CN104628516A - Cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method - Google Patents
Cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method Download PDFInfo
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- CN104628516A CN104628516A CN201310553773.8A CN201310553773A CN104628516A CN 104628516 A CN104628516 A CN 104628516A CN 201310553773 A CN201310553773 A CN 201310553773A CN 104628516 A CN104628516 A CN 104628516A
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- aminomethyl phenyl
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- isobutyl phenenyl
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Abstract
The present invention relates to a cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method. According to the preparation method, in a solvent, p-iodotoluene diacetate and isobutyl 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 the 4-isopropylphenyl-4'-methylphenyl iodonium p-toluene sulfonate; and finally the 4-isopropylphenyl-4'-methylphenyl iodonium p-toluene sulfonate and potassium hexafluorophosphate 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-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate.
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 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate.
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.As the IRGACURE250 of BASF AG, chemistry is by name: 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, to can be used alone or used in combination with suitable photosensitizers (as thiazolone) through test, for UV curing inks, tackiness agent, the varnish of paper, metal and frosting.Time used in combination with Alpha-hydroxy ketone initiator, fabulous surface cure effect and speed can be obtained.IRGACURE250 has good application in graphic art imaging and adhesive area.
formula one: IRGACURE250 structural formula
Have isobutyl-benzene 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 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, 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.
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 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate of industrialization scale operation.
Object of the present invention can be achieved through the following technical solutions: a kind of preparation method of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, it is characterized in that, in a solvent, oxalic acid is carried out reaction to methiodide benzene under tosic acid exists obtain with Isobuytel Benzene single stage method, 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 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, last and Potassium Hexafluorophosphate carries out ion-exchange and obtains product.
Described solvent is trifluoroethanol.
The consumption of described trifluoroethanol is oxalic acid to the volume ratio 1:3-10 (g/ml) of the weight of methiodide benzene and trifluoroethanol.
The mol ratio of described oxalic acid to methiodide benzene and tosic acid and Isobuytel Benzene is 1:1 ~ 3:1 ~ 3.
Described ion-exchange is that 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate is obtained 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate in acetone with phosphofluoric acid nak response.
Compared with prior art, the present invention with the oxalic acid easily prepared to methiodide benzene for raw material, in trifluoroethanol, first react with tosic acid and then directly add isobutyl-benzene again and react, obtain 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, intermediate is solid, facilitates preparation and purification, finally carries out ion-exchange with Potassium Hexafluorophosphate in acetone and obtains 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate 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 being applicable to industrialization scale operation, is suitability for industrialized production 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate provides favourable condition.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
First oxalic acid forms Acibenzolar with tosic acid to methiodide benzene, 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 Potassium Hexafluorophosphate obtains 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate the finished product, and reaction principle is as follows:
Embodiment 1
(1) oxalic acid is to the preparation of methiodide benzene, comprises the following steps:
In the reaction flask of 5L, add 35% Peracetic Acid to starting to drip 1800 milliliters under methyl iodobenzene 750 grams of (3.45mol) room temperatures, within about 3 hours, add, be heated to 35-40 degree, be then incubated and react 12 hours at 40-45 degree, be then as cold as room temperature, separate out oxalic acid to methiodide benzene, pale yellow powder, obtains 695 grams, yield 60%.
(2) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, comprises the following steps:
Oxalic acid adds 300 milliliters of trifluoroethanols to methiodide benzene 33.6 grams (0.1mol), 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 isobutyl-benzene 39.9 grams (0.3mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain 45 grams, yield 86.0%, white powder.
(3) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, comprises the following steps:
4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate 5.23 grams (0.01mol), add 100 milliliters, acetone, then Potassium Hexafluorophosphate 2.21 grams (0.012mol) is added under room temperature, room temperature reaction spends the night, then concentrate, add ethanol, filter, concentrate to obtain faint yellow viscous material.Obtain 3.5 grams, yield 70.5%.
Embodiment 2
(1) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, the method comprises the following steps:
Oxalic acid adds 1800 milliliters of trifluoroethanols to methiodide benzene 504 grams (1.5mol), 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 isobutyl-benzene 300 grams (2.25mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain 620 grams, yield 78.9%, white powder.
(2) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, the method comprises the following steps:
4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate 52.3 grams (0.1mol), adds 1000 milliliters, acetone, then adds Potassium Hexafluorophosphate 22.1 grams (0.12mol) under room temperature, room temperature reaction spends the night, and then concentrates, and adds ethanol, filter, concentrate to obtain faint yellow viscous material.Obtain 35 grams, yield 70.5%.
Embodiment 3
(1) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, the method comprises the following steps:
Oxalic acid adds 1008 milliliters of trifluoroethanols to methiodide benzene 336 grams (1mol), 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 isobutyl-benzene 133 grams (1mol) then room temperature continuation reaction 4-24 hour, after concentration and recovery trifluoroethanol, add sherwood oil crystallization and obtain 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate.
(2) preparation of 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, the method comprises the following steps:
4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate 52.3 grams (0.1mol), adds 1000 milliliters, acetone, then adds Potassium Hexafluorophosphate 22.1 grams (0.12mol) under room temperature, room temperature reaction spends the night, and then concentrates, and adds ethanol, filter, concentrate to obtain faint yellow viscous material.Obtain 35 grams, yield 70.5%.
Claims (5)
1. the preparation method of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate, it is characterized in that, in a solvent, oxalic acid is carried out reaction to methiodide benzene under tosic acid exists obtain with Isobuytel Benzene single stage method, 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 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate, last and Potassium Hexafluorophosphate carries out ion-exchange and obtains product.
2. the preparation method of a kind of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate according to claim 1, it is characterized in that, described solvent is trifluoroethanol.
3. the preparation method of a kind of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate according to claim 2, it is characterized in that, the consumption of described trifluoroethanol is oxalic acid to the volume ratio 1:3-10 (g/ml) of the weight of methiodide benzene and trifluoroethanol.
4. the preparation method of a kind of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate according to claim 1, it is characterized in that, the mol ratio of described oxalic acid to methiodide benzene and tosic acid and Isobuytel Benzene is 1:1 ~ 3:1 ~ 3.
5. the preparation method of a kind of cation light initiator 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate according to claim 1, it is characterized in that, described ion-exchange is that 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine tosilate is obtained 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate in acetone with phosphofluoric acid nak response.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107300828A (en) * | 2016-04-15 | 2017-10-27 | 常州强力电子新材料股份有限公司 | A kind of photosensitive resin for 3D printing |
| CN113979834A (en) * | 2021-11-11 | 2022-01-28 | 南通新纳希新材料有限公司 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
| WO2023195774A1 (en) * | 2022-04-06 | 2023-10-12 | 이피캠텍 주식회사 | Diphenyliodonium salt for photoinitiator and preparation method therefor |
-
2013
- 2013-11-08 CN CN201310553773.8A patent/CN104628516A/en active Pending
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| ELEANOR A.MERRITT ET AL.: "Facile Synthesis of Koser’s Reagent and Derivatives from Iodine or ArylIodides", 《J.ORG.CHEM.》 * |
| MARCIN BIELAWSKI AND BERIT OLOFSSON: "High-yielding one-pot synthesis of diaryliodonium triflates from arenes and iodine or aryl iodides", 《CHEM. COMMUN.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107300828A (en) * | 2016-04-15 | 2017-10-27 | 常州强力电子新材料股份有限公司 | A kind of photosensitive resin for 3D printing |
| CN113979834A (en) * | 2021-11-11 | 2022-01-28 | 南通新纳希新材料有限公司 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
| CN113979834B (en) * | 2021-11-11 | 2023-01-17 | 南通新纳希新材料有限公司 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
| WO2023195774A1 (en) * | 2022-04-06 | 2023-10-12 | 이피캠텍 주식회사 | Diphenyliodonium salt for photoinitiator and preparation method therefor |
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Application publication date: 20150520 |