CN110004471A - A kind of preparation method of green alkaline admiro complexing agent - Google Patents
A kind of preparation method of green alkaline admiro complexing agent Download PDFInfo
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- CN110004471A CN110004471A CN201910423874.0A CN201910423874A CN110004471A CN 110004471 A CN110004471 A CN 110004471A CN 201910423874 A CN201910423874 A CN 201910423874A CN 110004471 A CN110004471 A CN 110004471A
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- complexing agent
- admiro
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- alkaline
- organic amine
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of preparation method of green alkaline admiro complexing agent, the preparation method of the green alkaline admiro complexing agent includes: the p-hydroxyphenylhydantion of the cis-butenedioic anhydride of 50~200g/L and the reactant of organic amine and 2~10g/L.Complexing agent prepared by the preparation method of green alkaline admiro complexing agent of the present invention, complexing power is strong, the complex property of formation is stablized, it can directly be converted from zincate galvanizing to admiro, the content of nickel in alloy layer is easily controllable between 10%~16%, current efficiency and crystallization of refinement can be improved to a certain extent, the temperature range of operation is wide, dispersion and deep plating performance are good, the plating solution for using complexing agent of the present invention to form as additive, 5~50 DEG C of temperature range, 0.5~5A/dm2 of current density, 10~60min of electroplating time, obtained coating, nickel content is between 10%~15%, it is about 30hr that the white rust time, which occurs, in the neutral salt spray test of no passivation, the red rust time occur is about 800hr or so.
Description
Technical field
The present invention relates to ZnO, NiSO4With the alkaline zincate system admiro surface treatment neck that NaOH is raw material
Domain more particularly to a kind of preparation method of green alkaline admiro complexing agent.
Background technique
Admiro is a kind of anti-corrosion coating for nearly twenty or thirty year just causing to pay attention to extensively.Currently, main anode is anti-
Shield property coating is zinc coat, but the raising of the needs and industry requirement with national industry upgrading, and traditional monometallic coating is not
It is able to satisfy existing demand, compared with other alloys, admiro has higher anti-corrosive properties, wear resistance and thermal-shock resistance；
Thus by extensive concern both domestic and external and application, shared specific gravity is also increasing in protective coating.
Admiro has the advantage that (1) excellent corrosion resistance compared to other monometallic coating.Nickeliferous 10% or less
Zn-ni alloy deposits it is 3~5 times higher than the zinc coat corrosion resistance of stack pile；Nickeliferous 10%~16% alloy layer is (most preferably
13%) 6~10 times higher than zinc coat, also superior to cadmium and cadmium titanium alloy.(2) excellent mechanical performance.Do not change steel after plating
Yield strength, tensile strength and elongation, plasticity are good.Cadmium plating layer, notch pull test are comparable in torsion-pull test
It is outstanding for cadmium coater on space flight neighborhood with satisfied low hydrogen brittleness.(3) excellent soldering.Under various conditions all
It is easy welding, while without the disadvantage of long whisker.(4) small to workpiece corrosion, coating internal stress is small.(5) solution dispersibility,
Covering power is good, coating is bright smooth.
Currently, environmentally friendly alkaline zinc-nickel alloy additive in the market is largely imported product, price is higher；Domestic adds
Add agent manufacturer to be mostly used organic amine and sodium potassium tartrate tetrahydrate etc. to use as alkaline zinc-nickel alloy complexing agent, performance is not sufficiently stable, plating
The nickel content of the alloy layer of formation also has biggish difference, so market in urgent need one kind is cheap, the alkali of function admirable
Property Zinc-nickel alloy electroplating complexing agent and corresponding additive product.
China Patent Publication No. CN105350037A discloses a kind of alkaline non-cyanogen galvanization nickel alloy plating solution, consisting of sulphur
Sour 5~200g/L of zinc, 1~150g/L of nickel sulfate, 5~435g/L of potassium carbonate, main 20~400g/L of complexant, auxiliary complexing agent 5
~300g/L, wherein main complexant is hydantoins and its derivative, and auxiliary complexing agent is organic amine, organic acid and its salt, gathers
The one or more of ethylene glycol, sulphite, urea or thiocarbamide etc.；The admiro of available nickel content 10%~16% plates
Layer.United States Patent (USP) US20050133376A1 discloses a kind of Electroplate liquid of alkaline zinc-nickel alloy, and group becomes 1~100g/L of zinc, nickel
0.1~50g/L, at least one nickel ion complexing agent and at least one 0.1~50g/L non-ionic polyoxyethylene ether surface active
Agent, complexing agent are one or more of aliphatic amine polymer, ethyleneamines or polyethyleneimine of low molecular weight, available to contain
There is the alloy layer of a large amount of γ crystal phases.
For Electrodeposition of Zn-ni Alloy In Alkaline Bath system, the complexing agent mainly used is mostly organic amine or polyphosphinates
(HEDP) etc., the concentration of such complexing agent is high, strong toxicity, although zn-ni alloy deposits can be obtained, in coating, nickel content is not
It is easy to control, it may also result in the eutrophication of water quality after discharge of wastewater, irreversible harm can be caused to environment, be not suitable for big
Range applications.
Summary of the invention
In order to overcome the shortcomings of Related product in the prior art, the present invention proposes a kind of green alkaline admiro complexing
The preparation method of agent, by carrying out structural modification, the organic compound synthesized, thus it is possible to vary the deposition of nickel ligand to organic amine
Current potential, make the sedimentation potential of nickel complex and Zn complex further to, can not only make the equilibrium potential of metal ion to
Negative direction is mobile, moreover it is possible to increase cathodic polarization, improve current efficiency to a certain extent；This complexing agent is used directly for Alkaline Zinc
In the zinc-plated conversion to admiro of hydrochlorate, it is not necessary to prepare plating solution again, save the cost, intermediate synthetic method is simple, does not make
With autoclave, it is not related to pyroreaction, is conducive to industrialization.
The present invention provides a kind of preparation methods of green alkaline admiro complexing agent, including following component: 50~
The p-hydroxyphenylhydantion of the cis-butenedioic anhydride of 200g/L and the reactant of organic amine and 2~10g/L.
In some embodiments of the present invention, the synthesis step of the reactant of the cis-butenedioic anhydride and organic amine includes:
Deionized water is put into the reaction flask with heating, stirring and reflux condensing tube, the organic of 1~5mol is then added
Amine is to slowly warm up to 50~80 DEG C；
When temperature reaches 50 DEG C or so in reaction flask, it is slowly added to the finely ground cis-butenedioic anhydride powder of 2~20mol in batches, reacts
After, pH value is adjusted to 6~7 or so with liquid alkaline.
In some embodiments of the present invention, the synthesis step further include:
After the reactant and 2~10g/L p-hydroxyphenylhydantion of 50~200g/L cis-butenedioic anhydride and organic amine are mixed, supplement
Deionized water is uniformly mixed, and is settled to 1L.
In some embodiments of the present invention, the organic amine uses monomethyl amine, dimethylamine, diethylamine, N, N diformazan
Any combination of one or more of base amino propylamine, ethylenediamine, diethylenetriamine, triethylene tetramine or other ethyleneamines.
Compared with prior art, the present invention has the following advantages:
Complexing agent prepared by the preparation method of green alkaline admiro complexing agent of the present invention, complexing power
By force, the complex property of formation is stablized, and can directly be converted from zincate galvanizing to admiro, the nickel in alloy layer contains
It measures easily controllable between 10%~16%, current efficiency and crystallization of refinement can be improved to a certain extent.The temperature of operation
Range is wide, and dispersion and deep plating performance are good, the plating solution for using complexing agent of the present invention to form as additive, and 5~50 DEG C of temperature range,
0.5~5A/dm2 of current density, 10~60min of electroplating time, obtained coating, nickel content is between 10%~15%, without blunt
It is about 30hr that the white rust time, which occurs, in the neutral salt spray test of change, and the red rust time occur is about 800hr or so.
Specific embodiment
It in order to enable those skilled in the art to better understand the solution of the present invention, below will be to the skill in the embodiment of the present invention
Art scheme is clearly and completely described, it is clear that and described embodiments are only a part of the embodiments of the present invention, rather than
Whole embodiments.The invention can be realized in many different forms, however it is not limited to embodiment described herein, on the contrary
Ground, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.Those skilled in the art explicitly and implicitly understand, implementation described herein
Example can be combined with other embodiments.
The preparation method of the green alkaline admiro complexing agent include include following component: 50~200g/L's is suitable
The p-hydroxyphenylhydantion of the reactant and 2~10g/L of acid anhydride and organic amine.
Wherein, the preparation route of the reactant of cis-butenedioic anhydride and organic amine is as follows:
In an embodiment of the present invention, the synthesis step of the reactant of the cis-butenedioic anhydride and organic amine includes:
Deionized water is put into the reaction flask with heating, stirring and reflux condensing tube, the organic of 1~5mol is then added
Amine is to slowly warm up to 50~80 DEG C；
When temperature reaches 50 DEG C or so in reaction flask, it is slowly added to the finely ground cis-butenedioic anhydride powder of 2~20mol in batches, reacts
After, pH value is adjusted to 6~7 or so with liquid alkaline；
After the reactant and 2~10g/L p-hydroxyphenylhydantion of 50~200g/L cis-butenedioic anhydride and organic amine are mixed, supplement
Deionized water is uniformly mixed, and is settled to 1L.
In an embodiment of the present invention, the organic amine uses monomethyl amine, dimethylamine, diethylamine, N, N dimethyl amino
Any combination of one or more of propylamine, ethylenediamine, diethylenetriamine, triethylene tetramine or other ethyleneamines.
In an embodiment of the present invention, the process for preparation of basal liquid specifically: the solid sodium hydroxide of calculation amount is added
In coating bath, the water of about 1/3 volume of bath solution is added, then it is molten to be slowly added into sodium hydroxide by stirring and dissolving for the zinc oxide of calculation amount
It is stirring while adding in liquid, it is allowed to be completely dissolved, then adds water to prescribed volume, low current can try to plate after electrolysis a period of time；
Or zincate galvanizing working solution is taken, after low current electrolysis falls original additive, it can be used to Zinc-nickel alloy electroplating basal liquid.
Embodiment one
In the 500ml four-hole bottle with stirring, heating and reflux condensing tube of clean dried, 250ml deionized water is added
With 40% monomethyl amine solution of 78g (1mol)；50 DEG C or so are to slowly warm up under stirring, by 200g (2.0mol) horse finely ground in advance
Carry out acid anhydrides solid powder, in addition reaction flask in batches, exothermic heat of reaction opens condensed water, prevents monomethyl amine from volatilizing, control charging
Rate makes the temperature of system be no more than 80 DEG C；After adding, then insulation reaction 30min is heated to 80 DEG C of insulation reactions
3hr is cooled to 20 DEG C or so after completion of the reaction, is adjusted the pH value of system to 7 or so with 35% liquid alkaline, spare after cooling.
It taking the above-mentioned reactant of 120g to pour into 1000ml flask, 4g p-hydroxybenzene hydantoins is added, stirring is extremely dissolved,
Then addition deionized water arrives alkaline zinc-nickel alloy complexing agent to 1L.
Application example
RG-285 is Wuhan Jie Ruisi metal Surface Treatment Technique Co., Ltd alkaline zinc-nickel alloy product.
It takes above-mentioned solution 500ml to be added in the slot of Hull, anode is done with No. zero zine plate, takes throwing through cotton piece buff with a thickness of 0.3mm
Light is cathode at the iron plate (6.5cm × 20cm) of mirror surface, and Hull slot is placed in water bath with thermostatic control, controls 25 DEG C of test piece temperature, electric current
Density 1A/dm2, electroplating time 20min obtains full sheet uniform bright coating, successively takes a little in test piece, use X fluorescence spectrum
Calibrator measures the thickness and nickel content of different parts, the result is as follows:
| Serial number | Thickness μm | Nickel content % |
| A | 8.52 | 13.01 |
| B | 8.01 | 13.22 |
| C | 7.79 | 13.35 |
| D | 7.32 | 13.52 |
| E | 7.19 | 13.61 |
Embodiment two
In 500ml four-hole bottle of the clean dried with stirring, heating and reflux condensing tube, be added 50ml deionized water and
Then 72g (1mol) ethylenediamine stirs uniform to system at 15~20 DEG C；50 DEG C or so are to slowly warm up under stirring, it will
392.4g (4.0mol) finely ground maleic anhydride solid powder in advance, in addition reaction flask in batches, exothermic heat of reaction opens condensation
Water prevents ethylenediamine from volatilizing, and controls feed rate, and the temperature of system is made to be no more than 80 DEG C；After adding, insulation reaction 30min, so
After be heated to 80 DEG C of insulation reaction 3hr, after completion of the reaction, 20 DEG C or so are cooled to, with 35% liquid alkaline by the pH of system
Value is adjusted to 7 or so, spare after cooling.
It taking the above-mentioned reactant of 150g to pour into 1000ml flask, 6g p-hydroxybenzene hydantoins is added, stirring is extremely dissolved,
Then addition deionized water arrives alkaline zinc-nickel alloy complexing agent to 1L.
Application example
RG-259 is Wuhan Aobang Surface Technique Co., Ltd.'s alkaline zinc-nickel alloy product.
Take above-mentioned solution 500ml to be added in the slot of Hull, anode done with nickel plate, take with a thickness of 0.3mm through buffing at
The iron plate (6.5cm × 20cm) of mirror surface be cathode, 25 DEG C of test piece temperature, current density 1A/dm2, electroplating time 15min obtains
Full sheet uniform bright coating, using X fluorescence spectrum calibrator measurement the area test piece Shang Congdi Qu Zhigao different parts thickness and
Nickel content, the result is as follows:
| Serial number | Thickness μm | Nickel content % |
| A | 7.12 | 12.68 |
| B | 7.58 | 12.93 |
| C | 8.20 | 13.01 |
| D | 8.53 | 13.11 |
| E | 9.01 | 13.55 |
Embodiment three
In the 500ml four-hole bottle with stirring, heating and reflux condensing tube of clean dried, 250ml deionized water is added
With 52g (0.5mol) diethylenetriamine and 51g (0.5mol) N, N- dimethylamino propylamine, then stirred at 15~20 DEG C to
System is uniform；50 DEG C or so are to slowly warm up under stirring, by 343.35g (3.5mol) maleic anhydride solid powder finely ground in advance
End, in addition reaction flask in batches, exothermic heat of reaction opens condensed water, controls feed rate, and the temperature of system is made to be no more than 80
℃；After adding, then insulation reaction 30min is heated to 80 DEG C of insulation reaction 3hr, after completion of the reaction, is cooled to 20 DEG C of left sides
The right side is adjusted the pH value of system to 7 or so with 35% liquid alkaline, spare after cooling.
It takes the above-mentioned reactant of 200g to pour into 1000ml flask, 10g p-hydroxybenzene hydantoins is added, stir to molten
Solution, then be added deionized water to 1L to get arrive alkaline zinc-nickel alloy complexing agent.
Application example
A-1100AB is Wuhan Aobang Surface Technique Co., Ltd.'s alkaline zinc-nickel alloy product.
Take above-mentioned solution 500ml to be added in the slot of Hull, anode done with nickel plate, take with a thickness of 0.3mm through buffing at
The iron plate (6.5cm × 20cm) of mirror surface be cathode, 35 DEG C of test piece temperature, current density 2A/dm2, electroplating time 10min obtains
Full sheet uniform bright coating, using the thickness and nickel content of X fluorescence spectrum calibrator measurement different parts, the result is as follows:
The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.More than
Only the embodiment of the present invention is not intended to limit the scope of the patents of the invention, although carrying out with reference to the foregoing embodiments to the present invention
Detailed description still can be to recorded in aforementioned each specific embodiment for coming for those skilled in the art
Technical solution modify, or to part of technical characteristic carry out equivalence replacement.It is all to utilize in description of the invention
Hold done equivalence replacement, be directly or indirectly used in other related technical areas, similarly protects model in the invention patent
Within enclosing.
Claims (4)
1. a kind of preparation method of green alkaline admiro complexing agent, which is characterized in that including following component: 50~
The p-hydroxyphenylhydantion of the cis-butenedioic anhydride of 200g/L and the reactant of organic amine and 2~10g/L.
2. the preparation method of green alkaline admiro complexing agent according to claim 1, which is characterized in that described suitable
The synthesis step of the reactant of acid anhydride and organic amine includes:
Deionized water is put into the reaction flask with heating, stirring and reflux condensing tube, the organic amine of 1~5mol is then added,
It is to slowly warm up to 50~80 DEG C；
When temperature reaches 50 DEG C or so in reaction flask, it is slowly added to the finely ground cis-butenedioic anhydride powder of 2~20mol, end of reaction in batches
Afterwards, pH value is adjusted to 6~7 or so with liquid alkaline.
3. the preparation method of green alkaline admiro complexing agent according to claim 2, which is characterized in that the conjunction
At step further include:
By the reactant and 2~10g/L p-hydroxyphenylhydantion of 50~200g/L cis-butenedioic anhydride and organic amine mix after, supplement go from
Sub- water, is uniformly mixed, and is settled to 1L.
4. the preparation method of green alkaline admiro complexing agent according to claim 1, which is characterized in that described
Organic amine uses monomethyl amine, dimethylamine, diethylamine, N, N dimethyl amino propylamine, ethylenediamine, diethylenetriamine, triethylene tetramine
Or any combination of one or more of other ethyleneamines.
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