CN100577671C - Synthetic method of 4,4'-didodecylphenyliodonium hexafluoroantimonate - Google Patents
Synthetic method of 4,4'-didodecylphenyliodonium hexafluoroantimonate Download PDFInfo
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- CN100577671C CN100577671C CN200710053131.6A CN200710053131A CN100577671C CN 100577671 C CN100577671 C CN 100577671C CN 200710053131 A CN200710053131 A CN 200710053131A CN 100577671 C CN100577671 C CN 100577671C
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- dodecylbenzene
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- -1 hexafluoroantimonate Chemical compound 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011630 iodine Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 16
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000001230 potassium iodate Substances 0.000 claims abstract description 10
- 229940093930 potassium iodate Drugs 0.000 claims abstract description 10
- 235000006666 potassium iodate Nutrition 0.000 claims abstract description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 33
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229940045511 barium chloride Drugs 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- IVUSOGDLVUEEQB-UHFFFAOYSA-N oxido(dioxo)-$l^{5}-stibane Chemical compound [O-][Sb](=O)=O IVUSOGDLVUEEQB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
The present invention relates to a synthesizing method for 4,4 double hexabromocyclododecane alkyl benzene iodine fluorin antimonite, which is made with the following steps: (1) 4,4 double hexabromocyclododecane alkyl benzene iodine is prepared by the reaction with barium chloride under the function of vitriol taking detergent alkylate and potassium iodate as the material, and acetic anhydride as the solution; (2) 4,4 double hexabromocyclododecane alkyl benzene iodine fluorin antimonite is prepared by the ion reaction between 4,4 double hexabromocyclododecane alkyl benzene iodine and fluorin potassium metaantimonate in cyclohexane, chloroform or dichloroethane solution agent. The 4,4 double hexabromocyclododecane alkyl benzene iodine fluorin antimonite synthesized by the present invention has much better solidified performance to the resin.
Description
Technical field
The invention belongs to organic chemical industry's synthesis technical field, relate to a kind of synthetic method of cation light initiator, be specifically related to the synthetic method of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
Background technology
Along with the generally attention of people to environment protection, tradition is solidified and need be used the volatile organic solvent of more contaminate environment restricted greatly because of it, and photocuring is low with its solidification value, curing speed fast, pollute remarkable advantage such as little and enjoy favor.Light trigger as one of photocuring composition main ingredient has become the research object of heat naturally.The Crivello of the mid-1970s General Electric Corporation and Lam have reported research and the application of diaryl group iodized salt as cation light initiator, come into the picture at once, and have obtained commercialization soon.Diaryl group iodized salt had both been inherited the diazonium salt photodissociation and has been generated the long lifetime positively charged ion, removes that irradiation can continue initiated polymerization and to O
2Insensitive needn't N
2The advantage of protection, its exploitation makes the cationic photopolymerization photosensitive polymerization obtain develop rapidly in theory research and practical application.In recent years, still very surging with salt compounded of iodine as the research of the photocuring system of light trigger.It has sizable development again in the practical application of aspects such as tackiness agent, printing ink, coating, sealing material.Along with going deep into of research, the photosensitized initiation system of forming with it has also caused people's very big interest, and the research report of this respect is also increasing year by year.
Because salt compounded of iodine is insoluble to non-polar solvent, be that the photopolymerization system of initiator must be come dissolved monomer with polar solvent to show it, again because of its positively charged ion is poisonous, therefore limited its application to a great extent.At these problems, the novel salt compounded of iodine of synthetic mainly is in order to improve solvability and to reduce toxicity in recent years.
Improving the deliquescent practice has:
(A) introduce long alkyl chain or oxyalkyl chain on the aromatic ring, the introducing of aliphatic chain can improve the solvability of salt compounded of iodine greatly.In addition, the investigator finds that also the introducing of long alkoxy chain also makes λ
MaxRed shift, and toxicity also decreases.This two classes salt compounded of iodine has been widely used in photocuring system.(B) salt compounded of iodine being incorporated in the polymer chain, can be main chain, also can be side group.(C) negative ion is introduced in the polymer chain.
Summary of the invention
Of the present invention in order to improve the solvability of salt compounded of iodine in light-cured resin, the method of introducing long alkyl chain on aromatic ring prepares salt compounded of iodine, the present invention proposes a kind of synthetic route of new salt compounded of iodine, synthesized and have 4,4 ' good-two dodecylbenzene iodine hexafluoro antimonates of oil soluble.
With dodecylbenzene, Potassium Iodate is raw material, and acetic anhydride is a solvent, under the vitriolic effect, has prepared 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates; In cyclohexane solution, 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates and hexafluoro-antimonic acid potassium carry out ion-exchange and obtain purpose product 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.Reaction equation is:
The synthetic method of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates is carried out: (1), be raw material with dodecylbenzene, Potassium Iodate according to the following steps, acetic anhydride is a solvent, under the vitriolic effect, make 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates with the bariumchloride reaction again; (2), in hexanaphthene, chloroform or ethylene dichloride solvent, 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates and hexafluoro-antimonic acid potassium carry out ion-exchange and get 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
(1) 4, the preparation of 4 '-two dodecylbenzene salt compounded of iodine hydrochlorates: dodecylbenzene and acetic anhydride adding are had in three mouthfuls of reaction flasks of thermometer and electric mixer, subcooling is to 5--15 ℃, add Potassium Iodate then, under agitation drip the mixed solution of the vitriol oil and acetic anhydride, rate of addition should keep temperature to be no more than-5 ℃, dropwises, temperature of reaction rises to room temperature, reaction 5-25h; Be lower than under 5 ℃ the condition then, drip distilled water, standing demix extracts secondary at water layer with toluene, merges organic layer, in the organic solution that merges, add barium chloride solution, there is a large amount of white precipitates to separate out, filters, washing, dried filtrate gets 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates; Use anhydrous methanol, ethanol or Virahol recrystallization then, get white solid; (2), 4, the preparation of 4 '-two dodecylbenzene iodine hexafluoro antimonates: get (1) make 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates join in three mouthfuls of reaction flasks that have thermometer and electric mixer, add hexanaphthene, chloroform or ethylene dichloride, and heating makes 4, after 4 '-two dodecylphenyl salt compounded of iodine hydrochlorate dissolvings, add hexafluoro-antimonic acid potassium stirring and refluxing, temperature of reaction is at 25-80 ℃, reaction times 2-10h, concentrate reddish-brown oily matter 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
The mole proportioning of dodecylbenzene and Potassium Iodate is 1.8-2.5: 1; The mole proportioning of dodecylbenzene and acetic anhydride is 1: 1.2-2.4; Dodecylbenzene and vitriolic mole proportioning are 1: 1.2-2.0.
Intermediate 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates and hexafluoro-antimonic acid potassium mole proportioning are 1: 1.0-2.0.The consumption of hexanaphthene, chloroform or ethylene dichloride is 3-5 a times of salt compounded of iodine weight.
Synthetic 4,4 ' of the present invention-two dodecylbenzene iodine hexafluoro antimonates, through ultimate analysis, UV spectrum, infrared spectra and nuclear magnetic resonance measuring, its structure has obtained conclusive evidence.
Results of elemental analyses:
(C
36H
58ISbF
6) calculated value: C:49.60%; H:6.85%; I:14.86%; Sb:14.26%; F:13.35%
Assay determination value: C:49.50%; H:6.75%
-ultraviolet spectrogram
Adopt N, dinethylformamide (DMF) is a solvent, and the uv atlas of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates is seen Fig. 1.As shown in Figure 1, owing to introduced the long carbochain of dodecyl on the phenyl ring, make its maximal ultraviolet absorption move to the long wave direction.λ
Max〉=299nm, the absorbing wavelength λ under the condition of same solvent DMF than xylyl salt compounded of iodine and di-tert-butyl salt compounded of iodine
Max〉=270nm is much longer.
Infrared spectra:
The infrared spectrum of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates is seen Fig. 2.Its infrared absorption has: the C-H absorption of vibrations of phenyl ring: 3059cm
-1, 3025cm
-1The skeletal vibration of phenyl ring absorbs: 1604cm
-1, 1577cm
-1, 1465cm
-1The hydrocarbon plane vibration peak of phenyl ring: 1108cm
-1, 994cm
-1, the absorption of vibrations of methyl: 2956cm
-1, 2925cm
-1, 2854cm
-1, 1406cm
-1The replacement peak of phenyl ring: 827cm
-1Hexafluoroantimonic anion P-F absorbs: 660cm
-1Can see from collection of illustrative plates.Methyl and methylene radical have very strong absorption peak, and this is because have the long carbochain of dodecyl in the structure.At 660cm
-1There is the absorption peak of stronger hexafluoroantimonic anion at the place, proves that hydrochloride has converted stibnate effectively to.
Nucleus magnetic resonance:
Fig. 3 is the nmr spectrum of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.δ 7.2ppm is the chemical shift that phenyl ring iodine atom replaces ortho-hydrogens (a); δ 7.8ppm is the chemical shift that phenyl ring iodine atom replaces contraposition hydrogen (b); δ 2.5ppm is the chemical shift of the methylene radical hydrogen (c) that links to each other with phenyl ring of the long carbochain of dodecyl; δ 0.7-0.9 is the chemical shift of the hydrogen (d) of other methylene radical; 1.2 of δ are the chemical shift near the methylene radical hydrogen (e) of methyl; δ 0.7 is the chemical shift of the methyl hydrogen (f) on the long carbochain of dodecyl.The ratio of phenyl ring hydrogen and dodecyl hydrogen peak integration is roughly 8: 50, and this may be because there is C
11And C
13Due to the chain.
The curing performance of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates
Get resin 3,4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester 6g (UVR-6110), diluting monomer Viscoat 295 1.2g (TMPTA), 4,4 '-two dodecylbenzene iodine hexafluoro antimonate 0.24g mix, under ultrasonic wave, be uniformly dispersed, mixture is coated on the blank sheet of paper, placed under the UV-light and solidify 30s.Then, cured film is washed with ethanol.Calculate the amount of insoluble cured article, experimental result shows that the solidification effect of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates is very good, to 3, and 4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester has solidification fast.
Description of drawings
Fig. 1 is the ultraviolet spectrogram of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
Fig. 2 is the infrared spectrogram of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
Fig. 3 is the nmr spectrum of 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
Embodiment
Example 1:
The preparation of 1,4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates
Getting the dodecylbenzene of 20mL and the acetic anhydride adding of 20mL has in three mouthfuls of reaction flasks of 250mL of thermometer and electric mixer, subcooling is to-5 ℃, add the 20g Potassium Iodate then, under agitation drip the mixed solution that 14mL concentration is 98% vitriol oil and 20mL acetic anhydride, rate of addition should keep temperature to be no more than-5 ℃, dropwise, temperature of reaction rises to room temperature, continues reaction 8h, is being lower than under 5 ℃ the condition then, drip 40mL distilled water, standing demix with 20mL toluene extraction secondary, merges organic layer at water layer, in the toluene liquid that merges, add the 10g barium chloride solution, there is a large amount of white precipitates to separate out, filters, washing, dried filtrate gets 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates are used the dehydrated alcohol recrystallization then, get white solid, fusing point: 64-65 ℃, yield 52.8%.
The preparation of 2,4,4 '-two dodecylbenzene iodine hexafluoro antimonates
Get 130g4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates join in the three mouthfuls of reaction flasks of 500ml that have thermometer and electric mixer, add chloroform 300ml, after the heating for dissolving, add 68g hexafluoro-antimonic acid potassium stirring and refluxing 6h, temperature of reaction is at 60-80 ℃, concentrate reddish-brown oily matter 4,4 '-two dodecylbenzene iodine hexafluoro antimonate 155g, yield 91.3%.
Example 2:
The preparation of 1,4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates
Getting the dodecylbenzene of 100g and the acetic anhydride adding of 200mL has in three mouthfuls of reaction flasks of 500mL of thermometer and electric mixer, subcooling is to 10--5 ℃, add the 40g Potassium Iodate then, under agitation drip 60mL concentration and be 98% the vitriol oil, rate of addition should keep temperature to be no more than-5 ℃, dropwise, temperature of reaction rises to room temperature, continues reaction 5h; Being lower than under 5 ℃ the condition, drip 80mL distilled water, standing demix then, with 100mL extracted with diethyl ether secondary, merge organic layer at water layer, in the ether solution that merges, add the 50g barium chloride solution, there is a large amount of white precipitates to separate out, filters, washing, dried filtrate gets 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates are used the anhydrous isopropyl alcohol recrystallization then, get white solid, fusing point: 64-65 ℃, yield 61.8%.
The preparation of 2,4,4 '-two dodecylbenzene iodine hexafluoro antimonates
Get 127g 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates join in the three mouthfuls of reaction flasks of 500ml that have thermometer and electric mixer, add ethylene dichloride 300ml, after the heating for dissolving, add 77g hexafluoro-antimonic acid potassium stirring and refluxing 2h, temperature of reaction is at 60-80 ℃, concentrate reddish-brown oily matter 4,4 '-two dodecylbenzene iodine hexafluoro antimonate 147g, yield 88.7%
Claims (2)
- The synthetic method of 1,4,4 '-two dodecylbenzene iodine hexafluoro antimonates is carried out: (1), be raw material with dodecylbenzene, Potassium Iodate according to the following steps, acetic anhydride is a solvent, under the vitriolic effect, make 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates with the bariumchloride reaction again; (2), in hexanaphthene, chloroform or ethylene dichloride solvent, 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates and hexafluoro-antimonic acid potassium carry out ion-exchange and get 4,4 '-two dodecylbenzene iodine hexafluoro antimonates, and the mole proportioning of dodecylbenzene and Potassium Iodate is 1.8-2.5: 1; The mole proportioning of dodecylbenzene and acetic anhydride is 1: 1.2-2.4; Dodecylbenzene and vitriolic mole proportioning are 1: 1.2-2.0, and intermediate 4,4 '-two dodecylbenzene salt compounded of iodine hydrochlorates and hexafluoro-antimonic acid potassium mole proportioning are 1: 1.0-2.0, the consumption of hexanaphthene, chloroform or ethylene dichloride are 3-5 times of salt compounded of iodine weight.
- 2, according to claim 14, the synthetic method of 4 '-two dodecylbenzene iodine hexafluoro antimonates, it is characterized in that: (1) 4, the preparation of 4 '-two dodecylbenzene salt compounded of iodine hydrochlorates: dodecylbenzene and acetic anhydride adding are had in three mouthfuls of reaction flasks of thermometer and electric mixer, subcooling is to-15-5 ℃, add Potassium Iodate then, under agitation drip the mixed solution of the vitriol oil and acetic anhydride, rate of addition should keep temperature to be no more than-5 ℃, dropwise, temperature of reaction rises to room temperature, reaction 5-25h; Being lower than under 5 ℃ the condition, drip distilled water then, standing demix extracts secondary at water layer with toluene, merge organic layer, in the organic liquor that merges, add barium chloride solution, have a large amount of white precipitates to separate out, filter, washing, dried filtrate gets 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates; Use anhydrous methanol, ethanol or Virahol recrystallization then, get white solid; (2), 4, the preparation of 4 '-two dodecylbenzene iodine hexafluoro antimonates: get (1) make 4,4 '-two dodecylphenyl salt compounded of iodine hydrochlorates join in three mouthfuls of reaction flasks that have thermometer and electric mixer, add hexanaphthene, chloroform or ethylene dichloride, and heating makes 4, after 4 '-two dodecylphenyl salt compounded of iodine hydrochlorate dissolvings, add hexafluoro-antimonic acid potassium stirring and refluxing, temperature of reaction is at 25-80 ℃, reaction times 2-10h, concentrate reddish-brown oily matter 4,4 '-two dodecylbenzene iodine hexafluoro antimonates.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710053131.6A CN100577671C (en) | 2007-09-05 | 2007-09-05 | Synthetic method of 4,4'-didodecylphenyliodonium hexafluoroantimonate |
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| CN102241562A (en) * | 2011-05-18 | 2011-11-16 | 常州大学 | Preparation method of symmetrical aryl iodide onium hydrochloride |
| CN106192038B (en) * | 2016-07-21 | 2018-09-21 | 江南大学 | The preparation method of blue light luminous fiber |
| KR102740005B1 (en) * | 2022-04-06 | 2024-12-06 | 이피캠텍 주식회사 | Diphenyliodonium salts used as photoinitiator and producing method thereof |
Citations (3)
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|---|---|---|---|---|
| US4151175A (en) * | 1976-12-09 | 1979-04-24 | General Electric Company | Method for making diarylhalonium salts |
| US4238394A (en) * | 1978-10-30 | 1980-12-09 | General Electric Company | Method for making diaryliodonium salts |
| US4607116A (en) * | 1983-03-09 | 1986-08-19 | Nippon Petrochemicals Company Limited | Process for preparing diaryls |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151175A (en) * | 1976-12-09 | 1979-04-24 | General Electric Company | Method for making diarylhalonium salts |
| US4238394A (en) * | 1978-10-30 | 1980-12-09 | General Electric Company | Method for making diaryliodonium salts |
| US4607116A (en) * | 1983-03-09 | 1986-08-19 | Nippon Petrochemicals Company Limited | Process for preparing diaryls |
Non-Patent Citations (2)
| Title |
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| 4，4‘-二乙酰胺基二苯基碘六氟磷酸盐的合成. 谢川等.精细化工，第Vol.23卷第No.3期. 2006 * |
| 四氟硼酸二芳基碘鎓盐的合成及其表征. 许素莲等.长春理工大学学报，第Vol.26卷第No.4期. 2003 * |
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Assignee: Rudong Zhenfeng Yiyang Chemical Co. Ltd. Assignor: Wuhan Institute of Technology Contract record no.: 2011320000176 Denomination of invention: 4,4 '- ethyl benzene synthesis method of iodine? Six Hexafluoroantimonate salt Granted publication date: 20100106 License type: Exclusive License Open date: 20080312 Record date: 20110308 |
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