WO2015103785A1 - 一种络合剂及其制备方法和用途 - Google Patents

一种络合剂及其制备方法和用途 Download PDF

Info

Publication number
WO2015103785A1
WO2015103785A1 PCT/CN2014/070526 CN2014070526W WO2015103785A1 WO 2015103785 A1 WO2015103785 A1 WO 2015103785A1 CN 2014070526 W CN2014070526 W CN 2014070526W WO 2015103785 A1 WO2015103785 A1 WO 2015103785A1
Authority
WO
WIPO (PCT)
Prior art keywords
complexing agent
plating
acid
copper
reaction liquid
Prior art date
Application number
PCT/CN2014/070526
Other languages
English (en)
French (fr)
Inventor
孙松华
孙婧
Original Assignee
孙松华
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 孙松华 filed Critical 孙松华
Priority to JP2016547031A priority Critical patent/JP6263636B2/ja
Priority to KR1020167022170A priority patent/KR101850639B1/ko
Priority to PCT/CN2014/070526 priority patent/WO2015103785A1/zh
Priority to US15/111,291 priority patent/US20160333032A1/en
Publication of WO2015103785A1 publication Critical patent/WO2015103785A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/098—Esters of polyphosphoric acids or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/06—Potassium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • 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
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the invention relates to a compound, in particular to a complexing agent, a preparation method thereof and a use thereof, and belongs to the technical field of chemical industry. Background technique
  • the complexing agent is a compound capable of forming complex ions with metal ions.
  • plating solution except for a small number of plating solutions, such as acidic solution iron plating, nickel plating, chrome plating, copper plating, or not using a complexing agent, most of the others Plating solutions, such as alkaline solution silver plating, gold plating, copper plating, galvanizing, tin plating, copper-plated tin alloy, etc., require the use of a complexing agent.
  • cyanide cyanide plating
  • cyanide plating is the best plating method due to its excellent complexing ability. It is widely used in the electroplating industry, but it is highly toxic to use cyanide plating for NaCN, KCN, CuCN, etc. Compound, its lethal dose to humans is only 0.005g. Cyanide harms the health of the operator and pollutes the environment, and the wastewater is difficult to treat. The sewage treatment cost is extremely high. Therefore, in order to protect the environment and reduce pollution, it is urgent to develop. A complexing agent that replaces cyanide is used in a cyanide-free plating process.
  • the cyanide-free electroplating process and the cyanide-free complexing agent used mainly include the following: 1. Pyrophosphate copper plating: potassium pyrophosphate as a complexing agent, potassium pyrophosphate has good complexing property, copper ion
  • the quality of the plating solution using potassium pyrophosphate as a chelating agent is stable, and the range of processes that can be used is wide, but the disadvantages are: Electroplating cannot be directly performed on the steel substrate, otherwise the surface of the substrate will be replaced and the bonding force will be poor.
  • HEDP copper plating HEDP is an organic phosphonate with good Complexity When it is combined with various metals, it can form a relatively stable substance.
  • the quality of the plating solution prepared by HEDP as a complexing agent is stable, and the dispersion of the plating solution is good.
  • the disadvantages are: The process of the plating solution is found in actual production. The current density range is narrow, the coating is easy to produce copper powder, and the plating solution The iron impurities in the medium reduce the deposition rate, and the bonding force between the plating layer and the substrate is deteriorated. Therefore, the plating solution prepared by using HEDP as a complexing agent has not been widely used. Summary of the invention
  • Object of the present invention is to solve the disadvantages of the prior art non-cyanide complexing agent is provided a quan agent strong complexing ability of the complexing agent, complexation with copper ion stability constant up to 1026 ⁇ 27.
  • the preparation method is simple in operation, and the obtained complexing agent has stable quality and high purity.
  • Still another object of the present invention is to provide a use of a complexing agent for the preparation of a plating solution, the ability of the plating solution prepared by the complexing agent to be stable, and the dispersion of the plating solution is good.
  • the process current density range is wide, and the plating solution has a wide application range.
  • a preparation method of a complexing agent the specific operation is as follows: mixing an alkali, carbonate or hydrogencarbonate containing M with phosphoric acid, a monobasic organic acid containing an R group or an acid salt of a polybasic organic acid, Then, the reaction solution is polymerized at a temperature of 100 to 800 ° C for 0.5 to 10 hours to obtain a finished complex; or the above reaction liquid is dried first, and then polymerized at 100 to 800 ° C for 0.5 to 10 hours to obtain a finished complex product.
  • the acid-base neutralization reaction is firstly performed, that is, the alkali salt of the M, the carbonate or the hydrogen sulphate and the acid salt of the phosphoric acid, the R-containing monobasic organic acid or the polybasic organic acid are massaged.
  • dehydration polymerization there are two ways of dehydration polymerization: 1. Directly spray the reaction solution into the rotary kiln at 100 ⁇ 800 °C to complete the polymerization step to complete the complexing agent. Finished product; 2.
  • reaction solution is dried in a short time by spray drying or flash drying to obtain a partially polymerized intermediate powder, and the intermediate powder is placed in a device similar to a drier dryer at 100 to 800 ° C. Polymerization 0.5 ⁇ 10h to obtain the finished complexing agent.
  • M is Na +
  • sodium hydroxide, sodium carbonate or sodium hydrogencarbonate is mixed with phosphoric acid, an R-containing monobasic organic acid or a polybasic organic acid acid salt, and then the reaction liquid is at 200.
  • the temperature of ⁇ 400 ° C next polymerization 0.5 ⁇ 10h to obtain the finished complex; or the above reaction liquid is dried first, and then polymerized at 200 ⁇ 400 ° C for 0.5 ⁇ 10h to obtain the finished complex.
  • M is Na+
  • the formula of the complexing agent is NaHP n ⁇ 3n+1 R II
  • the R group is acetyl
  • its structural formula is as shown in formula (7). Show:
  • the structural formula (7); the complexing agent represented by the structural formula (7) is prepared as follows: Mixing sodium hydroxide with phosphoric acid, acetic acid molar ratio I: n: n, after the reaction is completed, the reaction liquid is obtained by flash drying.
  • the partially polymerized intermediate powder is obtained by dispersing the partially polymerized intermediate powder in a crucible stirrer at 200 to 400 ° C for 0.5 to 10 h to obtain a finished complexing agent as shown in the structural formula (7).
  • the potassium hydroxide, carbonic acid or potassium hydrogencarbonate is mixed with phosphoric acid, the R-containing monobasic organic acid or the polybasic organic acid acid salt, and then the reaction liquid is at 250.
  • the next step of polymerization is 0.5 ⁇ 10h to obtain the finished product of the complexing agent; or the above reaction liquid is dried first, and then polymerized at 250 ⁇ 800 °C for 0.5 ⁇ 10h to obtain the finished product of the complexing agent.
  • the structural formula is as shown in formula (8). :
  • the structural formula (8); the complexing agent represented by the structural formula (8) is prepared as follows: The potassium hydroxide is mixed with phosphoric acid and acetic acid in a molar ratio of ⁇ : ⁇ : 2, and the reaction liquid is spray-dried to obtain a portion after the reaction is completed.
  • the polymerized intermediate powder is obtained by dispersing the partially polymerized intermediate powder in a crucible stirrer at 250 to 800 ° C for 0.5 to: I0h to obtain a finished complexing agent as shown in Structural Formula (8).
  • the ammonia salt, ammonium carbonate or ammonium hydrogencarbonate is mixed with phosphoric acid, the R-containing monobasic organic acid or the polybasic organic acid acid salt, and then the reaction solution is at 100 ⁇ 300°.
  • the C condition is further polymerized for 0.5 ⁇ 10h to obtain the finished product of the complexing agent; or the above reaction liquid is dried first, and then polymerized at 100 ⁇ 300 °C for 0.5 ⁇ 10h to obtain the finished product of the complexing agent.
  • a use of a complexing agent for the preparation of a plating bath is a use of a complexing agent for the preparation of a plating bath.
  • the plating solution is copper plated, tin plated, copper plated zinc alloy, copper plated tin alloy, plated o
  • any one of a nickel-tin alloy, a nickel-plated cobalt alloy, a tin-plated cobalt alloy, and a nickel-plated tin-cobalt alloy is any one of a nickel-tin alloy, a nickel-plated cobalt alloy, a tin-plated cobalt alloy, and a nickel-plated tin-cobalt alloy.
  • the amount of the complexing agent in the plating solution is 10% by mass.
  • the invention has the advantages that: the raw material o has wide source, low price, simple preparation process, transportation, storage and use, and low production cost; the complexing agent of the invention is applied to the production of electroplating solution, and the processing is convenient, and the prepared electroplating solution is The complexing ability of the metal OOP is strong.
  • the complexing agent of the present invention has a complexing constant for copper ions of 10 26 -27 , which is far superior to the conventional complexing agent in the prior art, and is prepared by the complexing agent.
  • the quality of the plating solution obtained is stable, the dispersion of the plating solution is good, the range of process current density that can be used is wide, and the application range of the plating solution is wide.
  • M is K + , R
  • R For the acetyl group, the specific structural formula is as follows:
  • the preparation method of the complexing agent is as follows: mixing potassium hydroxide, phosphoric acid and acetic acid in a molar ratio of 3:2:1, and the reaction liquid is spray-dried to obtain a partially polymerized intermediate powder, and the intermediate powder is placed in a crucible The polymerization reaction was carried out in a dryer at 250 ° C for 10 h, and a complexing agent was obtained after the polymerization reaction was completed.
  • Example 2 Example 2:
  • the preparation method of the complexing agent is as follows: mixing sodium hydroxide, phosphoric acid and acetic acid in a molar ratio of 3:3:2, and the reaction liquid is obtained by flash drying to obtain a partially polymerized intermediate powder, and the intermediate powder is placed in a sputum type.
  • the polymerization was carried out in a dryer at 20 CTC for 10 h, and after completion of the polymerization, a complexing agent was obtained to obtain Example 3:
  • the acyl group formed by dehydration of acetyl and sodium hydrogen tartrate has the following specific structure: COONa
  • the preparation method of the complexing agent is as follows: mixing sodium hydrogencarbonate, phosphoric acid, acetic acid and sodium hydrogen tartrate in a molar ratio of 5:5:1:1, and then the reaction liquid is obtained by flash drying to obtain a partially polymerized intermediate powder, The intermediate powder was placed in a crucible dryer for polymerization at 40 CTC for 0.5 h, and the finished complexing agent was obtained after the end of the polymerization reaction.
  • the preparation method of the complexing agent is as follows: mixing sodium hydroxide, potassium hydroxide, phosphoric acid and sodium hydrogen tartrate in a molar ratio of 1:9:10:1, and the reaction liquid is spray-dried to obtain a partially polymerized intermediate powder, The intermediate powder was placed in a kneading dryer at 80 CTC for 0.5 h, and after completion of the polymerization, a complexing agent product was obtained.
  • the acyl group formed after dehydration of disodium hydrogen citrate has the following structural formula:
  • the preparation method of the complexing agent is as follows: sodium carbonate, phosphoric acid and disodium hydrogen citrate molar ratio
  • reaction liquid was subjected to flash drying to obtain a partially polymerized intermediate powder, and the intermediate powder was placed in a kneader dryer at 40 CTC for 0.5 h, and the completion of the polymerization reaction was carried out to obtain a finished complex product.
  • the complexing agent is prepared by the following steps: mixing sodium hydrogencarbonate, phosphoric acid and alanine in a ratio of 1:100:1, and the reaction solution is subjected to flash drying to obtain a partially polymerized intermediate powder, and the intermediate powder is placed.
  • the polymerization reaction was carried out at 300 ° C for 2.5 h in a rake dryer, and the finished complexing agent was obtained after the completion of the polymerization reaction.
  • the preparation method of the complexing agent is as follows: mixing sodium hydrogen sulphate, phosphoric acid and acetic acid in a molar ratio of 1:100:1, and the reaction liquid is subjected to flash drying to obtain a partially polymerized intermediate powder, and the intermediate powder is placed in a crucible.
  • the polymerization was carried out at 300 ° C for 2.5 h in a dryer, and the finished complex was obtained after the completion of the polymerization.
  • acyl group formed by dehydration of methyl group by acid, and the specific structural formula is as follows: OH
  • the preparation method of the complexing agent is as follows: mixing sodium hydroxide, phosphoric acid and methyl acid acid in a molar ratio of 3:2:1, and the reaction liquid is obtained by flash drying to obtain a partially polymerized intermediate powder, and the intermediate is obtained.
  • the powder was placed in a rake dryer for polymerization at 300 ° C for 5 h, and the complexing agent was obtained after the end of the polymerization.
  • the above complexing agent is used for preparing a plating solution, which is copper plating, tin plating, copper-zinc alloy plating, copper-plated tin alloy, nickel-tin-nickel alloy, nickel-plated cobalt alloy, tin-plated cobalt alloy and nickel-plated tin-cobalt. Any of the alloys.
  • Example 7 The complexing agent prepared in Example 7 was used for the preparation of a cyanide-free pre-plating copper plating solution prepared as follows:
  • Example 8 The complexing agent prepared in Example 8 was used for the preparation of a cyanide-free pre-plating copper plating solution prepared as follows:
  • Example 9 The plating solution prepared in Example 9 and Example 10 was subjected to filming at a temperature of 25 ° C, circuit 1A (steady flow), air agitation for 5 min, and steady flow was observed during the filming process. Under the condition, the groove pressure is also relatively stable and the plated sheet exhibits a semi-light spot and a fine crystal structure on a large area.
  • the plating solution prepared in Example 9 and Example 10 was subjected to a Hull tablet to determine an optimum current density range at a temperature of 55 ° C, a current of 1 A, and a time of 10 mm.
  • the sheet selected for filming was 0.5*70*100 A3.
  • Calculate the current density at each point of the test piece with reference to the empirical formula J k I ( 5.1- 5.24 LgL ). It can be concluded from the tableting and current density calculation that the current density of the plating solutions prepared in Example 9 and Example 10 is in the range of 0.5 A/dm 2 to 2.5 A/dm 2 .
  • the current efficiency of the plating solution prepared in Example 9 was 93.0% as measured by a copper coulometer, and the current efficiency of the plating solution prepared in Example 10 was 93.8%.
  • the dispersing ability of electroplating solution was measured by curved cathode method. The condition was current 1A, oil-free air stirring, temperature 55 ° C, time 30 min. The test material was 0.5*70*100 A3 copper sheet, 600 # ⁇ , paper polishing and polishing.
  • the cathode current density is 0. 5A.
  • the cathode current density is 0. 5A.
  • the cathode current density is 0. 5A.
  • the cathode current density is 0. 5A.
  • the cathode current density is 0. 5A. / dm 2 , time 5mm.
  • the electroplating solutions of Examples 9 and 10 were used as experimental electroplating solutions. After the experiment, the plated test pieces were repeatedly bent to break, and there was no peeling at the cracks, which proved that the plating layer and the substrate were not separated.
  • the plating solution of Examples 9 and 10 was used as the experimental plating solution. After the experiment, the plated test piece was baked in an oven to 20 CTC, and continuously baked for 1 hour. Immediately after being taken out, it was immersed in 0 ° C water and quenched. The coating was found to be foaming and peeling.
  • the experimental results show that the plating solutions formed in the plating solutions prepared in Examples 9 and 10 as the experimental objects have a porosity of 1 / dm 2 .
  • Example 9 The electroplating solutions prepared in Example 9 and Example 10 were further subjected to a pilot test, and the pilot process parameters were as follows:
  • Ultrasonic degreasing degreasing powder concentration 50 ⁇ 5g / L, temperature 70 ⁇ 5 ° C, current density l-5A / dm2, Time 5 minutes ⁇ ⁇ .
  • Cathode electric de-oil The electric de-oil powder concentration is 50 ⁇ 5g/L and the temperature is 70 ⁇ 5. C, current density 1 -5A/dm2, time 5 ⁇ 7 minutes.
  • Anode electric de-oil The electric de-oil powder concentration is 50 ⁇ 5g L, the temperature is 70 ⁇ 5°C, the current density is 1-5 A/dm 2 , and the time is 3 to 5 minutes.
  • Electroplating solution of Example 9 or 10 Baume degree 32-36, pH value 8.5 ⁇ 9.5, temperature 50 ⁇ 55 °C, current density 0.5 ⁇ 2.5 A/dm2, time 5mm to several hours, practice proved, plating As for ⁇ ⁇ leveling, the brightness is still very good.
  • the 50L pilot electroplating line was continuously transported for 20 months, and the 350L pilot electroplating line was continuously operated for 11 months. It was verified that the electroplating solution prepared in Example 9 or 10 was reliable, and the bath performance was stable and stable. The consumption is 10 ⁇ 50ml/KAH.
  • Example 9 or 10 Based on the above pilot experiments, the plating solution prepared in Example 9 or 10 was obtained for the industrial production process conditions.
  • Zinc alloy workpiece Process: zinc alloy workpiece ⁇ hot dip wax removal ⁇ ultrasonic wax removal ⁇ water washing 1 ⁇ water washing 2 ⁇ ultrasonic degreasing ⁇ water washing 1 ⁇ water washing 2 ⁇ anode electric oil removal ⁇ water washing 1 ⁇ water washing 2 ⁇ acid salt activation ⁇ water washing 1 ⁇ Washing 2 ⁇ Ultrasonic prepreg pre-dip 30s ⁇ Electroplating solution of Example 9 or 10 (charged into tank 25 ⁇ 35°C) ⁇ Recovery ⁇ Washing 1 ⁇ Washing 2 ⁇ Acid activation ⁇ Acid copper.
  • the area ratio of yin and yang 1 : 1.5 ⁇ 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

本发明涉及一种络合剂及其制备方法和用途，所述络合剂的通式为MxHyPnO3n+1Rz，其中M为碱金属离子和NH4+中的任意一种或多种；R为酰基；x、n和z均为正整数，y为0或正整数，x+y+z=n+2。络合剂的制备方法如下：将含M的碱、碳酸盐或碳酸氢盐与磷酸、含R基的一元有机酸或多元有机酸的酸式盐按摩尔比混合反应，然后反应液在100~800°C条件下一步聚合0.5-10h获得洛合剂成品；或者上述反应液先干燥，然后再在100~800°C条件下聚合0.5-10h获得络合剂成品。本发明的洛合剂应用于生产电镀液，加工方便，制得的电镀液对金属的洛合能力强，对铜离子的络合常数可达到1026〜27，远远优于现有技术中的无氰络合剂，由该络合剂制得的电镀液质量稳定，分散性好，可采用的工艺电流密度范围较宽，电镀液应用范围广。

Description

一种絡合剂及其制备方法和用途
技术领域
本发明涉及一种化合物， 具体的说是涉及一种络合剂及其制备方法和 用途， 属于化工技术领域。 背景技术
络合剂为能与金属离子形成络合离子的化合物， 在电镀溶液中， 除少 数电镀液， 如酸性溶液镀铁、 镀镍、 镀铬、 镀铜没有使用或不必使用絡合 剂外， 其他大多数电镀液， 如碱性溶液镀银、 镀金、 镀铜、 镀锌、 镀锡、 镀铜锡合金等都需要使用絡合剂。
常用的絡合剂如氰化物， 由于氰离子具有优秀的络合能力， 氰化电镀 是最好的电镀方式，广泛应用于电镀行业，但是氰化电镀要用到 NaCN、 KCN、 CuCN等是剧毒化合物， 它对人的致死量仅为 0.005g， 氰化物既危害操作者 的身体健康， 同时又污染环境， 而且废水难于治理， 其污水处理费用极高， 因此为了保护环境， 减少公害， 亟待开发一种替代氰化物的絡合剂用于无 氰电镀工艺。
目前无氰电镀工艺及用到的无氰络合剂主要有以下几种： 1.焦磷酸盐 镀铜： 以焦磷酸钾作为络合剂， 焦磷酸钾具有较好的络合性能， 铜离子与 焦磷酸根形成的絡合物稳定常数 K,=6. 7 , Κ2=9. 0， 以焦磷酸钾做绺合剂的 电镀液质量稳定， 可采用的工艺范围较宽， 但不足在于： 钢铁基体上不能 直接进行电镀， 否则基体表面会产生置换导致结合力不好， 因此， 以焦磷 酸钾做絡合剂的电镀液的应用范围有限； 2.柠檬酸盐镀铜： 柠檬酸絡合能 力较强， 能与铜离子在镀液中生产非常稳定的物质， 铜离子与柠檬酸根的 络合物稳定常数1^=19. 30 ,采用该工艺镀铜铁基体表面不会出现置换现象， 不足之处是： 以柠檬酸做絡合剂的电镀液质量不够稳定， 电镀液的分散性 有待提高， 电镀液在高温时会变质； 3. HEDP镀铜： HEDP是一种有机膦酸盐， 具有良好的络合能力， 在与多种金属作用时， 都能形成比较稳定的物质， 由 HEDP作为络合剂制得的电镀液质量稳定，电镀液分散性好，不足之处是： 实际生产中发现该电镀液的工艺电流密度范围窄， 镀层易产生铜粉， 镀液 中的铁杂质会降低沉积速率， 使得镀层与基体的结合力变差， 因此由 HEDP 作为络合剂制得的电镀液并未得到广泛的应用。 发明内容
本发明的目的在于解决现有技术中的无氰络合剂的不足， 提供一种绻 合剂， 该络合剂络合能力强， 与铜离子的络合稳定常数可达 1 026~27。
该制备方法操作 简单， 制得的络合剂质量稳定， 纯度高。
本发明还有一个目的是提供一种络合剂的用途， 该络合剂用于电镀液 的制备， 合能力， 由该络合剂制得的电镀液质 量稳定， 电镀液分散性好， 可采用的工艺电流密度范围较宽， 电镀液的应 用范围广。
本发明解决其技术问题所采用的技术方案是：
一种络合剂， 所述络合剂的通式为 MxHyPn03n+1Rz， 其中 M为碱金属 离子和 NH4+中的任意一种或多种； R为酰基； x、 n和 z均为正整数， y 为 0或正整数， x+y+z=n+2。
下面以几个例子以解释上述技术方案：
a: 当 x=l , y=l时， z=n, 络合剂的通式为 MHPn03n+1Rn， 其结构式如 式 （ 1 ) 所示：
Figure imgf000003_0001
R ， 结构式 （1 );
b: 当 x=n， y=0时， z=2， 絡合剂的同时为 MnPn03n+1 , 其结构式如 式 （2 ) 所示：
Figure imgf000004_0001
e: 当 y=l时， x=n, 絡合剂的通式为 MnHPn03n+1R, 其结构式如式（5 ) 所示: 式 （5 );
f: 当 y
Figure imgf000005_0001
其结构式如式
( 6 ) 所示:
Figure imgf000005_0002
H ， 结构式（6 );
一种络合剂的制备方法， 具体操作如下： 将含 M的碱、 碳酸盐或碳酸 氢盐与磷酸、 含 R基的一元有机酸或多元有机酸的酸式盐按摩尔比混合反 应， 然后反应液在 100~800°C条件下一步聚合 0.5~10h获得络合剂成品； 或 者上述反应液先干燥，然后再在 100〜800°C条件下聚合 0.5~10h获得絡合剂 成品。
本发明的络合剂的制备方法中首先酸碱中和反应， 即将含 M的碱、 碳 酸盐或破酸氢盐与磷酸、 含 R基的一元有机酸或多元有机酸的酸式盐按摩 尔比混合， 然后再脱水聚合反应获得络合剂成品， 脱水聚合的方式有两种： 1、 直接将反应液喷入回转炉内在 100~800°C条件下烘干聚合一步完成获得 络合剂成品； 2、 将反应液通过喷雾干燥或闪蒸干燥方式在极短时间内干燥 获得部分聚合的中间体粉末， 将中间体粉末置于类似于耙式干燥机的设备 内于 100~800°C聚合 0.5~10h获得络合剂成品。
作为优选， 当 M为 Na+时， 将氢氧化钠、 碳酸钠或碳酸氢钠与磷酸、 含 R基的一元有机酸或多元有机酸的酸式盐按摩尔比混合反应， 然后反应 液在 200〜400°C条件下一步聚合 0.5〜10h获得络合剂成品；或者上述反应液 先干燥， 然后再在 200~400°C条件下聚合 0.5~10h获得络合剂成品。 如： M为 Na+， 当 x=l， y=l时， z=n, 络合剂的通式为 NaHPn〇3n+1R II， R基为乙酰基， 其结构式如式 （7 ) 所示：
Figure imgf000006_0001
， 结构式 （7 ); 结构式（7 )所示的络合剂的制备方法如下： 将氢氧化钠与磷酸、 乙酸 按摩尔比 I： n: n混合反应， 反应结束后反应液经过闪蒸干燥获得部分聚 合的中间体粉末， 将所述部分聚合的中间体粉末置于耙式搅拌器内于 200~400°C聚合 0.5~l0h, 获得如结构式 （7 ) 所示的络合剂成品。
作为优选， 当 M为 K+时， 将氢氧化钾、 碳酸钟或碳酸氢钾与磷酸、 含 R基的一元有机酸或多元有机酸的酸式盐按摩尔比混合反应， 然后反应液 在 250~800°C条件下一步聚合 0.5~l0h获得絡合剂成品；或者上述反应液先 干燥， 然后再在 250~800°C条件下聚合 0.5~l0h获得絡合剂成品。
如： M为 K+， 当 x=n， y=0时， z=2， 络合剂的通式为 KPn〇3n+lR2， R 基为乙 其结构式如式（8 ) 所示：
Figure imgf000006_0002
， 结构式 （8 ); 结构式（8 )所示的络合剂的制备方法如下： 将氢氧化钾与磷酸、 乙酸 按摩尔比 η: η: 2混合反应， 反应结束后反应液经过喷雾干燥获得部分聚 合的中间体粉末， 将所述部分聚合的中间体粉末置于耙式搅拌器内于 250〜800°C聚合 0.5〜： I0h， 获得如结构式 （8 ) 所示的络合剂成品。 作为优选， 当 M为 NH4+时， 将氨水、 碳酸铵或碳酸氢铵与磷酸、 含 R基的一元有机酸或多元有机酸的酸式盐按摩尔比混合反应， 然后反应液 在 100~300°C条件下一步聚合 0.5~10h获得络合剂成品；或者上述反应液先 干燥， 然后再在 100~300°C条件下聚合 0.5~10h获得絡合剂成品。
一种络合剂的应用， 用于制备电镀液。
作为优选， 所述电镀液为镀铜、 镀锡、 镀铜锌合金、 镀铜锡合金、 镀 o
镍锡合金、 镀镍钴合金、 镀锡钴合金和镀镍锡钴合金中的任意一种。
作为优选， 所述电镀液中络合剂的用量以质量百分数计为 1 0%。 本发明的有益效果是： 原料 o来源广泛， 价格低廉， 制备工艺、 运输、 存储和使用简单， 生产成本低； 本发明的络合剂应用于生产电镀液， 加工 方便， 制得的电镀液对金属的络合能力 OOP强NI ， 如本发明的络合剂对铜离子的 络合常数可达到 1026〜27， 远远优于现有技术中的常规络合剂， 由该络合剂 制得的电镀液质量稳定， 电镀液分散性好， 可采用的工艺电流密度范围较 宽， 电镀液的应用范围广。
具体实施方式
下面通过具体实施例， 对本发明的技术方案作进一步的具体说明。 下列各实施例中的试剂或原料均系市购常规原料， 纯度为分析純。 实施例 1:
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz， 其中 x=3， y=0， n=2， z=l， M为 K+, R为乙酰基， 具体结构式如下：
0
II
0- C-CH3
K 该絡合剂的制备方法如下： 将氢氧化钾、磷酸和乙酸按摩尔比 3:2:1混 合反应， 反应液通过喷雾干燥获得部分聚合的中间体粉末， 将该中间体粉 末置于耙式干燥机内于 250'C聚合反应 10h,聚合反应结束后获得络合剂成 实施例 2:
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz， 其中 x=3， y=0， n=3 , z=2, M为 K+和 Na+， R为乙酰基， 具体结构式如下： 3
Figure imgf000008_0001
该絡合剂的制备方法如下： 将氢氧化钠、磷酸和乙酸按摩尔比 3:3:2混 合反应， 反应液通过闪蒸干燥获得部分聚合的中间体粉末， 将该中间体粉 末置于耙式干燥机内于 20CTC聚合反应 10h,聚合反应结束后获得络合剂成 实施例 3:
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz， 其中 x=5， y=0， n=5, z=2， M为 Na+， R为乙酰基和酒石酸氢钠脱水后形成的酰基， 具体 结构 如下： COONa
Figure imgf000008_0002
该络合剂的制备方法如下： 将碳酸氢钠、 磷酸、 乙酸和酒石酸氢钠按 摩尔比 5:5:1 :1混合反应， 然后反应液通过闪蒸干燥获得部分聚合的中间体 粉末， 将该中间体粉末置于耙式干燥机内于 40CTC聚合反应 0.5h, 聚合反 应结束后获得络合剂成品。
实施例 4:
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz, 其中 x=10, y=l , n=10, z=l , M为 K+和 Na+， R为酒石酸氢钠脱水后形成的酰基， 具体结 构式如下：
Figure imgf000009_0001
该络合剂的制备方法如下： 将氢氧化钠、 氢氧化钾、 磷酸和酒石酸氢 钠按摩尔比 1 :9: 10:1 混合反应， 反应液通过喷雾干燥获得部分聚合的中间 体粉末， 将该中间体粉末置于耙式干燥机内于 80CTC聚合反应 0.5h， 聚合 反应结束后获得络合剂成品。
实施例 5:
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz, 其中 x=10, y=l , n=10， z=l , M为 Na+， R为柠檬酸氢二钠脱水后形成的酰基， 具体结构式 如下：
Na-
Figure imgf000009_0002
a
该络合剂的制备方法如下： 将碳酸钠、 磷酸和柠檬酸氢二钠按摩尔比
5: 10:1 混合反应， 反应液通过闪蒸干燥获得部分聚合的中间体粉末， 将该 中间体粉末置于耙式干燥机内于 40CTC聚合反应 0.5h, 聚合反应结束后获 得絡合剂成品。
实施例 6:
一种络合剂， 所述絡合剂的通式为 MxHyPn03n+lRz， 其中 x=l， y=100, n=100, z=l， M为 Na+， R为丙氨酸脱水后形成的酰胺基， 具体结构式如
Figure imgf000010_0001
该络合剂的制备方法如下：将碳酸氢钠、磷酸和丙氨酸按摩尔比 1： 100: 1 混合反应， 反应液通过闪蒸干燥获得部分聚合的中间体粉末， 将该中间体 粉末置于耙式干燥机内于 300°C聚合反应 2.5h， 聚合反应结束后获得络合 剂成品。
实施例 7:
一种络合剂， 所述絡合剂的通式为 MxHyPn03n+lRz， 其中 x=l， y=100, n=100, z=l , M为 Na+， R为乙酰基， 具体结构式如下：
Figure imgf000010_0002
该絡合剂的制备方法如下： 将破酸氢钠、 磷酸和乙酸按摩尔比 1 :100:1 混合反应， 反应液通过闪蒸干燥获得部分聚合的中间体粉末， 将该中间体 粉末置于耙式干燥机内于 300°C聚合反应 2.5h， 聚合反应结束后获得络合 剂成品。
实施例 8
一种络合剂， 所述络合剂的通式为 MxHyPn03n+lRz， 其中 x=3， y=0， n=2， z=l , M为 Na+， R为甲基騎酸脱水有形成的酰基， 具体结构式如下： OH
Figure imgf000011_0001
a 该絡合剂的制备方法如下：将氢氧化钠、磷酸和甲基碼酸按摩尔比 3： 2： 1 混合反应， 反应液通过闪蒸干燥获得部分聚合的中间体粉末， 将该中间体
N ool
粉末置于耙式干燥机内于 300°C聚合反应 5h， 聚合反应结束后获得络合剂 成品。
上述络合剂用于制备电镀液， 所述电镀液为镀铜、 镀锡、 镀铜锌合金、 镀铜锡合金、 镀镍锡合金、 镀镍钴合金、 镀锡钴合金和镀镍锡钴合金中的 任意一种。
下面以镀铜电镀液为例， 具体如下：
实施例 9:
以实施例 7制得的络合剂用于无氰预镀铜电镀液的制备， 所述电镀液 的制备方法如下：
( 1 )铜盐的制备： 将实施例 7制得的絡合剂与硫酸铜按摩尔比 2: 1 混合均匀， 于常温反应 l .Ohu 反应结束后经过离心分离并干燥得铜盐， 该 铜盐的结构式如下；
Figure imgf000012_0001
H
(2) 电镀液的制备： 将 1% (质量百分数） 实施例 7的络合剂、 0.5% 步骤（1 )制得的铜盐和 98.5%的纯化水按比例混合均勾， 然后用氢氧化钾 调 pH值至 8.5， 获得无氰预镀铜电镀液。
实施例 10:
以实施例 8制得的絡合剂用于无氰预镀铜电镀液的制备， 所述电镀液 的制备方法如下：
(1)铜盐的制备： 将实施例 8制得的络合剂与硫酸铜按摩尔比 2: 3 混合均匀， 于常温反应 1.0h， 反应结束后经过离心分离并干燥得铜盐， 该 铜盐的结构式如
Figure imgf000012_0002
( 2 )电镀液的制备： 将 60% (质量百分数）的实施例 1的絡合剂、 5% 的步骤 ( 1 )获得的铜盐和 35%的纯化水按比例混合均匀， 然后氢氧化钾调 pH值至 9.5， 获得预镀铜电镀液。
对实施例 9和 10制得的无氰预镀铜电镀液进行了下列研究：
1、 Hull槽试验 ( 267ml )
1.1 初步试验： 对实施例 9和实施例 10制得的电镀液在温度 25 °C， 电 路 1A (稳流）、 空气搅拌的条件下打片， 时间 5min， 打片过程中观察到在 稳流条件下， 槽压也相对稳定且镀片在较大面积上表现出半光点、 晶体细 致的特点。
1.2 Hull槽试验确定电流密度范围：
以实施例 9和实施例 10制得的电镀液在温度 55°C， 电流 1A， 时间 10mm, 通过 Hull 打片确定最佳电流密度范围， 打片选用的片材采用 0.5*70*100 的 A3 钢片， 600 #水磨砂纸打磨抛光。 参考经验公式 Jk=I ( 5.1- 5.24LgL ) 计算试片每一点的电流密度。 通过打片和电流密度计算可 以得出， 实施例 9和实施例 10制得的电镀液的电流密度范围是 0.5A/dm2 到 2.5 A/dm2之间。
2 电镀液和电镀性能测试
2.1 电流效率的测定： 采用铜库仑计测量， 实施例 9 制得的电镀液的 电流效率为 93.0%, 实施例 10制得的电镀液的电流效率为 93.8%。
2.2 电镀液分散能力测定： 用弯曲阴极法测电镀液的分散能力， 条件 为电流 1A， 无油空气搅拌， 温度 55°C， 时间 30min， 试材选用 0.5*70*100 的 A3铜片， 600 #水磨 、纸打磨抛光。
测得的实施例 9的电镀液的分散能力为 93. 5%, 实施例 10的电镀液的 分散能力为 93. 1%。
2. 3 覆盖能力的测定： 采用内孔法测量镀液的覆盖能力， 铜管尺寸 10mm* 10 Omm, 采用通孔和盲孔法， 电镀液温度为 55 °C， 阴极电流密度为 0. 5A/ dm2， 时间 5mm。 实验后剖开铁管， 观察管内镀层情况。
以实施例 9和 10的电镀液为实验电镀液， 实验完毕后发现通孔和盲孔 全部镀上了铜层，说明实施例 9和实施例 10制得的电镀液的覆盖能力良好。 2.4 结合力测试
2.4.1 弯曲实验： 采用厚度为 0.5mm的抛光铁片 （A3 ), 电镀液的温度 为 55°C， 阴极电流密度为 2 A/ dm2， 时间 15min。
以实施例 9和 10的电镀液为实验电镀液， 实验完毕后将镀好的试片反 复弯曲至断裂， 裂口处无脱皮现象， 证明镀层和基体不分离。
2.4.2 热震实验： 采用厚度为 0.5mm的抛光铁片 （A3 ), 电镀液的温度 为 55°C， 阴极电流密度为 2 A/ dm2， 时间 15min。
以实施例 9和 10的电镀液为实验电镀液， 实验完毕后将镀好的试片放 在烘箱中烘烤至 20CTC， 连续烘烤 lh， 取出后立即浸入 0°C水中骤冷， 结 果未发现镀层起泡和脱皮现象。
2.5 镀层韧性实验： 将 lmm厚的 A3钢片用铬酸钝化， 清洗后直接挂 在实施例 9和 10制得的电镀液中， 镀层的厚度达到 20 μ πι后， 将镀层剥 离下来， 弯曲 180°C， 并挤压弯曲处， 镀层不断裂， 表明镀层韧性好。
2.6镀层孔隙率实验： 采用厚度为 0.5mm 的抛光铁片 （A3 ), 电镀液 的温度 55°C， 阴极电流密度 1A/ dm2， 时间 20mm, 用铁氰化钟溶液贴滤纸 实验法进行孔隙率实验。
铁氰化钾 lOg L; 氯化钠 20g L。
实验结果表明， 实施例 9和实施例 10制得的电镀液作为实验对象形成 的电镀层的孔隙率均 1个 / dm2。
2.7 沉积速度的测定： 设定电流 1A， 温度 55°C， 时间 30min， 测定结 果表明， 实施例 9制得的电镀液的沉积速度为 0.6 μ m/min, 实施例 10制得 的电镀液的沉积速度为 0.52 μ m/min。
对实施例 9和实施例 10制得的电镀液进一步进行中试实验， 中试工艺 参数如下：
工艺流程：钢铁工件→超声波除油→水洗 1→水洗 2→阳极电解除油→ 水洗 1→水洗 2→酸洗除油→水洗 1→水洗 2→盐酸洗→水洗 1→水洗 2→终 端电解除油→水洗 1→水洗 2→酸活化→水洗 1→水洗 2→实施例 9或 10的 电镀液→回收→水洗 1→水洗 2→酸活化→酸铜。
超声波除油：除油粉浓度 50 ± 5g/L，温度 70士 5°C，电流密度 l-5A/dm2， 时间 5分^ ^。
阴极电解除油： 电解除油粉浓度 50 ± 5g/L， 温度 70 ± 5。C， 电流密度 1 -5A/dm2， 时间 5〜7分钟。
阳极电解除油： 电解除油粉浓度 50 ± 5g L， 温度 70 ± 5°C， 电流密度 1-5 A/dm2, 时间 3~5分 4中。
酸洗： 工业盐酸浓度 15〜20%, 时间 8~10min， 室温。
活化： 工业盐酸浓度 5〜： 10%， 时间 3〜5min， 室温。
实施例 9或 10的电镀液： 波美度 32-36， pH值 8.5~9.5， 温度 50~55 °C， 电流密度 0.5~2.5 A/dm2， 时间 5mm至数小时不等， 实践证明， 镀至 ΙΟΟ μ πι整平性、 光亮度还非常好。
通过 50L中试电镀生产线连续运 ^亍 20个月， 350L中试电镀生产线连 续运行 11个月， 验证了实施例 9或 10制得的电镀液具有可靠性， 镀液性 能稳、定， 镀液的消耗为 10~50ml/KAH。
在上述中试的实验基础上，获得实施例 9或 10制得的电镀液用于工业 化生产的工艺条件。
1、 钢铁工件：
工艺流程：钢铁工件→超声波除油→水洗 1→水洗 2→阳极电解除油→ 水洗 1→水洗 2→酸洗除油→水洗 1→水洗 2→盐酸洗→水洗 1→水洗 2→终 端电解除油→水洗 1→水洗 2→酸活化→水洗 1→水洗 2→预浸→实施例 9 或 10的电镀液→回收→水洗 1→水洗 2→酸活化→酸铜。
工艺条件：
电镀液密度： 32~36波美度
温度 45~60°C
pH值： 8.60-9.50
搅拌： 空气搅拌加阴极移动
阳极： 电解铜或无氧电解铜
阴阳面积比： 1 :1.5〜2。
电流： 0.5~2.5A/dm2
2、 锌合金工件： 工艺流程：锌合金工件→热浸除蜡→超声波除蜡→水洗 1→水洗 2→超 声波除油→水洗 1→水洗 2→阳极电解除油→水洗 1→水洗 2→酸盐活化→ 水洗 1→水洗 2→超声波预浸液预浸 30s→实施例 9或 10的电镀液（带电入 槽 25〜35°C ) →回收→水洗 1→水洗 2→酸活化→酸铜。
工艺条件：
电镀液密度： 32~38波美度
温度 25-35 Γ
pH值： 8.60-9.50
搅拌： 空气搅拌加阴极移动
阳极： 电解铜或无氧电解铜
阴阳面积比： 1 :1.5~2。
电流： 0.5-1.5A/dm2
以上所述的实施例只是本发明的一种较佳的方案， 并非对本发明作任 何形式上的限制， 在不超出权利要求所记载的技术方案的前提下还有其它 的变体及改型。

Claims

一 权利 要 求 书 WO 2015/103785 PCT/CN2014/070526
1. 一种络合剂， 其特征在于： 所述缮合剂的通式为 MxHyPn03n+1Rz, 其 中 M为碱金属离子和 NH4+中的任意一种或多种； R为酰基； X、 Π和 Z均 为正整数， y为 0或正整数， x+y+z=n+2。
2. 根据权利要求 1 所述的絡合剂， 其特征在于： 所述绺合剂的通式为 MxHyPn03n+1R, 其中 M为 Na+、 K+和 ΝΉ4+中的任意一种或多种； R为酰基； X和 η均为正整数， y为 0或正整数， x+y =n+l。
3. —种权利要求 1或 2所述的络合剂的制备方法， 其特征在于： 具体操 作如下： 将含 M的碱、 碳酸盐或碳酸氢盐与磷酸、 含 R基的一元有机酸或 多元有机酸的酸式盐按摩尔比混合反应， 然后反应液在 100〜800°C条件下 一步聚合 0.5〜； I Oh 获得络合剂成品； 或者上述反应液先干燥， 然后再在 100~800°C条件下聚合 0.5~10h获得络合剂成品。
4.根据权利要求 3所述的絡合剂的制备方法，其特征在于，当 M为 Na+ 时， 将氢氧化钠、 碳酸钠或碳酸氢钠与磷酸、 含 R基的一元有机酸或多元 有机酸的酸式盐按摩尔比混合反应， 然后反应液在 200〜400°C条件下一步 聚合 0.5〜； I Oh获得络合剂成品； 或者上述反应液先干燥， 然后再在 200〜400 条件下聚合 0.5-1 Oh获得络合剂成品。
5.根据权利要求 3所述的络合剂的制备方法， 其特征在于， 当 M为 K+ 时， 将氢氧化钾、 碳酸钾或碳酸氢钾与磷酸、 含 R基的一元有机酸或多元 有机酸的酸式盐按摩尔比混合反应， 然后反应液在 250~800°C条件下一步 聚合 0.5〜： 1 Oh获得络合剂成品； 或者上述反应液先干燥， 然后再在 250〜800 条件下聚合 0.5-1 Oh获得絡合剂成品。 一 权利 要 求 书
WO 2015/103785 PCT/CN2014/070526
6.根据权利要求 3 所述的絡合剂的制备方法， 其特征在于， 当 M 为 ΝΉ4+时， 将氨水、碳酸铵或碳酸氢铵与磷酸、含 R基的一元有机酸或多元 有机酸的酸式盐按摩尔比混合反应， 然后反应液在 100~300°C条件下一步 聚合 0.5~10h获得絡合剂成品； 或者上述反应液先干燥， 然后再在 100~300 条件下聚合 0.5-1 Oh获得络合剂成品。
7. 一种权利要求 1或 2所述的络合剂的应用， 其特征在于： 用于制备 电镀液。
8. 根据权利要求 7所述的絡合剂的应用， 其特征在于： 所述电镀液为 镀铜、 镀锡、 镀铜锌合金、 镀铜锡合金、 镀镍锡合金、 镀镍钴合金、 镀锡 钴合金和镀镍锡钴合金中的任意一种。
9. 根据权利要求 7所述的络合剂的应用， 其特征在于： 所述电镀液中 络合剂的用量以质量百分数计为 1~60%。
PCT/CN2014/070526 2014-01-13 2014-01-13 一种络合剂及其制备方法和用途 WO2015103785A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2016547031A JP6263636B2 (ja) 2014-01-13 2014-01-13 錯化剤、その製造方法及び用途
KR1020167022170A KR101850639B1 (ko) 2014-01-13 2014-01-13 착화제 및 이의 제조방법과 용도
PCT/CN2014/070526 WO2015103785A1 (zh) 2014-01-13 2014-01-13 一种络合剂及其制备方法和用途
US15/111,291 US20160333032A1 (en) 2014-01-13 2014-01-13 Complexing Agent and Preparation Method and Use Thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/070526 WO2015103785A1 (zh) 2014-01-13 2014-01-13 一种络合剂及其制备方法和用途

Publications (1)

Publication Number Publication Date
WO2015103785A1 true WO2015103785A1 (zh) 2015-07-16

Family

ID=53523475

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/070526 WO2015103785A1 (zh) 2014-01-13 2014-01-13 一种络合剂及其制备方法和用途

Country Status (4)

Country Link
US (1) US20160333032A1 (zh)
JP (1) JP6263636B2 (zh)
KR (1) KR101850639B1 (zh)
WO (1) WO2015103785A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105401177A (zh) * 2015-12-14 2016-03-16 广东美的暖通设备有限公司 换热器的防腐处理方法、换热器和空调器

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3364947B1 (en) 2015-10-20 2021-09-15 B. Braun Melsungen AG Aqueous composition comprising dantrolene
CN113234107A (zh) * 2021-06-02 2021-08-10 风之虎研盐实验室科技(江苏)有限公司 防盐结块剂、防盐结块剂中间体及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1873058A (zh) * 2005-03-31 2006-12-06 Tdk株式会社 镀敷液、导电性材料和导电性材料的表面处理方法
CN101030481A (zh) * 2006-12-22 2007-09-05 东莞市东阳光电容器有限公司 铝电解电容用阳极箔的化成方法
CN103755738A (zh) * 2014-01-13 2014-04-30 孙松华 一种络合剂及其制备方法和用途

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW420729B (en) * 1996-02-12 2001-02-01 Gould Electronics Inc A non-cyanide brass plating bath and a method of making metallic foil having a brass layer using the non-cyanide brass plating bath
JP4942302B2 (ja) * 2005-03-11 2012-05-30 三洋電機株式会社 非水電解質二次電池用電極及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1873058A (zh) * 2005-03-31 2006-12-06 Tdk株式会社 镀敷液、导电性材料和导电性材料的表面处理方法
CN101030481A (zh) * 2006-12-22 2007-09-05 东莞市东阳光电容器有限公司 铝电解电容用阳极箔的化成方法
CN103755738A (zh) * 2014-01-13 2014-04-30 孙松华 一种络合剂及其制备方法和用途

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SIGEL, H. ET AL.: "Stability and Structure of Metal Ion Complex Formed in Solution with Acetyl Phosphate and Acetonylphosphate; Quantification of Isomeric Equilibria", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 121, no. 26, 30 June 1999 (1999-06-30) *
YIN, XIN ET AL.: "Preparation of Acetylphosphate Dilithium and Its Assay", CHINESE JOURNAL OF BIOCHEMICAL PHARMACEUTICS, vol. 4, no. 24, 30 September 2003 (2003-09-30) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105401177A (zh) * 2015-12-14 2016-03-16 广东美的暖通设备有限公司 换热器的防腐处理方法、换热器和空调器

Also Published As

Publication number Publication date
KR20160108501A (ko) 2016-09-19
US20160333032A1 (en) 2016-11-17
JP2017509591A (ja) 2017-04-06
JP6263636B2 (ja) 2018-01-17
KR101850639B1 (ko) 2018-04-19

Similar Documents

Publication Publication Date Title
WO2015103786A1 (zh) 一种无氰预镀铜电镀液及其制备方法
CN103806041B (zh) 一种无氰铜锌合金电镀液及其制备方法
CN101387000A (zh) 无氰预镀铜工艺方法
WO2015103785A1 (zh) 一种络合剂及其制备方法和用途
CN110592623B (zh) 用于提高钕铁硼磁体镀层均匀分布性的电镀镍溶液配方及其方法
CN103789803B (zh) 一种无氰铜锡合金电镀液及其制备方法
CN101922031B (zh) 双镀层钢带及电镀工艺
EP3168332B1 (en) Electrolytic stripping agent for removing palladium from a jig
CN104451616A (zh) 一种用于4Cr13不锈钢的化学镀镍方法
CN103755738B (zh) 一种络合剂及其制备方法和用途
CN103806033A (zh) 一种锌压铸件表面电镀金属层的方法
CN103789801B (zh) 一种无氰预镀铜电镀液及其制备方法
CN110172684A (zh) 一种abs无铬粗化液及其制备方法与应用
CN111519225A (zh) Abs塑料的无铬无锰粗化液及其使用方法
WO2019045047A1 (ja) Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
JP6551563B1 (ja) Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
JP2003239100A (ja) 水素脆性防止のメッキ処理法
CN104178789A (zh) 一种电磁纯铁沉积镍铜合金工艺
JP2007126745A (ja) クロム酸−硫酸混液によるエッチング処理の後処理剤
CN110144609A (zh) 一种多次沉锌的电镀加工方法
JP2009001856A (ja) 水処理技術
TWI354035B (zh)
EP3191616A1 (en) Metal connector or adaptor for hydraulic or oil dynamic application at high pressure and relative galvanic treatment for corrosion protection
CN106835224A (zh) 一种邦迪管用钢带电镀方法
CN116397310A (zh) 金属表面抗氧化电镀处理工艺及电镀液处理方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14877978

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016547031

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15111291

Country of ref document: US

ENP Entry into the national phase

Ref document number: 20167022170

Country of ref document: KR

Kind code of ref document: A

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205N DATED 20.09.2016)

122 Ep: pct application non-entry in european phase

Ref document number: 14877978

Country of ref document: EP

Kind code of ref document: A1