare and are easy to get, and are relatively applicable to suitability for industrialized production.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of rational technology is provided, simple to operate, production safety, is applicable to the preparation method of cation light initiator (the pungent alkoxyl phenyl of 4-) the benzene iodine hexafluoro antimonate of industrialization scale operation.
Object of the present invention can be achieved through the following technical solutions: the preparation method of a kind of cation light initiator (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, it is characterized in that, in a solvent, iodobenzene diacetate is carried out under tosic acid exists reaction to obtain with the pungent alkoxy benzene single stage method of 4-, temperature of reaction is room temperature, reaction times is 4-24 hour, reaction terminates rear concentrating and removes solvent, then add sherwood oil crystallization and obtain (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, last and sodium hexafluoroantimonate carries out ion-exchange and obtains product.
Described solvent is trifluoroethanol.
The consumption of described trifluoroethanol is the weight of iodobenzene diacetate and the volume ratio 1: 3-10 (g/ml) of trifluoroethanol.
The mol ratio of described iodobenzene diacetate and tosic acid and the pungent alkoxy benzene of 4-is 1: 1 ~ 3: 1 ~ 3.
Described ion-exchange is that (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate is reacted (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate in acetone with sodium hexafluoroantimonate.
Compared with prior art, the present invention with the iodobenzene diacetate easily prepared for raw material, in trifluoroethanol, first react with tosic acid and then directly add the pungent alkoxy benzene of 4-again and react, obtain (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, intermediate is solid, facilitates preparation and purification, last with carry out ion-exchange with sodium hexafluoroantimonate in acetone and obtain (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate the finished product.Reaction is at room temperature carried out, simple to operate, and intermediate is separated and also facilitates, and purifies also than being easier to, and is applicable to industrialization scale operation, for suitability for industrialized production (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate provides favourable condition.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
First iodobenzene diacetate forms Acibenzolar with tosic acid, and directly in trifluoroethanol, form iodine tosilate with aromatic hydrocarbon without separation, intermediate is solid, easily by after concentration and recovery trifluoroethanol, can add sherwood oil crystallization.Finally carrying out ion-exchange in acetone with sodium hexafluoroantimonate obtains (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate the finished product, and reaction principle is as follows:
Embodiment 1
(1) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, comprises the following steps:
Iodobenzene diacetate 32.2 grams (0.1mol) adds 300 milliliters of trifluoroethanols, stirred at ambient temperature dissolves, then tosic acid 51.6 grams (0.3mol) is added, temperature of reaction maintains room temperature, reacts after 1-2 hour, adds 4-pungent alkoxy benzene 61.6 grams (0.3mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain 37 grams, yield 63.6%, white powder.
(2) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, comprises the following steps:
(the pungent alkoxyl phenyl of 4-) benzene iodine tosilate 5.81 grams (0.01mol), add 100 milliliters, acetone, then sodium hexafluoroantimonate 3.1 grams (0.012mol) is added under room temperature, room temperature reaction spends the night, then concentrate, add ethanol, filter, concentrate to obtain off-white powder product, yield 89%.
Embodiment 2
(1) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, the method comprises the following steps:
Iodobenzene diacetate 483 grams (1.5mol) adds 1800 milliliters of trifluoroethanols, stirred at ambient temperature dissolves, then tosic acid 516 grams (3mol) is added, temperature of reaction maintains room temperature, reacts after 1-2 hour, adds 4-pungent alkoxy benzene 462 grams (2.25mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain 520 grams, yield 59.6%, white powder.
(2) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, comprises the following steps:
(the pungent alkoxyl phenyl of 4-) benzene iodine tosilate 58.1 grams (0.1mol), add 1000 milliliters, acetone, then sodium hexafluoroantimonate 31 grams (0.12mol) is added under room temperature, room temperature reaction spends the night, and then concentrates, and adds ethanol, filter, concentrate to obtain off-white powder, obtain 57 grams, yield 88.3%.
Embodiment 3
(1) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, the method comprises the following steps:
Iodobenzene diacetate 322 grams (1mol) adds 966 milliliters of trifluoroethanols, stirred at ambient temperature dissolves, then tosic acid 172 grams (1mol) is added, temperature of reaction maintains room temperature, react after 1-2 hour, add 4-pungent alkoxy benzene 205 grams (1mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate.
(2) preparation of (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, comprises the following steps:
(the pungent alkoxyl phenyl of 4-) benzene iodine tosilate 58.1 grams (0.1mol), add 1000 milliliters, acetone, then sodium hexafluoroantimonate 31 grams (0.12mol) is added under room temperature, room temperature reaction spends the night, then concentrate, add ethanol, filter, concentrate to obtain off-white powder product, yield 90%.
Claims (5)
1. the preparation method of cation light initiator (the pungent alkoxyl phenyl of a 4-) benzene iodine hexafluoro antimonate, it is characterized in that, in a solvent, iodobenzene diacetate is carried out under tosic acid exists reaction to obtain with the pungent alkoxy benzene single stage method of 4-, temperature of reaction is room temperature, reaction times is 4-24 hour, reaction terminates rear concentrating and removes solvent, then add sherwood oil crystallization and obtain (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate, last and sodium hexafluoroantimonate carries out ion-exchange and obtains product.
2. the preparation method of a kind of cation light initiator according to claim 1 (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, it is characterized in that, described solvent is trifluoroethanol.
3. the preparation method of a kind of cation light initiator according to claim 2 (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, it is characterized in that, the consumption of described trifluoroethanol is the weight of iodobenzene diacetate and the volume ratio 1: 3-10 (g/ml) of trifluoroethanol.
4. the preparation method of a kind of cation light initiator according to claim 1 (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, it is characterized in that, the mol ratio of described iodobenzene diacetate and tosic acid and the pungent alkoxy benzene of 4-is 1: 1 ~ 3: 1 ~ 3.
5. the preparation method of a kind of cation light initiator according to claim 1 (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate, it is characterized in that, described ion-exchange is that (the pungent alkoxyl phenyl of 4-) benzene iodine tosilate is reacted (the pungent alkoxyl phenyl of 4-) benzene iodine hexafluoro antimonate in acetone with sodium hexafluoroantimonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310553758.3A CN104628540A (en) | 2013-11-08 | 2013-11-08 | Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310553758.3A CN104628540A (en) | 2013-11-08 | 2013-11-08 | Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104628540A true CN104628540A (en) | 2015-05-20 |
Family
ID=53207837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310553758.3A Pending CN104628540A (en) | 2013-11-08 | 2013-11-08 | Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104628540A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232497A (en) * | 2017-07-10 | 2019-01-18 | 上海予利生物科技股份有限公司 | A kind of Coumarins cation light initiator and preparation method thereof |
| CN111349226A (en) * | 2020-03-17 | 2020-06-30 | 北京化工大学 | Method for improving epoxy rotor phase photopolymerization conversion rate by using long-chain alkane and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882201A (en) * | 1988-03-21 | 1989-11-21 | General Electric Company | Non-toxic aryl onium salts, UV curable coating compositions and food packaging use |
| US4992571A (en) * | 1989-10-31 | 1991-02-12 | General Electric Company | Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts |
-
2013
- 2013-11-08 CN CN201310553758.3A patent/CN104628540A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882201A (en) * | 1988-03-21 | 1989-11-21 | General Electric Company | Non-toxic aryl onium salts, UV curable coating compositions and food packaging use |
| US4992571A (en) * | 1989-10-31 | 1991-02-12 | General Electric Company | Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts |
Non-Patent Citations (3)
| Title |
|---|
| MARCIN BIELAWSKI，ET AL.: "High-yielding one-pot synthesis of diaryliodonium triflates from arenes and iodine or aryl iodides", 《CHEM.COMMUN.》 * |
| ZHANG DONG，ET AL.: "Polymerizations of epoxides with microwave energy", 《JOURNAL OF POLYMER SCIENCE, PART B: POLYMER PHYSICS》 * |
| 彭荣等: "非对称阳离子光引发剂(4-辛烷氧基苯基)苯碘鎓六氟锑酸盐的合成研究", 《化学世界》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232497A (en) * | 2017-07-10 | 2019-01-18 | 上海予利生物科技股份有限公司 | A kind of Coumarins cation light initiator and preparation method thereof |
| CN111349226A (en) * | 2020-03-17 | 2020-06-30 | 北京化工大学 | Method for improving epoxy rotor phase photopolymerization conversion rate by using long-chain alkane and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Klikovits et al. | Novel photoacid generators for cationic photopolymerization | |
| CN105712917B (en) | Conjugated type sulfosalt light trigger, preparation method and applications with light trigger and photosensitizer dual-use function | |
| CN103694469B (en) | A kind of covalent organic frame material of thioether functionalization and synthetic method thereof | |
| CN100455518C (en) | Prepn process of nanometer nickel sulfide rod | |
| CN101943862A (en) | Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof | |
| CN103407992A (en) | Method for preparing hydrophilic temperature and pH dual-sensitive graphene through thiol-ene click chemistry method | |
| CN102141731A (en) | Toluylene-containing meta-substituted sulfonium salt photoproduction acid agent and preparation method thereof | |
| CN103934469A (en) | Method for preparing silver nanoclusters coated with glutathione | |
| CN104628516A (en) | Cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method | |
| CN103539742B (en) | A kind of preparation method of ionic liquid type hydroxylamine salt | |
| CN104628540A (en) | Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method | |
| CN107915655B (en) | Organic gel compound and preparation method and application thereof | |
| Yue et al. | Novel CS2 storage materials from ion-like liquids for one-step synthesis of active nano-metal sulfides in the photocatalytic reduction of CO2 | |
| CN102219723A (en) | 1,2,5-triphenyl substituted pyrrole derivative with gathering induced luminescence performance as well as preparation method and application thereof | |
| CN103194501B (en) | Method for synthetizing chiral cyclic alkyl amino acid by amino transferase | |
| CN105384603A (en) | Synthesis method of poly-fluorinated phenol compound | |
| CN101624408A (en) | Pendant naphthalene group-containing benzene ligand ferrocenium salt cationic photoinitiators and preparation method thereof | |
| CN105294408B (en) | Cation light initiator（2 hydroxy-tetradecyl oxygen phenyl）The preparation method of benzene iodine hexafluoro antimonate | |
| CN104628517A (en) | Cation photoinitiator 4-isopropylphenyl-4'-methylphenyl iodonium p-toluene sulfonate preparation method | |
| CN109134710A (en) | A kind of arylsulfonium salts oxime ester lightlike initiating agent and its synthesis and application | |
| WO2010118661A1 (en) | Method for preparation metal compounds of 8-hydroxyquinoline or derivatives | |
| CN104262371A (en) | IQ[6]-rare earth complex, as well as synthesis and application thereof | |
| CN102633644A (en) | Synthesis process of trifluoroacetyl ethyl acetate | |
| CN103664434B (en) | Quantum dot catalysis is prepared disulfide and is produced the method for hydrogen | |
| CN110092851B (en) | LED sensitive hybrid photoinitiator and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20150520 |