CN107082781A - Perylene diimide quaternary ammonium compound and its plating application - Google Patents
Perylene diimide quaternary ammonium compound and its plating application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
The present invention relates to organic synthesis field, specifically Yi Zhong perylene diimides quaternary ammonium compound and application thereof, Suo Shu perylene diimide quaternary ammonium compounds have structure shown in Formulas I.This invention Suo Shu perylene diimides quaternary ammonium compound can be applied as plating leveling agent in acid copper sulfate plating.
Description
Technical field
It is Yi Zhong perylene diimide quarternary ammonium salt compounds and application thereof specifically the present invention relates to organic synthesis field, makees
For application of the plating leveling agent in acid copper sulfate plating.
Background technology
Since the mid-term electroplating technology application of 19th century, the technology is constantly improved and developed.Especially into 21
After century, development and needs with electronic technology, copper electroplating layer because of it there is good electric conductivity, thermal conductivity and machinery to extend
The advantages of property and be widely used in the fields such as electronics and IT products.Electroplating technology is had evolved into national economic development can not
Or scarce important component, and be widely used in machinery, it is shipbuilding, Aero-Space, military project, electronics, nuclear industry, light industry, daily
Many aspects such as industry, with the corrosion resistance for improving product, ornamental and feature.Such as in the door handle, instrument board, business of automobile
The piece surfaces such as mark have been plated can make its outward appearance become more aesthetically pleasing after layer of metal coating；Hard chrome is plated in cylinder inner wall, can
The wearability of product is improved to extend the service life of product；Zinc is plated in fastener surface and through appropriate post processing flow
The corrosion resistance of product can be greatly improved afterwards；The coat of metal is plated on sanitaryware can improve the corrosion resistance of product, extension
The service life of product can make product appearance get a promotion again.Therefore, electroplate closely bound up with daily life, it is small to arrive
Lighter, spectacle frame, the greatly surface treatment to aircraft, automobile, most of product that we can see all are by plating
Reason.
Electroplating engineering is to study electroplating industry and the chemical process and physics mistake conducted in the production of other related industries
One engineering science of journey common law, is one of key technology of advanced manufacturing technology industrial chain.It is with chemistry, physics
A cross discipline based on, electronics, machinery and mathematics.
By the geomery that device is plated in industrial production is different, the current density of workpiece surface each point is each in electroplating bath
It is different, improve the mode such as convection current of plating solution if depending merely on to be difficult to obtain thickness distribution uniform and meet the copper plating of various functions requirement
Layer.Therefore industrially in order to obtain the uniform copper coating of surface-brightening, excellent physical properties, thickness distribution, conventional method is
Organic additive is added in sour copper electroplating liquid.
The additive commonly used in acid copper sulfate baths can be divided mainly into inhibitor, light by its effect in the plating solution
Three kinds of agent and leveling agent.In actual electroplating process, additive is by the case of diffusing step control, electroplating additive particle
Diffusion generally occurs, and adsorbs at the larger electrode surface protrusion of tension force and on the avtive spot of electro-deposition, causes
The metallic atom adsorbed at the electrode surface constantly moves to the recess of electrode surface and entered inside metal lattice, so that
Serve the bright levelling effect of additive.The concentration of additive often only has the 1/10 of concentration of metal ions2To 1/105Times, but
These a small amount of additives can bring coating morphology composition and crystal lattice orientation strong influence.Therefore, in order that plating material
The surface topography and physical property of material meet standard and the requirement of every profession and trade, and electroplating additive is played in acid copper sulfate plating
Unusual key effect.
As what relevant industries were required constantly increases, for fast in the system research in the past few decades of electroplating additive
Speed development.On the research of acidic copper plating additive, last century the forties can be traced back to earliest.1945,
Both mentioned in U.S.P2391289 patents in tank liquor plus substituting thioureido, wetting agent and dextrin as additive improve coating
Performance.The fifties are arrived again, it is external successively to report mercaptobenzimidazole (U.S.P 2700020), safranine dye
(U.S.P 2707166), thiazine dyestuff (U.S.P 2805193), the chemical combination such as kiton colors (U.S.P 2805194)
Thing makees hydrosulphate copper plating additive.To the sixties with organic sulfur compound, polyethers, grey phenodiazine anthracene dyes (safranine type)
(U.S.P 3261010) is compounded for hydrosulphate copper facing and is obtained the good copper coating of light, Surface flat.China's scientific research
Personnel have developed the wide temperature acid bright copper plating craft of no dyestuff in last century the seventies, and the technique is with M (2- sulfydryl benzene
And imidazoles), N (ethylene thiourea), PN (polyethyleneimine alkyl salt), P (polyethylene glycol) use and obtain as additive compound
Good result.Same time, foreign countries also report organic polysulfide, mercaptopyridine or mercaptoimidazole, poly- miaow
(U.S.P3804729), the reaction product (B.P 1415129) of Schiff polyethyleneimine and diphenyl carbazone, which is done, adds
Plus agent is used for hydrosulphate copper facing.Last century the eighties, report phthalocyanine compound (U.S.P 4272335), dioxane again
Base aminodithioformic acid+alkyl sulfonic acid (U.S.P 4376685), which does additive, is used for hydrosulphate copper facing.
Then from last century the nineties so far, external major Additive Production business (German Atotech, Japan is big and waits)
Being proposed the dye-type additive such as " 210 ", " Ultra " in the domestic market is used for general hardware electroplating industry copper facing.And dyestuff
The use of type electroplating additive can increase economy and the cost of environment in water pollution control, and the plating of existing dye-type adds
Plus agent has that species is few, difficult prepare (preparation technology complicated), easily decompose and the defect such as cost height.So research and development preparation technology is relative
Simply, it is inexpensive, and environmentally friendly reactive monoazo dyestuffs type electroplating additive enjoys the concern of this area scientist.
Perylene diimide compound is the intermediate of new function material, its derivative have larger conjugated system, compared with
Molecule coplanarity well, relatively low lumo energy, the flowing and transmission , perylene diimide class compounds for being conducive to electronics all have
Very strong fluorescence, absorbs also very strong from visible region to infrared region, with extraordinary heat, photochemistry and chemical stability, and
And also there is relatively high quantum yield, solar energy conversion, molecular switch, optical conductor, electrochemical luminescence, semi-conducting material,
Had a wide range of applications in terms of gas storage material, ion identification, biological fluorescent labeling.Ji Yu perylene diimide class chemical combination
The above characteristic of thing, synthesizing water-solubility perylene diimides analog derivative and by application for electroplating additive be the present invention need solution
Technical problem certainly.
The content of the invention
It is an object of the invention to provide the quarternary ammonium salt compound of Yi class Ji Yu perylene diimide structures, and it regard it as plating
Additive is used.After tested, the series compound shows preferably to suppress the chemical property of copper deposition.
It is a further object to provide the purposes of described Xin Xing perylene diimide quaternary ammonium compounds.
The first aspect of the present invention is there is provided Yi Zhong perylene diimide quaternary ammonium compounds, and it has the structure shown in Formulas I：
Wherein, R in Formulas I1ForR2For H or M, n, o, p and q are 0-18 integer, R1And R2Can be same
When equal, X-For acid radical anion, and X is Br, F, Cl, I, HSO3、HSO4、HCO3、CF3CO3、H2PO4, OTf, OTs or BF4。
It is preferred that, wherein R1ForR2For H orM is 1；N be 0,1,2,3,4,
5th, 6,7,8,9 or 10；P is 3,5 or 7；Q is 3,5,6,11,13 or 17；And x is Cl, Br, F or I.
It is preferred that, wherein R1ForR2For H orM is 1；O be 2,
3 or 4；P is 3,5 or 7；Q is 3,5,6,11,13 or 17；And x is Cl, Br, F or I.
It is preferred that, wherein R1ForR2ForM is 2；N is
0th, 1,2,3,4,5,6,7,8,9 or 10；O is 2,3 or 4；And x is Cl, Br, F or I.
It is preferred that, wherein R1ForR2For m
For 2；N is 0,1,2,3,4,5,6,7,8,9 or 10；O is 2,3 or 4；And x is Cl, Br, F or I.
In the optimal technical scheme of the present invention, R1ForR2Also it isM is 2；N is
0th, 1,2,3,4,5,6,7,8,9 or 10；And x is Cl, Br, F or I.
In another optimal technical scheme of the present invention, R1ForR2For
M is 2；N is 0,1,2,3,4,5,6,7,8,9 or 10；O is 2,3 or 4；And x is Cl, Br, F or I.
In another optimal technical scheme of the present invention, R1ForR2ForM is 1；N is
0th, 1,2,3,4,5,6,7,8,9 or 10；P is 3,5 or 7；And x is Cl, Br, F or I.
In another optimal technical scheme of the present invention, R1ForR2ForM is 1；N be 0,1,2,
3rd, 4,5,6,7,8,9,10 or 11；Q is 3,5,6,11,13 or 17；And x is Cl, Br, F or I.
In another optimal technical scheme of the present invention, R1ForR2Form
For 1；O is 2,3 or 4；P is 3,5 or 7；And x is Cl, Br, F or I.
In a preferred embodiment of the invention, the perylene diimide quaternary ammonium compound stated have as Formula Il,
Structure shown in III, IV, V, VI：
A series of naphthalimide quaternary ammonium compounds shown in Formulas I can be prepared with reference to existing technology of preparing.
There is provided a kind of Shang Shu perylene diimides quaternary ammonium compound (compound shown in Formulas I) for the second aspect of the present invention
It is used as the application of plating leveling agent.
It is preferred that, described plating is electroplated for copper.
It is furthermore preferred that Suo Shu perylene diimides quaternary ammonium compounds as plating leveling agent acid copper sulfate plating in
Application.
Perylene diimides quaternary ammonium compound synthesized by the present invention, this quaternary ammonium salt structure, by the nitrogen in structure just
Ion, i.e., quaternized center can effectively be adsorbed in cathode surface and can suppress the deposition of the copper at aperture and so that copper
Crystalline particle more refines and causes copper plate to obtain high preferentially high preferred orientation, it is used for as quaternary ammonium salt leveling agent
Acid copper plating.
Brief description of the drawings
Fig. 1 are the cyclic voltammetry curve of compound shown in Formula II；
Fig. 2 are the cyclic voltammetry curve of compound shown in formula III；
Fig. 3 are the cyclic voltammetry curve of compound shown in formula IV；
Fig. 4 are the cyclic voltammetry curve of compound shown in Formula V；
Fig. 5 are the cyclic voltammetry curve of compound shown in Formula IV；
Fig. 6 are the cyclic voltammetry curve of compound shown in formula JGB.
Embodiment
The embodiment provided with reference to embodiment the present invention elaborates.
Embodiment 1
Jiang perylene diimide (5.0g, 12.1mmol), 200mL isobutanols, N, N- dimethyl -1,3- diaminopropanes (15mL,
118mmol) mixing is placed in three-neck flask, is heated to 90 DEG C, stirring reaction 24h.Stop reaction, be cooled to room temperature, suction filtration is obtained
Washed to filter cake, and with 20mL deionized waters, 20mL ethanol washs filter cake successively, by obtained crude product with 5% hydroxide
Sodium water solution is heated to 90 DEG C of stirring 30min, to remove Wei reaction perylene diimide raw materials, then solid suction filtration is come out, and is used in combination
20mL deionized waters are washed, and 20mL ethanol washs filter cake and obtains red solid IIa (6.32g, 93%) successively.
Take compound IIa (3.0g) to be dissolved in 150mL toluene, then into reaction system add iodomethane (4.5mL,
72.2mmol), heating reflux reaction 3h under nitrogen protection.Question response liquid is cooled to room temperature, and reaction solution suction filtration is obtained into filter cake,
Crude product is obtained after being washed with ethyl acetate (50mL), drying obtains red brown solid II (4.31g, 93%).
Compound IIa:1H NMR(400MHz,CDCl3):δ 8.70 (d, J=8.0Hz, 4H), 8.42 (d, J=8.0Hz,
4H), 4.16 (t, J=7.6Hz, 4H), 3.46 (t, J=7.2Hz, 4H), 2.14 (s, 12H), 1.82 (m, 4H)；13C NMR
(100MHz,CDCl3):161.8,135.5,130.9,127.6,124.1,122.8,57.2,45.4,39.4,25.9；HRMS
(TOF-ESI)：m/z：calcd for C34H33N4O4：561.2496；Found：561.2491.
Compound II:1H NMR(400MHz,DMSO):δ 8.69 (d, J=8.0Hz, 4H), 8.41 (d, J=8.0Hz,
4H), 4.13 (t, J=7.6Hz, 4H), 3.42 (t, J=7.2Hz, 4H), 3.01 (s, 18H), 2.17 (m, 4H)；13C NMR
(100MHz,DMSO):161.5,135.2,130.5,127.7,124.0,122.5,57.1,45.2,39.2,25.7；HRMS
(TOF-ESI)：m/z：calcd for C18H19N2O2：295.1441；Found：295.1439.
Embodiment 2
Perylene diimide (2g, 5.1mmol) and ammoniacal liquor (1.7g, 100mmol) are dissolved in ethanol (40mL), heating stirring backflow
React 4h.Reaction solution is cooled to room temperature, suction filtration is depressurized and washs filter cake with acetic acid (50mL) and ether (100mL) and obtain dark red
Color solid IIIa (1.85g, 95%).
Take compound IIIa (0.78g, 2mmol), Isosorbide-5-Nitrae-dibromobutane (0.644g, 3mmol), potassium carbonate (0.552g,
2mmol), the KI of catalytic amount is dissolved in 40mLDMF (DMF), is heated to 60 DEG C, stirring reaction 24h.
Reaction solution is poured into 200mL water, a large amount of solids are separated out, decompression suction filtration obtains filter cake, filter cake is rinsed well with water (50mL), dries
Do to obtain red solid IIIb (0.84g, 80%).
Take compound IIIb (0.58g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium acid carbonate (0.84g,
10mmol) it is dissolved in 30mL acetonitriles, is heated to 80 DEG C, stirring reaction 12h.Question response liquid is cooled to room temperature, rotates acetonitrile molten
Agent, red solid III (0.49g, 85%) is obtained with methanol/recrystallized from acetonitrile.
Compound IIIb:1H NMR(400MHz,DMSO):δ 11.27 (s, 1H), 8.69 (d, J=8.0Hz, 4H), 8.39
(d, J=8.0Hz, 4H), 3.89 (t, J=7.6Hz, 2H), 3.16 (t, J=7.2Hz, 2H), 1.82 (m, 2H), 1.56 (m,
2H)；13C NMR(100MHz,DMSO):160.8,134.5,130.2,126.9,123.2,121.9,52.2,43.4,38.4,
26.9；HRMS(TOF-ESI)：m/z：calcd forC28H18BrN2O4：525.0444；Found：525.0443.
Compound III:1H NMR(400MHz,DMSO):δ 11.25 (s, 1H), 8.67 (d, J=8.0Hz, 4H), 8.38
(d, J=8.0Hz, 4H), 3.87 (t, J=7.6Hz, 2H), 3.56 (s, 9H), 3.15 (t, J=7.2Hz, 2H), 1.81 (m,
2H),1.54(m,2H)；13C NMR(100MHz,DMSO):161.4,135.3,131.2,127.4,123.9,121.7,54.8,
51.2,43.4,38.4,26.9；HRMS(TOF-ESI)：m/z：calcd for C31H26N3O4：504.1918；Found：
504.1917.
Embodiment 3
Perylene diimide (2g, 5.1mmol) and 6- bromines hexylamine (2.88g, 16mmol) are dissolved in 40mLDMF (N, N- dimethyl
Formamide) in, 50 DEG C of reaction 4h are heated to, 120 DEG C of reaction 12h are again heated to.Reaction solution is cooled to room temperature, rotated molten
Agent, obtains kermesinus crude product, then with the chromatography (10/1 dichloromethane/dichloromethane of acetone -10/3/acetone (2% first
Alcohol)) obtain dark red solid IVa (3.1g, 85%).
Take compound IVa (0.71g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium acid carbonate (0.84g,
10mmol) it is dissolved in 30mL acetonitriles, is heated to 80 DEG C, stirring reaction 18h.Question response liquid is cooled to room temperature, rotates acetonitrile molten
Agent, red solid IV (0.57g, 85%) is obtained with methanol/recrystallized from acetonitrile.
Compound IVa:1H NMR(400MHz,CDCl3):δ 8.69 (d, J=8.0Hz, 4H), 8.39 (d, J=8.0Hz,
4H), 3.87 (t, J=7.6Hz, 4H), 3.13 (t, J=7.2Hz, 4H), 1.82 (m, 4H), 1.67 (m, 4H), 1.28 (m, 8H)
；13C NMR(100MHz,CDCl3):160.8,134.5,130.2,126.9,123.2,121.9,52.2,48.8,45.6,
43.4,38.4,26.9；HRMS(TOF-ESI)：m/z：calcd forC36H33Br2N2O4：717.0781；Found：
717.0782.
Compound IV:1H NMR(400MHz,DMSO):δ 8.68 (d, J=8.0Hz, 4H), 8.37 (d, J=8.0Hz,
4H), 3.87 (t, J=7.6Hz, 4H), 3.65 (s, 18H), 3.13 (t, J=7.2Hz, 4H), 1.84 (m, 4H), 1.64 (m,
4H),1.23(m,8H)；13C NMR(100MHz,DMSO):160.8,134.5,130.2,126.9,123.2,121.9,54.8,
52.2,48.8,45.6,43.4,38.4,26.9；HRMS(TOF-ESI)：m/z：calcd for C21H25N2O2：337.1911；
Found：337.1910.
Embodiment 4
Take compound IIIa (0.78g, 2mmol), compound Va (1.65g, 6mmol), potassium carbonate (1.65g, 3mmol),
The KI of catalytic amount is dissolved in 30mLDMF (DMF), is heated to 120 DEG C, stirring reaction 20h.Will reaction
Liquid is poured into 200mL water, separates out a large amount of solids, and decompression suction filtration obtains filter cake, rinses filter cake well with water (50mL), dry secretly
Red solid, then obtain red solid Vb (1.17g, 75%) through chromatography (dichloromethane/acetone=10/3v/v).
Take compound Vb (0.78g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium acid carbonate (0.84g,
10mmol) it is dissolved in 30mL acetonitriles, is heated to 80 DEG C, stirring reaction 18h.Question response liquid is cooled to room temperature, rotates acetonitrile molten
Agent, red solid V (0.63g, 85%) is obtained with methanol/recrystallized from acetonitrile.
Compound Vb:1H NMR(400MHz,CDCl3):δ 8.75 (d, J=8.0Hz, 4H), 8.45 (d, J=8.0Hz,
4H), 4.16 (t, J=7.6Hz, 4H), 3.87 (t, J=7.6Hz, 4H), 3.41 (t, J=7.6Hz, 4H), 3.13 (t, J=
7.2Hz,4H),3.05(m,8H)；13C NMR(100MHz,CDCl3):160.8,134.5,130.2,126.9,123.2,
121.9,58.2,49.8,46.6,41.4,39.4,29.9；HRMS(TOF-ESI)：m/z：calcd for C36H33Br2N2O8：
781.0578；Found：781.0574.
Compound V:1H NMR(400MHz,DMSO):δ 8.75 (d, J=8.0Hz, 4H), 8.45 (d, J=8.0Hz, 4H),
4.16 (t, J=7.6Hz, 4H), 3.87 (t, J=7.6Hz, 4H), 3.41 (t, J=7.6Hz, 4H), 3.31 (s, 18H), 3.13
(t, J=7.2Hz, 4H), 3.05 (m, 8H)；13C NMR(100MHz,DMSO):160.8,134.5,130.2,126.9,123.2,
121.9,58.1,54.8,49.7,46.4,41.3,39.1,29.3；HRMS(TOF-ESI)：m/z：calcd for
C21H25N2O4：369.1809；Found：369.1807.
Embodiment 5
Take compound IIIa (0.78g, 2mmol), 1,1,2,2- tetrahydrochysene perfluoro-hexyl iodide (0.935g, 2.5mmol), carbonic acid
Potassium (1.656g, 3mmol), the KI of catalytic amount is dissolved in 30mLDMF (DMF), is heated to 100 DEG C, is stirred
Mix reaction 10h.It is cooled to after room temperature and pours into reaction solution in 200mL water, separate out a large amount of solids, decompression suction filtration obtains filter cake, used
Water (50mL) rinses filter cake well, and filter cake is recrystallized with ethanol as solvent, dry red solid VIa (0.63g,
50%).
Take compound VIa (0.512g, 1mmol), Isosorbide-5-Nitrae-dibromobutane (0.322g, 1.5mmol), potassium carbonate (0.552g,
2mmol), the KI of catalytic amount is dissolved in 30mLDMF (DMF), is heated to 100 DEG C, stirring reaction 14h.
It is cooled to after room temperature and pours into reaction solution in 200mL water, separate out a large amount of solids, decompression suction filtration obtains filter cake, rushed with water (50mL)
Wash clean filter cake, then dark red solid VIb is dried to obtain to filter cake progress chromatography (methylene chloride/methanol=50/1v/v)
(0.58,75%).
Take compound VIb (0.385g, 0.5mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium acid carbonate
(0.84g, 10mmol) is dissolved in 30mL acetonitriles, is heated to 80 DEG C, stirring reaction 18h.Question response liquid is cooled to room temperature, rotates
Acetonitrile solvent, red solid VI (0.35g, 85%) is obtained with methanol/recrystallized from acetonitrile.
Compound VIa:1H NMR(400MHz,DMSO):δ 11.27 (s, 1H), 8.66 (d, J=8.0Hz, 4H), 8.39
(d, J=8.0Hz, 4H), 3.79 (t, J=7.6Hz, 2H), 1.98 (m, 2H)；13C NMR(100MHz,DMSO):159.1,
138.6,135.8,124.6,124.0,121.3,120.6,118.5,117.2,109.5,28.9,24.7；19F NMR
(400MHz,CDCl3):δ-80.9(m,3F),-114.7(m,2F),-124.3(m,2F),-126.0(m,2F)；HRMS(TOF-
ESI)：m/z：calcd for C30H14F9N2O4：637.0804；Found：637.0805.
Compound VIb:1H NMR(400MHz,CDCl3):δ 8.66 (d, J=8.0Hz, 4H), 8.39 (d, J=8.0Hz,
4H), 3.72 (t, J=7.6Hz, 2H), 3.52 (t, J=7.2Hz, 2H), 3.14 (t, J=7.6Hz, 2H), 1.82-1.89 (m,
4H),1.56(m,2H)；13C NMR(100MHz,CDCl3):160.1,139.6,136.3,124.6,124.0,121.3,
120.6,118.5,117.2,109.5,69.3,67.9,50.5,46.7,29.1,24.7；19F NMR(400MHz,CDCl3):δ-
80.9(m,3F),-114.6(m,2F),-124.4(m,2F),-126.0(m,2F)；HRMS(TOF-ESI)：m/z：calcd for
C34H21BrF9N2O4:771.0535；Found:771.0534.
Compound VI:1H NMR(400MHz,DMSO):δ 8.66 (d, J=8.0Hz, 4H), 8.39 (d, J=8.0Hz,
4H), 3.72 (t, J=7.6Hz, 2H), 3.52 (t, J=7.2Hz, 2H), 3.47 (s, 9H), 3.14-3.18 (m, 2H), 2.13
(m,2H),1.58-1.61(m,4H)；13C NMR(100MHz,DMSO):159.1,138.6,135.8,124.6,124.0,
121.3,120.6,118.5,117.2,109.5,69.3,67.9,54.8,50.5,46.7,29.1,24.7；19F NMR
(400MHz,DMSO):δ-80.9(m,3F),-114.6(m,2F),-124.4(m,2F),-126.0(m,2F)；HRMS(TOF-
ESI)：m/z：calcd for C37H29F9N3O4：750.2009；Found：750.2008.
Embodiment 6
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e)s make
For working electrode, platinum rod as to electrode and Ag/AgCl as reference electrode, in the case that rotating speed is 2000 revs/min, in solution
In (100mL) every time be added dropwise 0.02mL according to compound II made from embodiment 1 (2.5g/L, behind all compound concentrations
It is such as consistent without other explanations), do cyclic voltammetry curve test (test result is shown in Fig. 1), additive during cyclic voltammetry
Addition is bigger, and obtained oxidation peak area is smaller, and corresponding is that inhibitory action is stronger, and when peak area ratio is less than 0.5,
The EOT end of test.Titration results (being shown in Table 1) are the amounts for having investigated the additive consumed when peak area ratio is by 0.8, and addition is got over
Show that the inhibitory action of compound is stronger less, the leveling effect played in electroplating process is also better.(it is conventional business to be good for that green to JGB
Product reagent) it is configured with the solution of same concentration and has made titrimetry (the results are shown in Table 1), cyclic voltammetry curve test (test
As a result Fig. 6 is seen).Data analysis can be obtained from table, the plating inhibition of synthesized perylene diimides quarternary ammonium salt compound
It is better than commercial reagents JGB electrochemistry inhibition.The application performance of compound of the present invention is placed on a reality
Apply in example.
Embodiment 7
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e)s make
For working electrode, platinum rod as to electrode and Ag/AgCl as reference electrode, in the case that rotating speed is 2000 revs/min, in solution
In (100mL) every time be added dropwise 0.02mL according to compound III made from embodiment 2 (2.5g/L, behind all compound concentrations
It is such as consistent without other explanations), cyclic voltammetry curve test (test result is shown in Fig. 2) is done, when peak area ratio is less than 0.5,
The EOT end of test.Titration results (being shown in Table 1) are the amounts for having investigated the additive consumed when peak area ratio is by 0.8.
Embodiment 8
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e)s make
For working electrode, platinum rod as to electrode and Ag/AgCl as reference electrode, in the case that rotating speed is 2000 revs/min, in solution
In (100mL) every time be added dropwise 0.02mL according to compound IV made from embodiment 4 (2.5g/L, behind all compound concentrations
It is such as consistent without other explanations), cyclic voltammetry curve test (test result is shown in Fig. 3) is done, when peak area ratio is less than 0.5,
The EOT end of test.Titration results (being shown in Table 1) are the amounts for having investigated the additive consumed when peak area ratio is by 0.8.
Embodiment 9
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e)s make
For working electrode, platinum rod as to electrode and Ag/AgCl as reference electrode, in the case that rotating speed is 2000 revs/min, in solution
In (100mL) every time be added dropwise 0.02mL according to compound V made from embodiment 4 (2.5g/L, behind all compound concentrations such as
It is consistent without other explanations), cyclic voltammetry curve test (test result is shown in Fig. 4) is done, when peak area ratio is less than 0.5, is surveyed
Examination is terminated.Titration results (being shown in Table 1) are the amounts for having investigated the additive consumed when peak area ratio is by 0.8.
Embodiment 10
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e)s make
For working electrode, platinum rod as to electrode and Ag/AgCl as reference electrode, in the case that rotating speed is 2000 revs/min, in solution
In (100mL) every time be added dropwise 0.02mL according to compound VI made from embodiment 4 (2.5g/L, behind all compound concentrations
It is such as consistent without other explanations), cyclic voltammetry curve test (test result is shown in Fig. 5) is done, when peak area ratio is less than 0.5,
The EOT end of test.Titration results (being shown in Table 1) are the amounts for having investigated the additive consumed when peak area ratio is by 0.8.
The cyclic voltammetry titration results of the compound of table 1
The preferred embodiment to the invention is illustrated above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make a variety of equivalent on the premise of without prejudice to the invention spirit
Modification or replacement, these equivalent modifications or replacement are all contained in the application claim limited range.
Claims (8)
1. Yi Zhong perylene diimide quaternary ammonium compounds, it has the structure shown in Formulas I：
Wherein, R1ForR2For H or M, n, o, p and q are 0-18 integer, R1And R2Can be simultaneously
It is equal, X-For acid radical anion, and X is Br, F, Cl, I, HSO3、HSO4、HCO3、CF3CO3、H2PO4, OTf, OTs or BF4。
2. according to claim 1 Suo Shu perylene diimide quaternary ammonium compounds, it is characterised in that wherein R1For
R2For H orM is 1；N is 0,1,2,3,4,5,6,7,8,9 or 10；P is 3,5 or 7；Q be 3,5,6,
11st, 13 or 17；And x is Cl, Br, F or I.
3. according to claim 1 Suo Shu perylene diimide quaternary ammonium compounds, it is characterised in that wherein R1ForR2For H orM is 1；O is 2,3 or 4；P is 3,5 or 77；Q be 3,
5th, 6,11,13 or 17；And x is Cl, Br, F or I.
4. according to claim 1 Suo Shu perylene diimide quaternary ammonium compounds, it is characterised in that wherein R1For
R2ForM is 2；N is 0,1,2,3,4,5,6,7,8,9 or 10；O be 2,3 or
4；And x is Cl, Br, F or I.
5. according to claim 1 Suo Shu perylene diimide quaternary ammonium compounds, it is characterised in that wherein R1ForR2ForM is 2；N be 0,1,2,3,4,5,6,
7th, 8,9 or 10；O is 2,3 or 4；And x is Cl, Br, F or I.
6. it is a kind of such as application of any Suo Shu perylene diimides quaternary ammonium compounds of claim 1-5 as plating leveling agent.
7. according to application of the claim 6 Suo Shu perylene diimides quaternary ammonium compounds as plating leveling agent, its feature exists
In described plating is electroplated for copper.
8. according to application of the claim 6 Suo Shu perylene diimides quaternary ammonium compounds as plating leveling agent, its feature exists
In application of the Suo Shu perylene diimides quaternary ammonium compounds as plating leveling agent in acid copper sulfate plating.
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