CN107082781B - Acid imide quaternary ammonium compound and its plating application - Google Patents
Acid imide quaternary ammonium compound and its plating application Download PDFInfo
- Publication number
- CN107082781B CN107082781B CN201710432586.2A CN201710432586A CN107082781B CN 107082781 B CN107082781 B CN 107082781B CN 201710432586 A CN201710432586 A CN 201710432586A CN 107082781 B CN107082781 B CN 107082781B
- Authority
- CN
- China
- Prior art keywords
- compound
- quaternary ammonium
- acid imide
- plating
- ammonium compound
- 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.)
- Active
Links
Classifications
-
- 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
-
- 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 a kind of acid imide quaternary ammonium compound and application thereof, the acid imide quaternary ammonium compound has structure shown in Formulas I.Acid imide quaternary ammonium compound of the present invention can be used as plating leveling agent and apply in acid copper sulfate plating.
Description
Technical field
The present invention relates to organic synthesis fields, specifically, being a kind of acid imide quarternary ammonium salt compound and application thereof, make
For application of the plating leveling agent in acid copper sulfate plating.
Background technique
Since the application of 19th century mid-term electroplating technology, which is constantly improved and is developed.Especially into 21
It after century, with the development of electronic technology and needs, copper electroplating layer is because it is with good electric conductivity, thermal conductivity and mechanical extension
The advantages that property and be widely used in the fields such as electronics and IT products.Electroplating technology has evolved into national economic development can not
Or scarce important component, and it is widely used in machinery, shipbuilding, aerospace, military project, electronics, nuclear industry, light industry, daily
Many aspects such as industry, to improve the corrosion resistance, decorative and functional of product.Such as door handle, instrument board, quotient in automobile
The piece surfaces such as mark can make its appearance become more aesthetically pleasing after having plated one layer of coat of metal；Hard chrome is plated in cylinder inner wall, it can
The wearability of product is improved to extend the service life of product；Zinc is plated in fastener surface and through post-processing process appropriate
The corrosion resistance of product can be greatly improved afterwards；The coat of metal is plated on sanitaryware i.e. can be improved the corrosion resistance of product, extends
The service life of product can make product appearance get a promotion again.Therefore, be electroplated and daily life it is closely bound up, it is small to arrive
Lighter, spectacle frame arrive greatly the surface treatment of aircraft, automobile, and most of product that we can see all is by plating
Reason.
Electroplating engineering is to study chemical process and physics mistake conducted in electroplating industry and the production of other related industries
One engineering science of journey common law is one of the key technology of advanced manufacturing technology industrial chain.It is with chemistry, physics
A cross discipline based on, electronics, machinery and mathematics.
Since the geomery of device plated in industrial production is different, the current density of workpiece surface each point is each in electroplating bath
It is different, it is difficult to obtain thickness distribution if depending merely on the modes such as the convection current for improving plating solution uniformly and meets the copper plating of various functional requirements
Layer.Therefore industrially in order to obtain the uniform copper coating of surface-brightening, excellent physical properties, thickness distribution, common method is
Organic additive is added in sour copper electroplating liquid.
Common additive can be divided mainly into inhibitor, light by its effect in the plating solution in acid copper sulfate baths
Agent and three kinds of leveling agent.In the case that additive is controlled by diffusing step in practical electroplating process, electroplating additive particle
It usually will appear diffusion, and be adsorbed at the biggish electrode surface protrusion of tension and on the active site of electro-deposition, cause
The metallic atom adsorbed at the electrode surface constantly moves to the recess of electrode surface and enters inside metal lattice, thus
Play the role of the bright levelling 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 to make be electroplated material
The surface topography and physical property of material meet the standard and requirement of every profession and trade, and electroplating additive plays in acid copper sulfate plating
Unusual key effect.
As what relevant industries required constantly increases, for fast in the system research in the past few decades of electroplating additive
Speed development.About the research of acidic copper plating additive, can be traced earliest to last century the forties.1945,
It had both been mentioned in U.S.P2391289 patent in tank liquor plus substituting thioureido, wetting agent and dextrin improves coating as additive
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)
Object makees hydrosulphate copper plating additive.To sixties organic sulfur compound, polyethers, grey phenodiazine anthracene dyes (safranine type)
(U.S.P 3261010) compounding is for hydrosulphate copper facing and obtains bright, the good copper coating of 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) used and obtained 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
Add agent for hydrosulphate copper facing.Last century the eighties, and report phthalocyanine compound (U.S.P 4272335), dioxane
Base aminodithioformic acid+alkyl sulfonic acid (U.S.P 4376685) does additive for hydrosulphate copper facing.
Then so far from last century the nineties, external major Additive Production quotient (German Atotech, Japan is big and waits)
It is proposed the dye-types additive such as " 210 ", " Ultra " in the domestic market for general hardware electroplating industry copper facing.And dyestuff
The use of type electroplating additive will increase the cost of economy and environment in water pollution control, and the plating of existing dye-type adds
Add agent there are types few, difficult the defects of preparing (preparation process is complicated), easily decomposing and is at high cost.So research and development preparation process is opposite
Simply, inexpensive, and environmentally friendly reactive monoazo dyestuffs type electroplating additive is by the concern of this field scientist.
Imide compound is the intermediate of new function material, its derivative have biggish conjugated system, compared with
Molecule coplanarity well, lower lumo energy, are conducive to the flowing and transmission of electronics, imide analog compounds all have
Very strong fluorescence absorbs also very by force from visible region to infrared region, has extraordinary heat, photochemistry and chemical stability, and
And also have relatively high quantum yield, solar energy conversion, molecular switch, optical conductor, electrochemical luminescence, semiconductor material,
Gas storage material, ion identification, biological fluorescent labeling etc. have a wide range of applications.Based on acid imide chemical combination
The above characteristic of object, the imide derivatives of synthesizing water-solubility and by application be electroplating additive be that the present invention needs to solve
Certainly the technical issues of.
Summary of the invention
Quarternary ammonium salt compound the purpose of the present invention is to provide one kind based on imide structure, and by conduct be electroplated
Additive carry out using.After tested, which shows the chemical property for preferably inhibiting copper deposition.
It is a further object to provide the purposes of the novel acid imide quaternary ammonium compound.
The first aspect of the present invention provides a kind of acid imide quaternary ammonium compound, with structure shown in Formulas I:
Wherein, R in Formulas I1ForR2For H or M, n, o, p and q are the integer of 0-18, R1And R2It can be with
Equal, X simultaneously-For acid radical anion, and X is Br, F, Cl, I, HSO3、HSO4、HCO3、CF3CO3、H2PO4, OTf, OTs or BF4。
Preferably, wherein R1ForR2For H orM is 1；N be 0,1,2,3,4,
5,6,7,8,9 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.
Preferably, 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.
Preferably, wherein R1ForR2ForM 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.
Preferably, wherein 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 an optimal technical scheme of the invention, R1ForR2Also it isM is 2；N is
0,1,2,3,4,5,6,7,8,9 or 10；And x is Cl, Br, F or I.
In another optimal technical scheme of the 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 invention, R1ForR2ForM is 1；N is
0,1,2,3,4,5,6,7,8,9 or 10；P is 3,5 or 7；And x is Cl, Br, F or I.
In another optimal technical scheme of the invention, R1ForR2ForM is 1；N be 0,1,2,
3,4,5,6,7,8,9,10 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 invention, R1ForR2For
M is 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 acid imide quaternary ammonium compound 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.
The second aspect of the present invention provides a kind of above-mentioned acid imide quaternary ammonium compound (compound shown in Formulas I)
Application as plating leveling agent.
Preferably, the plating is copper plating.
It is furthermore preferred that the acid imide quaternary ammonium compound is as plating leveling agent in acid copper sulfate plating
Application.
Acid imide quaternary ammonium compound synthesized by the present invention, this quaternary ammonium salt structure, just by the nitrogen in structure
Ion, i.e., quaternized center can effectively be adsorbed in cathode surface and be able to suppress the copper deposition at aperture and make copper
Crystalline particle more refines and copper plate is made to obtain high preferentially high preferred orientation, allows to be used for as quaternary ammonium salt leveling agent
Acid copper plating.
Detailed description of the invention
Fig. 1 is the cyclic voltammetry curve of compound shown in Formula II；
Fig. 2 is the cyclic voltammetry curve of compound shown in formula III；
Fig. 3 is the cyclic voltammetry curve of compound shown in formula IV；
Fig. 4 is the cyclic voltammetry curve of compound shown in Formula V；
Fig. 5 is the cyclic voltammetry curve of compound shown in Formula IV；
Fig. 6 is the cyclic voltammetry curve of compound shown in formula JGB.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
Embodiment 1
By acid imide (5.0g, 12.1mmol), 200mL isobutanol, N, N- dimethyl -1,3- diaminopropanes (15mL,
118mmol) mixing is placed in three-neck flask, is heated to 90 DEG C, is stirred to react for 24 hours.Stop reaction, is cooled to room temperature, filters
Washed to filter cake, and with 20mL deionized water, 20mL ethyl alcohol successively washs filter cake, by obtained crude product with 5% hydroxide
Sodium water solution is heated to 90 DEG C of stirring 30min, to remove unreacted acid imide raw material, then solid is filtered out, is used in combination
The washing of 20mL deionized water, 20mL ethyl alcohol successively wash filter cake and obtain red solid IIa (6.32g, 93%).
Take compound IIa (3.0g) to be dissolved in 150mL toluene, then into reaction system be added iodomethane (4.5mL,
72.2mmol), heating reflux reaction 3h under nitrogen protection.It is cooled to room temperature to reaction solution, reaction solution is filtered to obtain 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
Acid imide (2g, 5.1mmol) and ammonium hydroxide (1.7g, 100mmol) are dissolved in ethyl alcohol (40mL), heating stirring reflux
React 4h.Reaction solution is cooled to room temperature, decompression filter and with acetic acid (50mL) and ether (100mL) wash filter cake obtain it is dark red
Color solid IIIa (1.85g, 95%).
It takes compound IIIa (0.78g, 2mmol), Isosorbide-5-Nitrae-dibromobutane (0.644g, 3mmol), potassium carbonate (0.552g,
2mmol), the potassium iodide of catalytic amount is dissolved in 40mLDMF (n,N-Dimethylformamide), is heated to 60 DEG C, is stirred to react for 24 hours.
Reaction solution is poured into 200mL water, a large amount of solids are precipitated, decompression filters and obtains filter cake, rinses filter cake well with water (50mL), dries
Do to obtain red solid IIIb (0.84g, 80%).
It takes compound IIIb (0.58g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium bicarbonate (0.84g,
It 10mmol) is dissolved in 30mL acetonitrile, is heated to 80 DEG C, is stirred to react 12h.It is cooled to room temperature to reaction solution, it is molten to rotate acetonitrile
Agent obtains red solid III (0.49g, 85%) 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
Acid imide (2g, 5.1mmol) and 6- bromine 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, is rotated molten
Agent, obtains kermesinus crude product, then with chromatography (10/1 methylene chloride/- 10/3 methylene chloride of acetone/acetone (2% first
Alcohol)) obtain dark red solid IVa (3.1g, 85%).
It takes compound IVa (0.71g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium bicarbonate (0.84g,
It 10mmol) is dissolved in 30mL acetonitrile, is heated to 80 DEG C, is stirred to react 18h.It is cooled to room temperature to reaction solution, it is molten to rotate acetonitrile
Agent obtains red solid IV (0.57g, 85%) 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
It takes compound IIIa (0.78g, 2mmol), compound Va (1.65g, 6mmol), potassium carbonate (1.65g, 3mmol),
The potassium iodide of catalytic amount is dissolved in 30mLDMF (n,N-Dimethylformamide), is heated to 120 DEG C, is stirred to react 20h.It will reaction
Liquid pours into 200mL water, and a large amount of solids are precipitated, and decompression filters and obtains filter cake, rinses filter cake well with water (50mL), dry secretly
Red solid, then red solid Vb (1.17g, 75%) is obtained through chromatography (methylene chloride/acetone=10/3v/v).
It takes compound Vb (0.78g, 1mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium bicarbonate (0.84g,
It 10mmol) is dissolved in 30mL acetonitrile, is heated to 80 DEG C, is stirred to react 18h.It is cooled to room temperature to reaction solution, it is molten to rotate acetonitrile
Agent obtains red solid V (0.63g, 85%) 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
It takes compound IIIa (0.78g, 2mmol), 1,1,2,2- tetrahydro perfluoro-hexyl iodide (0.935g, 2.5mmol), carbonic acid
Potassium (1.656g, 3mmol), the potassium iodide of catalytic amount are dissolved in 30mLDMF (n,N-Dimethylformamide), are heated to 100 DEG C, stir
Mix reaction 10h.Reaction solution is poured into 200mL water after being cooled to room temperature, a large amount of solids are precipitated, decompression filters and obtains filter cake, uses
Water (50mL) rinses filter cake well, is recrystallized with ethanol as solvent to filter cake, dry red solid VIa (0.63g,
50%).
It takes compound VIa (0.512g, 1mmol), Isosorbide-5-Nitrae-dibromobutane (0.322g, 1.5mmol), potassium carbonate (0.552g,
2mmol), the potassium iodide of catalytic amount is dissolved in 30mLDMF (n,N-Dimethylformamide), is heated to 100 DEG C, is stirred to react 14h.
Reaction solution is poured into 200mL water after being cooled to room temperature, a large amount of solids are precipitated, decompression filters and obtains filter cake, is rushed with water (50mL)
Wash clean filter cake, then chromatography (methylene chloride/methanol=50/1v/v) is carried out to filter cake and dries to obtain dark red solid VIb
(0.58,75%).
It takes compound VIb (0.385g, 0.5mmol), trimethy-lammonium chloride (0.96g, 10mmol), sodium bicarbonate
(0.84g, 10mmol) is dissolved in 30mL acetonitrile, is heated to 80 DEG C, is stirred to react 18h.It is cooled to room temperature, rotates to reaction solution
Acetonitrile solvent obtains red solid VI (0.35g, 85%) 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) work
For working electrode, platinum stick is used as to electrode and Ag/AgCl as reference electrode, in the case that revolving speed is 2000 revs/min, in solution
Be added dropwise every time in (100mL) 0.02mL according to compound II made from embodiment 1 (2.5g/L, behind all compound concentrations
It is consistent if there is no other explanation), do cyclic voltammetry curve test (test result is shown in Fig. 1), additive when cyclic voltammetry
Additive amount is bigger, and obtained oxidation peak area is smaller, corresponding to be that inhibiting effect 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 to have investigated the amount of the consumed additive when peak area ratio is 0.8, and additive amount is got over
Show that the inhibiting effect of compound is stronger less, it is also better in the leveling effect that electroplating process plays.(it is common quotient that it is green to be good for that 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 see Fig. 6).Data analyze available, the plating inhibitory effect of synthesized acid imide quarternary ammonium salt compound from table
It is better than the electrochemistry inhibitory effect of commercial reagents JGB.The application performance of compound of the present invention is placed on a reality
It applies in example.
Embodiment 7
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e) work
For working electrode, platinum stick is used as to electrode and Ag/AgCl as reference electrode, in the case that revolving speed is 2000 revs/min, in solution
Be added dropwise every time in (100mL) 0.02mL according to compound III made from embodiment 2 (2.5g/L, behind all compound concentrations
It is consistent if there is no other explanation), 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 to have investigated the amount of the consumed additive when peak area ratio is 0.8.
Embodiment 8
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e) work
For working electrode, platinum stick is used as to electrode and Ag/AgCl as reference electrode, in the case that revolving speed is 2000 revs/min, in solution
Be added dropwise every time in (100mL) 0.02mL according to compound IV made from embodiment 4 (2.5g/L, behind all compound concentrations
It is consistent if there is no other explanation), 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 to have investigated the amount of the consumed additive when peak area ratio is 0.8.
Embodiment 9
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e) work
For working electrode, platinum stick is used as to electrode and Ag/AgCl as reference electrode, in the case that revolving speed is 2000 revs/min, in solution
Be added dropwise every time in (100mL) 0.02mL according to compound V made from embodiment 4 (2.5g/L, behind all compound concentrations such as
No other explanations are consistent), 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 terminates.Titration results (being shown in Table 1) are to have investigated the amount of the consumed additive when peak area ratio is 0.8.
Embodiment 10
Prepare a CuSO containing 50g/L4·5H2O and 250g/L H2SO4Copper-bath, with Pt rotating disk electrode (r.d.e) work
For working electrode, platinum stick is used as to electrode and Ag/AgCl as reference electrode, in the case that revolving speed is 2000 revs/min, in solution
Be added dropwise every time in (100mL) 0.02mL according to compound VI made from embodiment 4 (2.5g/L, behind all compound concentrations
It is consistent if there is no other explanation), 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 to have investigated the amount of the consumed additive when peak area ratio is 0.8.
The cyclic voltammetry titration results of 1 compound of table
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (2)
1. a kind of application of acid imide quaternary ammonium compound in acid copper sulfate plating as plating leveling agent；
The acid imide quaternary ammonium compound is compound shown in Formulas I:
In Formulas I, R1ForR2For H, X is Br or I；
Wherein, m is 1 or 2；N is 1,2 or 4；O is 2；P is 3.
2. application as described in claim 1；It is characterized in that, wherein the acid imide quaternary ammonium compound is following
It is a kind of in compound:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710432586.2A CN107082781B (en) | 2017-06-09 | 2017-06-09 | Acid imide quaternary ammonium compound and its plating application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710432586.2A CN107082781B (en) | 2017-06-09 | 2017-06-09 | Acid imide quaternary ammonium compound and its plating application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107082781A CN107082781A (en) | 2017-08-22 |
| CN107082781B true CN107082781B (en) | 2019-08-09 |
Family
ID=59605551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710432586.2A Active CN107082781B (en) | 2017-06-09 | 2017-06-09 | Acid imide quaternary ammonium compound and its plating application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107082781B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637015A (en) * | 2021-08-10 | 2021-11-12 | 南昌航空大学 | Quaternary ammonium salt functionalized perylene diimide micromolecule interface layer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2789310B1 (en) * | 1999-02-09 | 2001-05-04 | Oreal | USE OF CATIONIC CONDENSED POLYCYCLIC COMPOUNDS IN DYEING KERATINIC MATERIALS, DYE COMPOSITIONS AND DYEING METHODS |
| US20150243869A1 (en) * | 2014-02-20 | 2015-08-27 | The Regents Of The University Of California | Self doping materials and methods |
| CN104725383B (en) * | 2014-12-29 | 2017-04-05 | 华东理工大学 | Pyrrolo-pyrrole-dione (DPP) quaternary ammonium compound and its preparation and use |
-
2017
- 2017-06-09 CN CN201710432586.2A patent/CN107082781B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107082781A (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104725383B (en) | Pyrrolo-pyrrole-dione (DPP) quaternary ammonium compound and its preparation and use | |
| CN102884589B (en) | Nano ink composition | |
| Wang et al. | Quinacridone skeleton as a promising efficient leveler for smooth and conformal copper electrodeposition | |
| CN109824674B (en) | Heterocyclic pyrrolopyrrole dione quaternary ammonium salt compound and preparation method and application thereof | |
| Chen et al. | Synthesis of quaternary ammonium salts based on diketopyrrolopyrroles skeletons and their applications in copper electroplating | |
| CN103623741B (en) | Graphene dispersing agent, preparation method thereof and preparation method of graphene | |
| CN102617647B (en) | Terpyridyl ruthenium coordination compound, and preparation method and application thereof | |
| CN106749241B (en) | Four formoxyl diimide derivative of 1,4,5,8- naphthalene and application thereof | |
| CN102675897A (en) | Thiourea/urea aromatic amine dye, as well as preparation method and application thereof | |
| CN107082781B (en) | Acid imide quaternary ammonium compound and its plating application | |
| Chen et al. | Effects of alkyl chain length and anion on the optical and electrochemical properties of AIE-active α-cyanostilbene-containing triphenylamine derivatives | |
| CN103193777B (en) | Method for preparing zodi-perylene tetracarboxylic acid diimide derivative | |
| BRPI1006465B1 (en) | electrodepositable coating composition, substrate and method for preparing an electrodepositable coating composition | |
| CN110105357B (en) | Quinacridone quaternary ammonium salt compound and preparation method and application thereof | |
| CN105646346B (en) | Naphthalimide quaternary ammonium compound and application thereof | |
| Li et al. | Synthesis of coplanar quaternary ammonium salts with excellent electrochemical properties based on an anthraquinone skeleton and their application in copper plating | |
| CN110577497B (en) | Indanthrone quaternary ammonium salt compound and preparation method and application thereof | |
| CN105669721A (en) | Two-dimensional zinc coordination polymer of triazole heterocycle, preparation method and application thereof | |
| CN109897043B (en) | Fluorine-containing pyrrolopyrrole diketone quaternary ammonium salt compound and preparation method and application thereof | |
| CN104672237A (en) | Organic photosensitive dye based on phenanthroline as electron acceptor as well as preparation method and application of organic photosensitive dye | |
| CN110845518B (en) | Green phthalocyanine compound and preparation method thereof | |
| CN106632262A (en) | Triarylpyridine derivatives containing carbazole frameworks and preparation method and application thereof | |
| CN112250881A (en) | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material | |
| Xie et al. | Influence of 1, 8-naphthalimide derivatives as additives on the electrodeposition of tin from methanesulfonic acid system | |
| CN103554955A (en) | Bi-D-pi-A-methenyl cyanine dye and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |