CN103755738B - A kind of complexing agent and its production and use - Google Patents
A kind of complexing agent and its production and use Download PDFInfo
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Abstract
The present invention relates to a kind of complexing agent and its production and use, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein M be in alkalimetal ion and NH4+ any one or multiple; R is acyl group; X, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2. The preparation method of complexing agent is as follows: by containing the alkali of M, carbonate or supercarbonate with phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100��800 DEG C of condition next step polymerase 10 .5��10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��800 DEG C of conditions. The complexing agent of the present invention is applied to production electroplate liquid, easy to process, and obtained electroplate liquid is strong to the complex ability of metal, and the complexation constant of cupric ion can be reached 1026��27, it is far superior to of the prior art without cyanogen complexing agent, the electroplate liquid steady quality obtained by this complexing agent, good dispersity, the process current density a wider range that can adopt, electroplate liquid applied range.<!--2-->
Description
Technical field
The present invention relates to a kind of compound, relate to a kind of complexing agent and its production and use specifically, belong to chemical technology field.
Background technology
Complexing agent is can form the compound of complexing ion with metal ion, in electroplating solution, except minority electroplate liquid, do not use outside maybe need not using complexing agent such as acidic solution plating iron, nickel plating, chromium plating, copper facing, other most of electroplate liquids, as silver-plated in basic solution, gold-plated, copper facing, zinc-plated, zinc-plated, bronze (copper-tin alloy) electroplating etc. all need to use complexing agent.
Conventional complexing agent is such as prussiate; owing to cryanide ion has outstanding complex ability; cyanide electroplating is best plating mode; it is widely used in electroplating industry; but it is deadly poisonous compound that cyanide electroplating to be used NaCN, KCN, CuCN etc.; the lethal quantity of people is only 0.005g by it; prussiate had both endangered the healthy of operator; simultaneously contaminate environment again; and waste water is difficult to administer, its sewage disposal expense is extremely high, therefore in order to protection of the environment; reducing public hazards, the complexing agent urgently developing a kind of substitute is for cyanogenless electroplating technology.
Current cyanogenless electroplating technology and mainly containing without cyanogen complexing agent of using are following several: 1. pyrophosphate copper plating: using potassium pyrophosphate as complexing agent, and potassium pyrophosphate has good complex performance, the complex compound stability constant K that cupric ion and pyrophosphate are formed1=6.7, K2=9.0, the electroplate liquid steady quality of complexing agent is done with potassium pyrophosphate, the processing range that can adopt is wider, but deficiency is: steel substrate can not directly be electroplated, otherwise matrix surface can produce displacement causes bonding force not good, therefore, the range of application of the electroplate liquid making complexing agent with potassium pyrophosphate is limited; 2. citrate copper-plating: citric acid complex ability is relatively strong, can produce highly stable material in the plating solution with cupric ion, the complex compound stability constant K of cupric ion and citrate2=19.30, adopt this technique copper facing iron matrix surface to there will not be displacement phenomenon, weak point is: the electroplate liquid quality making complexing agent with citric acid is stable not, and the dispersion of electroplate liquid has much room for improvement, and electroplate liquid can go bad when high temperature; 3.HEDP copper facing: HEDP is a kind of organic phosphonate, there is good complex ability, when with various metals effect, more stable material can be formed, the electroplate liquid steady quality obtained as complexing agent by HEDP, electroplate liquid good dispersity, weak point is: the process current density narrow range finding this electroplate liquid in actual production, coating easily produces copper powder, iron contamination in plating liquid can reduce sedimentation rate, the bonding force of coating and matrix is deteriorated, is not therefore widely used as the electroplate liquid that complexing agent is obtained by HEDP.
Summary of the invention
It is an object of the invention to solve the deficiency without cyanogen complexing agent of the prior art, it is provided that a kind of complexing agent, this complexing agent complex ability is strong, can reach 10 with the complexing stability constant of cupric ion26��27��
It is a further object to provide the preparation method of a kind of complexing agent, this preparation method is simple to operate, obtained complexing agent steady quality, purity height.
It is a still further object of the present invention to provide the purposes of a kind of complexing agent, this complexing agent is used for the preparation of electroplate liquid, electroplate liquid can be improved to the complex ability of metal, the electroplate liquid steady quality obtained by this complexing agent, electroplate liquid good dispersity, the process current density a wider range that can adopt, the applied range of electroplate liquid.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein M be in alkalimetal ion and NH4+ any one or multiple; R is acyl group; X, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2.
Below with several examples to explain technique scheme:
A: work as x=1, during y=1, z=n, the general formula of complexing agent is MHPnO3n+1Rn, its structural formula as the formula (1):
Structural formula (1);
B: work as x=n, during y=0, z=2 is M while complexing agentnPnO3n+1R2, its structural formula as the formula (2):
Structural formula (2);
C: work as x=1, during y=n-1, R=2, the general formula of complexing agent is MHn-1PnO3n+1R2, its structural formula as the formula (1):
Structural formula (3)
As preferably, the general formula of described complexing agent is MxHyPnO3n+1R, wherein M is Na+��K+With in NH4+ any one or multiple; R is acyl group; X and n is positive integer, and y is 0 or positive integer, x+y=n+1.
Below with several examples to explain technique scheme:
D: as y=0, x=n+1, the general formula of complexing agent is Mn+1PnO3n+1R, its structural formula as the formula (4):
Structural formula (4);
E: as y=1, x=n, the general formula of complexing agent is MnHPnO3n+1R, its structural formula as the formula (5):
Structural formula (5);
F: as y=n-1, x=2, the general formula of complexing agent is M2Hn-1PnO3n+1R, its structural formula as the formula (6):
Structural formula (6);
The preparation method of a kind of complexing agent, concrete operation is as follows: by containing M alkali, carbonate or supercarbonate and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100��800 DEG C of condition next step polymerase 10 .5��10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��800 DEG C of conditions.
First acid-base neutralisation reaction in the preparation method of the complexing agent of the present invention, it is about to containing the alkali of M, carbonate or supercarbonate and phosphoric acid, mixes in molar ratio containing one yuan of organic acid of R base or the acid salt of poly-basic organic acid, and then dehydration polymerization reaction obtains complexing agent finished product, the mode of dehydration polymerization has two kinds: 1, is directly sprayed into by reaction solution and dries polymerisation step in rotary kiln under 100��800 DEG C of conditions and complete to obtain complexing agent finished product; 2, reaction solution is obtained partially polymerized intermediate powder by spraying dry or expansion drying mode at very short time inner drying, intermediate powder is placed in and is similar in the equipment of rake type drier in 100��800 DEG C of polymerase 10 .5��10h acquisition complexing agent finished products.
As preferably, when M is Na+Time, by sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 200��400 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 200��400 DEG C of conditions.
As: M is Na+, work as x=1, during y=1, z=n, the general formula of complexing agent is NaHPnO3n+1Rn, R base is ethanoyl, its structural formula as the formula (7):
Structural formula (7);
The preparation method of the complexing agent shown in structural formula (7) is as follows: by sodium hydroxide and phosphoric acid, acetic acid 1:n:n hybrid reaction in molar ratio, reaction terminates rear reaction solution and obtains partially polymerized intermediate powder through expansion drying, described partially polymerized intermediate powder is placed in mixer. in 200��400 DEG C of polymerase 10 .5��10h, obtains the complexing agent finished product as shown in structural formula (7).
As preferably, when M is K+Time, by potassium hydroxide, salt of wormwood or saleratus and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 250��800 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 250��800 DEG C of conditions.
As: M is K+, work as x=n, during y=0, z=2, the general formula of complexing agent is KPnO3n+1R2, R base is ethanoyl, its structural formula as the formula (8):
Structural formula (8);
The preparation method of the complexing agent shown in structural formula (8) is as follows: by potassium hydroxide and phosphoric acid, acetic acid n:n:2 hybrid reaction in molar ratio, reaction terminates rear reaction solution and obtains partially polymerized intermediate powder through spraying dry, described partially polymerized intermediate powder is placed in mixer. in 250��800 DEG C of polymerase 10 .5��10h, obtains the complexing agent finished product as shown in structural formula (8).
As preferably, when M is NH4+, by ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 100��300 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��300 DEG C of conditions.
An application for complexing agent, for the preparation of electroplate liquid.
As preferably, described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
As preferably, it is 1��60% that the consumption of described electroplate liquid complexing agent is calculated in mass percent.
The invention has the beneficial effects as follows: raw material sources are extensive, cheap, preparation technology, transport, storage and use are simple, and production cost is low; The complexing agent of the present invention is applied to production electroplate liquid, easy to process, and obtained electroplate liquid is strong to the complex ability of metal, and the complexation constant of cupric ion can be reached 10 by the complexing agent such as the present invention26��27, it is far superior to conventional complexing agent of the prior art, the electroplate liquid steady quality obtained by this complexing agent, electroplate liquid good dispersity, the process current density a wider range that can adopt, the applied range of electroplate liquid.
Embodiment
Below by specific embodiment, the technical scheme of the present invention is described in further detail.
Reagent or raw material in following each embodiment are all commercial conventional raw material, and purity is analytical pure.
Embodiment 1:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=3, y=0, n=2, z=1, M are K+, R is ethanoyl, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by potassium hydroxide, phosphoric acid and acetic acid 3:2:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by spraying dry, being placed in rake type drier by this intermediate powder in 250 DEG C of polyreaction 10h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 2:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=3, y=0, n=3, z=2, M are K+And Na+, R is ethanoyl, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, phosphoric acid and acetic acid 3:3:2 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 200 DEG C of polyreaction 10h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 3:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=5, y=0, n=5, z=2, M are Na+, R is the acyl group formed after ethanoyl and sodium hydrotartrate dewater, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid, acetic acid and sodium hydrotartrate 5:5:1:1 hybrid reaction in molar ratio, then reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 400 DEG C of polyreaction 0.5h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 4:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=10, y=1, n=10, z=1, M are K+And Na+, R is the acyl group formed after sodium hydrotartrate dewaters, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, potassium hydroxide, phosphoric acid and sodium hydrotartrate 1:9:10:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by spraying dry, being placed in rake type drier by this intermediate powder in 800 DEG C of polyreaction 0.5h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 5:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=10, y=1, n=10, z=1, M are Na+, R is the acyl group formed after Monobasic sodium citrate dewaters, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium carbonate, phosphoric acid and Monobasic sodium citrate 5:10:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 400 DEG C of polyreaction 0.5h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 6:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=1, y=100, n=100, z=1, M are Na+, R is the amide group formed after ala dehydratase, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid and L-Ala 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 300 DEG C of polyreaction 2.5h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 7:
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=1, y=100, n=100, z=1, M are Na+, R is ethanoyl, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid and acetic acid 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 300 DEG C of polyreaction 2.5h, polyreaction obtains complexing agent finished product after terminating.
Embodiment 8
A kind of complexing agent, the general formula of described complexing agent is MxHyPnO3n+1Rz, wherein x=3, y=0, n=2, z=1, M are Na+, R is the acyl group that the dehydration of methyl phosphoric acid has formation, and concrete structural formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, phosphoric acid and methyl phosphoric acid 3:2:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, being placed in rake type drier by this intermediate powder in 300 DEG C of polyreaction 5h, polyreaction obtains complexing agent finished product after terminating.
Above-mentioned complexing agent is for the preparation of electroplate liquid, and described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
Below for plating solution for copper-plating used, specific as follows:
Embodiment 9:
The preparation being used for non-cyanide pre-plating copper plating solution with the obtained complexing agent of embodiment 7, the preparation method of described electroplate liquid is as follows:
(1) preparation of mantoquita: by complexing agent obtained for embodiment 7 and copper sulfate in molar ratio 2:1 mix, in normal-temperature reaction 1.0h, reaction terminate after through centrifugation and dry must mantoquita, the structural formula of this mantoquita is as follows;
(2) preparation of electroplate liquid: by 1%(mass percent) the obtained mantoquita of the complexing agent of embodiment 7,0.5% step (1) and 98.5% purified water mix in proportion, then with potassium hydroxide adjust pH to 8.5, obtain non-cyanide pre-plating copper plating solution.
Embodiment 10:
The preparation being used for non-cyanide pre-plating copper plating solution with the obtained complexing agent of embodiment 8, the preparation method of described electroplate liquid is as follows:
(1) preparation of mantoquita: by complexing agent obtained for embodiment 8 and copper sulfate in molar ratio 2:3 mix, in normal-temperature reaction 1.0h, reaction terminate after through centrifugation and dry must mantoquita, the structural formula of this mantoquita is as follows;
(2) preparation of electroplate liquid: by 60%(mass percent) the complexing agent of embodiment 1, mantoquita that the step (1) of 5% obtains and 35% purified water mix in proportion, then potassium hydroxide adjust pH to 9.5, obtains pre-plating copper plating solution.
The obtained non-cyanide pre-plating copper plating solution of embodiment 9 and 10 has been carried out following research:
1, Hull groove test (267ml)
1.1 tentative experiments: electroplate liquid embodiment 9 and embodiment 10 obtained is temperature 25 DEG C, circuit 1A(current stabilization), pneumatic blending when beat sheet, time 5min, beating in sheet process observes when current stabilization, and groove pressure is also relatively stable and plating sheet shows the careful feature of half luminous point, crystal in larger area.
Current density range is determined in the test of 1.2Hull groove:
The electroplate liquid obtained with embodiment 9 and embodiment 10 is temperature 55 DEG C, and electric current 1A, time 10min, beats sheet by Hull and determine optimum current density range, makes the A3 steel disc of the sheet material employing 0.5*70*100 that sheet is selected, 600# silicon carbide paper sanding and polishing. With reference to experimental formula Jk=I(5.1-5.24LgL) calculate test piece any current density every. Calculating can draw by beating sheet and current density, the current density range of embodiment 9 and the obtained electroplate liquid of embodiment 10 is 0.5A/dm2To 2.5A/dm2Between.
2 electroplate liquids and plating performance test
The mensuration of 2.1 current efficiency: adopt copper voltameter to measure, the current efficiency of the obtained electroplate liquid of embodiment 9 is 93.0%, and the current efficiency of the obtained electroplate liquid of embodiment 10 is 93.8%.
2.2 electroplate liquid dispersive abilities measure
Survey the dispersive ability of electroplate liquid by bending cathode method, condition is electric current 1A, and without oil pneumatic blending, temperature 55 DEG C, time 30min, the A3 copper sheet of 0.5*70*100 selected by examination material, 600# silicon carbide paper sanding and polishing.
The dispersive ability of the electroplate liquid of the embodiment 9 recorded is 93.5%, and the dispersive ability of the electroplate liquid of embodiment 10 is 93.1%.
The mensuration of 2.3 covering powers
In adopting, hole method measures the covering power of plating liquid, copper tube size 10mm*100mm, adopts through hole and blind hole method, and temperature of electroplating solution is 55 DEG C, and cathode current density is 0.5A/dm2, time 5min. Iron pipe is cut open, coating situation in observation tube after experiment.
Taking the electroplate liquid of embodiment 9 and 10 as experiment electroplate liquid, after experiment, find that through hole and blind hole have all plated layers of copper, illustrate that the covering power of embodiment 9 and the obtained electroplate liquid of embodiment 10 is good.
2.4 bonding force tests
2.4.1 crooked experiment: employing thickness is polishing iron sheet (A3) of 0.5mm, and the temperature of electroplate liquid is 55 DEG C, and cathode current density is 2A/dm2, time 15min.
Taking the electroplate liquid of embodiment 9 and 10 as experiment electroplate liquid, by the test piece alternating bending plated to rupturing after experiment, breach place, without decortication phenomenon, proves that coating is not separated with matrix.
2.4.2 thermal shock experiment: employing thickness is polishing iron sheet (A3) of 0.5mm, and the temperature of electroplate liquid is 55 DEG C, and cathode current density is 2A/dm2, time 15min.
Taking the electroplate liquid of embodiment 9 and 10 as experiment electroplate liquid, the test piece plated being put and be baked to 200 DEG C in an oven, toast 1h continuously, immerse quenching in 0 DEG C of water after taking-up immediately after experiment, result does not find that coating bubbles and decortication phenomenon.
2.5 ductility of electrodeposited film experiments: by A3 steel disc chromic acid passivation thick for 1mm, directly hang in the obtained electroplate liquid of embodiment 9 and 10, after the thickness of coating reaches 20 ��m after cleaning, coating is stripped down, bending 180 DEG C, and extrude bending locating, coating does not rupture, and shows that ductility of electrodeposited film is good.
2.6 coating porosity experiments: employing thickness is polishing iron sheet (A3) of 0.5mm, the temperature of electroplate liquid 55 DEG C, cathode current density 1A/dm2, time 20min, paste filter paper laboratory method with potassium ferricyanide solution and carry out porosity experiment.
Tripotassium iron hexacyanide 10g/L; Sodium-chlor 20g/L.
Experimental result shows, the porosity of the electrolytic coating that embodiment 9 and the obtained electroplate liquid of embodiment 10 are formed as experimental subjects is equal��and 1/dm2��
The mensuration of 2.7 sedimentation velocities: setting electric current 1A, temperature 55 DEG C, time 30min, measurement result shows, the sedimentation velocity of the obtained electroplate liquid of embodiment 9 is 0.6 ��m/min, and the sedimentation velocity of the obtained electroplate liquid of embodiment 10 is 0.52 ��m/min.
Embodiment 9 and the obtained electroplate liquid of embodiment 10 are carried out pilot experiment further, and pilot process parameter is as follows:
Technical process: electroplate liquid �� recovery �� washing 1 �� washing, 2 �� acid activation �� acid copper of iron and steel parts �� ultrasonic oil removal �� washing 1 �� washing, 2 �� anode electrolysis oil removing �� washing, 1 �� washing, 2 �� pickling degreasing �� washing, 1 �� washing, 2 �� salt pickling �� washing, 1 �� washing, 2 �� terminal electrolytic degreasing �� washing, 1 �� washing, 2 �� acid activation �� washing, 1 �� washing, 2 �� embodiment 9 or 10.
Ultrasonic oil removal: oil removing powder concentration 50 �� 5g/L, temperature 70 �� 5 DEG C, current density 1-5A/dm2,5 minutes time.
Catholyte oil removing: electrolytic degreasing powder concentration 50 �� 5g/L, temperature 70 �� 5 DEG C, current density 1-5A/dm2,5��7 minutes time.
Anode electrolysis oil removing: electrolytic degreasing powder concentration 50 �� 5g/L, temperature 70 �� 5 DEG C, current density 1-5A/dm2, 3��5 minutes time.
Pickling: technical hydrochloric acid concentration 15��20%, time 8��10min, room temperature.
Activation: technical hydrochloric acid concentration 5��10%, time 3��5min, room temperature.
The electroplate liquid of embodiment 9 or 10: degree Beaume 32-36, pH value 8.5��9.5, temperature 50��55 DEG C, current density 0.5��2.5A/dm2, time 5min to a few hours not etc., not facts have proved, are plating to 100 ��m of Surface flat, luminance brightness also very good.
Running 20 months continuously by 50L pilot scale electroplating assembly line, 350L pilot scale electroplating assembly line runs 11 months continuously, demonstrates the obtained electroplate liquid of embodiment 9 or 10 and has reliability, and plating solution performance is stablized, and the consumption of plating liquid is 10��50ml/KAH.
On the experiment basis of above-mentioned pilot scale, obtain the processing condition that the obtained electroplate liquid of embodiment 9 or 10 is used for suitability for industrialized production.
1, iron and steel parts:
Technical process: electroplate liquid �� recovery �� washing 1 �� washing, 2 �� acid activation �� acid copper of iron and steel parts �� ultrasonic oil removal �� washing 1 �� washing, 2 �� anode electrolysis oil removing �� washing, 1 �� washing, 2 �� pickling degreasing �� washing, 1 �� washing, 2 �� salt pickling �� washing, 1 �� washing, 2 �� terminal electrolytic degreasing �� washing, 1 �� washing, 2 �� acid activation �� washing, 1 �� washing, 2 �� preimpregnation �� embodiment 9 or 10.
Processing condition:
Electroplate liquid density: 32��36 degree Beaume
Temperature 45��60 DEG C
PH value: 8.60��9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive area ratio: 1:1.5��2.
Electric current: 0.5��2.5A/dm2
2, zinc alloy workpiece:
Technical process: zinc alloy workpiece �� hot dipping is except wax �� ultrasonic wave is except electroplate liquid (charged enter groove 25��35 DEG C) �� recovery �� wash 1 �� wash 2 �� acid activation �� acid copper of wax �� washing 1 �� washing 2 �� ultrasonic oil removal �� washing, 1 �� washing, 2 �� anode electrolysis oil removing �� washing, 1 �� washing, 2 �� acid salt activating �� washing 1 �� wash 2 �� ultrasonic wave presoak preimpregnation 30s �� embodiment 9 or 10.
Processing condition:
Electroplate liquid density: 32��38 degree Beaume
Temperature 25��35 DEG C
PH value: 8.60��9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive area ratio: 1:1.5��2.
Electric current: 0.5��1.5A/dm2
Above-described embodiment is the one preferably scheme of the present invention, not the present invention is done any restriction in form, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (8)
1. a complexing agent, it is characterised in that: the structural formula of described complexing agent is such as formula shown in any one in (1), (2), (3), (4), (5) and (6):
Wherein M is Na+��K+And NH4+In any one or multiple; N is positive integer, and R is acyl group;
The preparation method of described complexing agent specifically operates as follows: by containing the alkali of M, carbonate or supercarbonate with phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100��800 DEG C of condition next step polymerase 10 .5��10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��800 DEG C of conditions.
2. the preparation method of a complexing agent according to claim 1, it is characterized in that, concrete operation is as follows: by containing M alkali, carbonate or supercarbonate and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution is at 100��800 DEG C of condition next step polymerase 10 .5��10h acquisition complexing agent finished products; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��800 DEG C of conditions.
3. the preparation method of complexing agent according to claim 2, it is characterised in that, when M is Na+Time, by sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 200��400 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 200��400 DEG C of conditions.
4. the preparation method of complexing agent according to claim 2, it is characterised in that, when M is K+Time, by potassium hydroxide, salt of wormwood or saleratus and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 250��800 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 250��800 DEG C of conditions.
5. the preparation method of complexing agent according to claim 2, it is characterized in that, when M is NH4+, by ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid, containing one yuan of organic acid of R base or the acid salt hybrid reaction in molar ratio of poly-basic organic acid, then reaction solution obtains complexing agent finished product at 100��300 DEG C of condition next step polymerase 10 .5��10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5��10h obtains complexing agent finished product under 100��300 DEG C of conditions.
6. the application of a complexing agent according to claim 1, it is characterised in that: for the preparation of electroplate liquid.
7. the application of complexing agent according to claim 6, it is characterised in that: described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
8. the application of complexing agent according to claim 7, it is characterised in that: it is 1��60% that the consumption of described electroplate liquid complexing agent is calculated in mass percent.
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| DE1192021B (en) * | 1963-01-12 | 1965-04-29 | Dehydag Gmbh | Galvanic baths |
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| CH572989A5 (en) * | 1973-04-27 | 1976-02-27 | Oxy Metal Industries Corp | |
| GB1594418A (en) * | 1978-05-30 | 1981-07-30 | Oxy Metal Industries Corp | Rhodium plating |
| JPS5565389A (en) * | 1978-11-09 | 1980-05-16 | Toshiba Corp | Forming method of black alloy plating film for selective absorption of solar heat |
| EP1961840B1 (en) * | 2007-02-14 | 2009-12-30 | Umicore Galvanotechnik GmbH | Copper-tin electrolyte and method for depositing bronze layers |
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Effective date of registration: 20170221 Address after: Zhejiang province Quzhou City Kecheng District 324200 Kaixuan Road No. 6 Building 1, room 106, block A 104 Patentee after: Zhejiang Fu Fu Technology Co., Ltd. Address before: 324200 Changshan County, Zhejiang Province Ecological Industrial Park Patentee before: Sun Songhua |