Copper plating additive and preparation method and application thereof

Abstract

The invention provides a copper plating additive and a preparation method and application thereof. The copper plating additive comprises a disulfide disubstituted aromatic sulfonate compound and a substituted polyoxypropylene ether compound, the structural general formula of the disulfide disubstituted aromatic sulfonate compound is shown as I: # imgabs0 #, R1 and R3 are independently selected from-OH,-CHO or-SH, and R2 and R4 are independently selected from-OH,-NH2 or-COONa; the structural general formula of the substituted polyoxypropylene ether compound is as shown in II: # imgabs 1 #, R1 is-CH2OH,-CH2CH2OH,-CH2CH (OH) CH3 or-CH2CH (OH) CH2CH2OH, and R2 is # imgabs 2 #. The copper plating additive is high in oxidation resistance, the consumption of the additive can be greatly reduced, TOC of a bath solution rises slowly, the copper plating effect of a printed circuit board can be improved, and the service life of the bath solution can be prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of printed circuit board processing, and in particular to a copper plating additive and a preparation method and application thereof. Background Art

[0002] With the diversified development trends such as the continuous reduction of hole size in printed circuit boards (PCBs), the continuous increase in the number of PCB layers, and the increase in the thickness-to-diameter ratio of holes, the improvement of the uniformity of copper metallization of PCB holes and the long-term stability of the bath liquid are key technical pain points that affect the production of printed circuits.

[0003] Adding a combination of additives to the PCB acid copper electroplating solution can achieve uniform and thick deposition of PCB hole metallization electroplating. Traditional copper plating additives use SPS, UPS, MPS, DPS and SH110 as lattice refiners, or accelerators. However, in some high-end special printed circuit manufacturing fields, transition metal coatings such as iridium oxide, tantalum oxide, platinum oxide and other insoluble anodes are used, and the anode reaction process is oxygen evolution reaction; in addition, in some high-end hole filling, insoluble anode pulse copper plating and other fields, in order to improve the performance of the coating, some solutions need to add additional oxidizing metal ions Fe 3+ , which makes the -SS- bonds and -SH groups contained in SPS, UPS, MPS, DPS and SH110 in traditional copper plating additives vulnerable to oxide attack and decomposition failure, greatly increasing the consumption of organic additives during the use of the plating solution, and also bringing about a rapid increase in by-products in the electroplating bath, as well as the problem of a rapid increase in the total organic carbon (TOC) of the bath. Although different additives have different tolerances to organic by-products, and printed circuit product manufacturers with different reliability requirements have different control over TOC content, usually when the TOC content of the copper plating bath exceeds 2500ppm~3500ppm, the bath needs to be maintained, such as activated carbon treatment or carbon core filtration, to improve the copper plating effect and extend the life of the bath; when the TOC content of the copper plating bath exceeds 4500ppm~5500ppm, the bath must be replaced, otherwise it will not meet the performance requirements of high-reliability printed circuit products, will have a negative impact on the copper plating reaction, and reduce the copper plating effect of the printed circuit board and the service life of the bath. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a copper plating additive having strong oxidation resistance, which can significantly reduce the consumption of additives and slowly increase the TOC of the bath solution, thereby improving the copper plating effect of the printed circuit board and the service life of the bath solution, as well as a preparation method and application thereof.

[0005] The objective of the present invention is achieved through the following technical solutions:

[0006] A copper plating additive, comprising a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound;

[0007] The general structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is shown in I:

[0008]

[0009] wherein R1 and R3 are independently selected from -OH, -CHO or -SH, and R2 and R4 are independently selected from -OH, -NH2 or -COONa;

[0010] The general structural formula of the substituted polyoxypropylene ether compound is shown in II:

[0011]

[0012] Wherein, R1 is -CH2OH, -CH2CH2OH, -CH2CH(OH)CH3 or -CH2CH(OH)CH2CH2OH, and R2 is

[0013] In one embodiment, the copper plating additive further includes a solvent.

[0014] In one embodiment, the solvent is water.

[0015] In one embodiment, the concentration of the disulfide disubstituted aromatic hydrocarbon sulfonate compound in the copper plating additive is 0.1 g / L to 10 g / L.

[0016] In one embodiment, the concentration of the substituted polyoxypropylene ether compound in the copper plating additive is 1 g / L to 50 g / L.

[0017] A method for preparing a copper plating additive, used for preparing the copper plating additive described in any of the above embodiments, the method for preparing the copper plating additive comprising the following steps:

[0018] Obtain disulfide disubstituted aromatic hydrocarbon sulfonate compounds and substituted polyoxypropylene ether compounds.

[0019] The disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound are subjected to solution preparation treatment to obtain a copper plating additive.

[0020] In one embodiment, obtaining a disulfide disubstituted aromatic hydrocarbon sulfonate compound comprises the following steps:

[0021] Propylene glycol and methanesulfonyl chloride derivative are mixed and heated to 80°C to 90°C, and stirred and refluxed for 3.5h to 4.5h to obtain a yellow liquid;

[0022] The yellow liquid is cooled to room temperature, and then n-butyl lithium is added to the yellow liquid and stirred for reaction for 2 h to 3 h to obtain a dark yellow liquid;

[0023] Add sodium thioacetate and hydrogen peroxide to the dark yellow liquid, heat to 38° C. to 45° C., and stir to react for 1.8 h to 2.5 h to obtain a yellow-brown liquid;

[0024] Adding water to the yellow-brown liquid, followed by chromatography, concentration and crystallization to obtain a disulfide disubstituted aromatic hydrocarbon sulfonate compound;

[0025]

[0026] In one embodiment, obtaining the substituted polyoxypropylene ether compound comprises the following steps:

[0027] Take 2-chloro-butylene oxide and an alcohol amine compound having a pyridine or piperidine group and dissolve them in ethyl acetate, then add boron trifluoride catalyst, heat to 80°C to 90°C, stir and reflux for 9h to 11h to obtain a yellow liquid;

[0028] Add water to the yellow liquid, let it stand to separate into layers, take a water sample of the lower layer, concentrate and separate, and obtain a substituted polyoxypropylene ether compound;

[0029]

[0030] In one embodiment, the water is deionized water.

[0031] An application of a copper plating additive, wherein the copper plating additive described in any of the above embodiments is applied to a copper plating solution.

[0032] In one embodiment, the copper plating solution further includes 50 g / L to 100 g / L of copper sulfate pentahydrate, 200 g / L to 300 g / L of sulfuric acid and 40 mg / L to 100 mg / L of chloride ions.

[0033] In one embodiment, the amount of the copper plating additive added to the copper plating solution is 1 mL / L to 10 mL / L.

[0034] In one of the embodiments, during use of the copper plating solution, the amount of copper plating additive added is 30 mL / kiloampere-hour to 80 mL / kiloampere-hour.

[0035] In one embodiment, the copper plating solution is used at a current density of 3.0 ASD to 8.0 ASD.

[0036] Compared with the prior art, the present invention has at least the following advantages:

[0037] The copper plating additive of the present invention adopts a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound to form a copper plating additive for a copper plating solution. The present invention adopts the disulfide disubstituted aromatic hydrocarbon sulfonate compound as a copper plating gloss agent, and reduces the risk of SS being oxidized by the steric hindrance of the symmetrical benzene ring added to the SS bond side chain and the reducing aldehyde group, phenol group, mercapto group and the like; adopts the substituted polyoxypropylene ether compound as an inhibitor component with a leveling effect, reduces the usage amount of the overall organic polymer in the additive, and reduces the risk of oxidation of the small molecule compound used, that is, the copper plating additive has a strong oxidation resistance, and the usage amount and consumption of the additive are greatly reduced, thereby making the TOC of the bath containing the copper plating additive rise slowly, thereby effectively ensuring the copper plating effect and service life of the bath containing the copper plating additive during use; in addition, the copper plating solution containing the copper plating additive has a good appearance gloss and good ductility through an insoluble anode to form a coating, thereby effectively improving the copper plating effect of the bath containing the copper plating additive during use, and can realize high-speed copper plating of the insoluble anode, thereby effectively improving the copper plating efficiency of the insoluble anode. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0039] Figure 1 is the general structural formula of a disulfide disubstituted aromatic hydrocarbon sulfonate compound according to one embodiment of the present invention;

[0040] Figure 2 is the general structural formula of a substituted polyoxypropylene ether compound according to one embodiment of the present invention;

[0041] Figure 3 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 1;

[0042] Figure 4 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 2;

[0043] Figure 5 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 3;

[0044] Figure 6 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 4;

[0045] Figure 7 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 5;

[0046] Figure 8 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 6;

[0047] Fig. 9 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 7;

[0048] Fig.10 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 8;

[0049] Fig.11 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 9;

[0050] Fig.12 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 10;

[0051] Fig.13 is the specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 11;

[0052] Fig.14 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 12;

[0053] Fig.15 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 13;

[0054] Fig.16 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 14;

[0055] Fig.17 The specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 15;

[0056] Fig.18It is the specific chemical structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound of Example 16. DETAILED DESCRIPTION

[0057] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0058] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are for illustrative purposes only and do not represent the only implementation method.

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0060] The present application provides a copper plating additive. In order to better understand the copper plating additive of the present application, the copper plating additive of the present application is further explained below:

[0061] The copper plating additive of one embodiment includes a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound;

[0062] The general structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is shown in I:

[0063]

[0064]

[0065] wherein R1 and R3 are independently selected from -OH, -CHO or -SH, and R2 and R4 are independently selected from -OH, -NH2 or -COONa;

[0066] The general structural formula of the substituted polyoxypropylene ether compound is shown in II:

[0067]

[0068] Wherein, R1 is -CH2OH, -CH2CH2OH, -CH2CH(OH)CH3 or -CH2CH(OH)CH2CH2OH, and R2 is

[0069] The above copper plating additive adopts a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound to form a copper plating additive for a copper plating solution. The present invention adopts a disulfide disubstituted aromatic hydrocarbon sulfonate compound as a copper plating gloss agent, and reduces the risk of SS being oxidized by adding steric hindrance of the symmetrical benzene ring and reducing aldehyde groups, phenol groups, thiol groups, etc. on the SS bond side chain; and adopts a substituted polyoxypropylene ether compound as an inhibitor component with a leveling effect, thereby reducing the amount of the overall organic polymer used in the additive, and at the same time reducing the risk of oxidation of the small molecule compound used, that is, the copper plating additive The agent has strong oxidation resistance, and the usage and consumption of the additive are greatly reduced, so that the TOC of the bath containing the copper plating additive rises slowly, thereby effectively ensuring the copper plating effect and service life of the bath containing the copper plating additive during use; in addition, the coating formed by the copper plating solution containing the copper plating additive on the insoluble anode has good appearance gloss and good ductility, thereby effectively improving the copper plating effect of the bath containing the copper plating additive during use, and realizing high-speed copper plating of the insoluble anode, thereby effectively improving the copper plating efficiency of the insoluble anode.

[0070] In one embodiment, the copper plating additive further includes a solvent.

[0071] In one embodiment, the solvent is water.

[0072] In one embodiment, the concentration of the disulfide disubstituted aromatic hydrocarbon sulfonate compound in the copper plating additive is 0.1 g / L to 10 g / L.

[0073] In one embodiment, the concentration of the substituted polyoxypropylene ether compound in the copper plating additive is 1 g / L to 50 g / L.

[0074] The present application also provides a method for preparing a copper plating additive. The method for preparing the copper plating additive comprises the following steps: obtaining a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound; and performing solution preparation treatment on the disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound to obtain a copper plating additive.

[0075] In one embodiment, obtaining a disulfide disubstituted aromatic hydrocarbon sulfonate compound comprises the following steps:

[0076] Propylene glycol and methanesulfonyl chloride derivative are mixed and heated to 80°C to 90°C, and stirred and refluxed for 3.5h to 4.5h to obtain a yellow liquid;

[0077] The yellow liquid is cooled to room temperature, and then n-butyl lithium is added to the yellow liquid and stirred for reaction for 2 h to 3 h to obtain a dark yellow liquid;

[0078] Add sodium thioacetate and hydrogen peroxide to the dark yellow liquid, heat to 38° C. to 45° C., and stir to react for 1.8 h to 2.5 h to obtain a yellow-brown liquid;

[0079] Adding water to the yellow-brown liquid, followed by chromatography, concentration and crystallization to obtain a disulfide disubstituted aromatic hydrocarbon sulfonate compound;

[0080]

[0081] In one embodiment, obtaining the substituted polyoxypropylene ether compound comprises the following steps:

[0082] Take 2-chloro-butylene oxide and an alcohol amine compound having a pyridine or piperidine group and dissolve them in ethyl acetate, then add boron trifluoride catalyst, heat to 80°C to 90°C, stir and reflux for 9h to 11h to obtain a yellow liquid;

[0083] Add water to the yellow liquid, let it stand to separate into layers, take a water sample of the lower layer, concentrate and separate, and obtain a substituted polyoxypropylene ether compound;

[0084]

[0085] In one embodiment, the water is deionized water.

[0086] In one embodiment, the hydrogen peroxide is 30% hydrogen peroxide.

[0087] In one embodiment, the mass ratio of propylene glycol to the methanesulfonyl chloride derivative is (2-3):(3-4), and further, the mass ratio of propylene glycol to the methanesulfonyl chloride derivative is 30:39.

[0088] In one embodiment, the mass ratio of n-butyl lithium to the methanesulfonyl chloride derivative is (4-5):(12-15). Further, the mass ratio of n-butyl lithium to the methanesulfonyl chloride derivative is 13:39.

[0089] In one embodiment, the mass ratio of sodium thioacetate to 30% hydrogen peroxide is (9-12):(20-25), and further, the mass ratio of sodium thioacetate to 30% hydrogen peroxide is 10:23.

[0090] In one embodiment, the mass ratio of sodium thioacetate to the methanesulfonyl chloride derivative is 1:(1.8-2.1), and further, the mass ratio of sodium thioacetate to the methanesulfonyl chloride derivative is 20:39.

[0091] In one embodiment, the mass ratio of 2-chloro-butylene oxide and the alcoholamine compound having a pyridine or piperidine group is (20-23): (28-32), and further, the mass ratio of 2-chloro-butylene oxide and the alcoholamine compound having a pyridine or piperidine group is 21:30.

[0092] In one embodiment, the amount of boron trifluoride catalyst added is 0.5% to 0.8% of the total mass of the alcoholamine compound having a pyridine or piperidine group.

[0093] In one embodiment, 2-chloro-butylene oxide and an alcohol amine compound having a pyridine or piperidine group are dissolved in ethyl acetate, and the amount of ethyl acetate used is such that the 2-chloro-butylene oxide and the alcohol amine compound having a pyridine or piperidine group are completely dissolved.

[0094] The present application also provides an application of a copper plating additive, wherein the copper plating additive described in any of the above embodiments is applied to a copper plating solution.

[0095] The copper plating solution adopts a copper plating additive, so that the TOC of the copper plating solution rises slowly, thereby effectively ensuring the copper plating effect and service life of the copper plating solution during use, and making the coating formed by the copper plating solution on the insoluble anode have good appearance gloss and good ductility, and can realize high-speed copper plating of the insoluble anode, thereby effectively improving the copper plating efficiency of the insoluble anode.

[0096] In one embodiment, the copper plating solution further includes 50 g / L to 100 g / L of copper sulfate pentahydrate, 200 g / L to 300 g / L of sulfuric acid and 40 mg / L to 100 mg / L of chloride ions.

[0097] In one embodiment, the amount of the copper plating additive added to the copper plating solution is 1 mL / L to 10 mL / L.

[0098] In one of the embodiments, during use of the copper plating solution, the amount of copper plating additive added is 30 mL / kiloampere-hour to 80 mL / kiloampere-hour.

[0099] In one embodiment, the copper plating solution is used at a current density of 3.0 ASD to 8.0 ASD.

[0100] Compared with the prior art, the present invention has at least the following advantages:

[0101] The copper plating additive of the present invention adopts a disulfide disubstituted aromatic hydrocarbon sulfonate compound and a substituted polyoxypropylene ether compound to form a copper plating additive for a copper plating solution, so that the copper plating additive has strong oxidation resistance, thereby greatly reducing the consumption of the additive, and the TOC of the bath containing the copper plating additive rises slowly, thereby effectively ensuring the copper plating effect and service life of the bath containing the copper plating additive during use; in addition, the appearance glossiness and ductility of the coating formed by the copper plating solution containing the copper plating additive on the insoluble anode are good, thereby effectively improving the copper plating effect of the bath containing the copper plating additive during use, and realizing high-speed copper plating of the insoluble anode, thereby effectively improving the copper plating efficiency of the insoluble anode.

[0102] Some specific examples are listed below, and if % is mentioned, it means percentage by weight. It should be noted that the following examples do not exhaust all possible situations, and the materials used in the following examples can be obtained from commercial sources unless otherwise specified.

[0103] Example 1

[0104] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -SH, and R2 and R4 substituents are -OH. The preparation method is as follows: 150 g of propylene glycol and 195 g of (5-hydroxy-3-mercaptophenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0105] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of [ethyl(hexahydropyridin-4-yl)amino]methanol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0106] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 2.5 g / L, the content of the substituted polyoxypropylene ether compound is 28 g / L, and the balance is DI water.

[0107] The solution was implemented with a tank volume of 5 mL / L, a kiloampere-hour addition of 60 mL / L, and a copper plating current density of 4.5 ASD.

[0108] Example 2

[0109] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -CHO, and R2 and R4 substituents are -OH. The preparation method is as follows: 150 g of propylene glycol and 195 g of (5-formyl-3-hydroxyphenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0110] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 2-[ethyl(hexahydropyridin-4-yl)amino]ethan-1-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0111] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 2.5 g / L, the content of the substituted polyoxypropylene ether compound is 28 g / L, and the balance is DI water.

[0112] The solution was implemented with a tank volume of 5 mL / L, a kiloampere-hour addition of 60 mL / L, and a copper plating current density of 4.5 ASD.

[0113] Example 3

[0114] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -OH, and R2 and R4 substituents are -OH. The preparation method is as follows: 150 g of propylene glycol and 195 g of (3,5-dihydroxyphenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0115] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 4-[ethyl(pyridin-4-ylmethyl)amino]butane-1,3-diol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0116] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 5.8 g / L, the content of the substituted polyoxypropylene ether compound is 35 g / L, and the balance is DI water.

[0117] The solution was implemented with a tank volume of 2 mL / L, a kiloampere-hour addition of 40 mL / L, and a copper plating current density of 6.0 ASD.

[0118] Example 4

[0119] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -SH, and R2 and R4 substituents are -NH2. The preparation method is as follows: 150 g of propylene glycol and 195 g of (3-amino-5-mercaptophenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0120] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH3, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 1-[ethyl(hexahydropyridin-4-yl)amino]propan-2-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0121] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 2.5 g / L, the content of the substituted polyoxypropylene ether compound is 28 g / L, and the balance is DI water.

[0122] The solution was implemented with a tank volume of 5 mL / L, a kiloampere-hour addition of 60 mL / L, and a copper plating current density of 4.5 ASD.

[0123] Example 5

[0124] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -CHO, and R2 and R4 substituents are -NH2. The preparation method is as follows: 150 g of propylene glycol and 195 g of (3-formyl-5-hydroxyphenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0125] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH3, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 1-[ethyl(pyridin-4-yl)amino]propan-2-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0126] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0127] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0128] Example 6

[0129] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 and R3 substituents are -OH, and R2 and R4 substituents are -NH2. The preparation method is as follows: 150 g of propylene glycol and 195 g of (3-amino-5-hydroxyphenyl) methanesulfonyl chloride are mixed and heated to 80° C., stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65 g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100 g of sodium thioacetate and 230 g of 30% hydrogen peroxide are added, heated to 40° C., stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0130] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 4-[ethyl(hexahydropyridin-4-ylmethyl)amino]butane-1,3-diol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0131] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 5.8 g / L, the content of the substituted polyoxypropylene ether compound is 35 g / L, and the balance is DI water.

[0132] The solution was implemented with a tank volume of 2 mL / L, a kiloampere-hour addition of 40 mL / L, and a copper plating current density of 6.0 ASD.

[0133] Example 7

[0134] The disulfide disubstituted aromatic sulfonate compound has a structure in which R1 and R3 substituents are -OH, and R2 and R4 substituents are -COONa. The preparation method is as follows: 150 g of propylene glycol and 195 g of [({3-[(chlorodioxy-λ 6 [-thio)methyl]-5-hydroxyphenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0135] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH3, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 1-[ethyl(pyridin-4-ylmethyl)amino]propan-2-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0136] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 5.8 g / L, the content of the substituted polyoxypropylene ether compound is 35 g / L, and the balance is DI water.

[0137] The solution was implemented with a tank volume of 2 mL / L, a kiloampere-hour addition of 40 mL / L, and a copper plating current density of 6.0 ASD.

[0138] Example 8

[0139] The disulfide disubstituted aromatic sulfonate compound has a structure in which R1 and R3 substituents are -SH, and R2 and R4 substituents are -COONa. The preparation method is as follows: 150 g of propylene glycol and 195 g of [({3-[(chlorodioxy-λ 6 -thio)methyl]phenyl}carbonyl)oxy]sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic sulfonate compound of the present invention;

[0140] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 2-[ethyl(pyridin-4-ylmethyl)amino]ethan-1-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0141] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 2.5 g / L, the content of the substituted polyoxypropylene ether compound is 28 g / L, and the balance is DI water.

[0142] The solution was implemented with a tank volume of 5 mL / L, a kiloampere-hour addition of 60 mL / L, and a copper plating current density of 4.5 ASD.

[0143] Example 9

[0144] The disulfide disubstituted aromatic sulfonate compound has a structure in which R1 and R3 substituents are -CHO, and R2 and R4 substituents are -COONa. The preparation method is as follows: 150 g of propylene glycol and 195 g of [({3-[(chlorodioxy-λ 6[-thio)methyl]-5-formylphenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0145] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of [ethyl(pyridin-4-ylmethyl)amino]methanol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0146] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0147] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0148] Example 10

[0149] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 substituent is -OH, R3 substituent is -CHO, R2 substituent is -OH, and R4 substituent is -NH2. The preparation method is as follows: 150g of propylene glycol, 195g of (3-amino-5-formylphenyl) methanesulfonyl chloride and (3,5-dihydroxyphenyl) methanesulfonyl chloride are mixed and heated to 80°C, stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide are added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0150] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of [ethyl(pyridin-4-yl)amino]methanol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0151] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0152] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0153] Embodiment 11

[0154] The disulfide disubstituted aromatic sulfonate compound structure has R1 substituent as -OH, R3 substituent as -SH, R2 substituent as -OH, and R4 substituent as -COONa. The preparation method is as follows: 150 g of propylene glycol, 195 g of (3,5-dihydroxyphenyl) methanesulfonyl chloride and [({3-[(chlorodioxy-λ 6 [-thio)methyl]-5-mercaptophenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0155] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 2-[ethyl(pyridin-4-yl)amino]ethan-1-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0156] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0157] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0158] Example 12

[0159] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 substituent is -CHO, R3 substituent is -OH, R2 substituent is -NH2, and R4 substituent is -OH. The preparation method is as follows: 150g of propylene glycol, 195g of (3,5-dihydroxyphenyl) methanesulfonyl chloride and (3-amino-5-formylphenyl) methanesulfonyl chloride are mixed and heated to 80°C, stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium is added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide are added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water is added, chromatographic separation is performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0160] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 4-[ethyl(pyridin-4-yl)amino]butane-1,3-diol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0161] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0162] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0163] Embodiment 13

[0164] The disulfide disubstituted aromatic sulfonate compound has a structure in which R1 is a substituent of -CHO, R3 is a substituent of -SH, R2 is a substituent of -NH2, and R4 is a substituent of -COONa. The preparation method is as follows: 150 g of propylene glycol, 195 g of (3-amino-5-formylphenyl) methanesulfonyl chloride and [({3-[(chlorodioxy-λ 6[-thio)methyl]-5-mercaptophenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0165] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of [ethyl(hexahydropyridin-4-ylmethyl)amino]methanol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0166] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0167] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0168] Embodiment 14

[0169] The disulfide disubstituted aromatic sulfonate compound structure has R1 substituent as -SH, R3 substituent as -OH, R2 substituent as -COONa, and R4 substituent as -OH. The preparation method is as follows: 150 g of propylene glycol, 195 g of (3,5-dihydroxyphenyl) methanesulfonyl chloride and [({3-[(chlorodioxy-λ 6 [-thio)methyl]-5-mercaptophenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0170] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 2-[ethyl(hexahydropyridin-4-ylmethyl)amino]ethan-1-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0171] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0172] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0173] Embodiment 15

[0174] The disulfide disubstituted aromatic sulfonate compound has a structure in which R1 is a -SH substituent, R3 is a -CHO substituent, R2 is a -COONa substituent, and R4 is a -NH2 substituent. The preparation method is as follows: 150 g of propylene glycol, 195 g of (3-amino-5-formylphenyl) methanesulfonyl chloride and [({3-[(chlorodioxy-λ 6 [-thio)methyl]-5-mercaptophenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0175] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH3, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 1-[ethyl(hexahydropyridin-4-ylmethyl)amino]propan-2-ol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower water sample is taken, and the substituted polyoxypropylene ether compound of the present invention is obtained by concentration and separation;

[0176] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0177] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0178] Example 16

[0179] The disulfide disubstituted aromatic hydrocarbon sulfonate compound has a structure in which R1 is a substituent of -CHO, R3 is a substituent of -CHO, R2 is a substituent of -NH2, and R4 is a substituent of -COONa. The preparation method is as follows: 150 g of propylene glycol, 195 g of (3-amino-5-formylphenyl) methanesulfonyl chloride and [({3-[(chlorodioxy-λ 6 [-thio)methyl]-5-formylphenyl}carbonyl)oxy] sodium was mixed and heated to 80°C, stirred and refluxed for reaction for 4 hours to obtain a yellow liquid; after cooling to room temperature, 65g of n-butyl lithium was added, stirred and reacted for 2 hours to obtain a dark yellow liquid; 100g of sodium thioacetate and 230g of 30% hydrogen peroxide were added, heated to 40°C, stirred and reacted for 2 hours to obtain a yellow-brown liquid; DI water was added, chromatographic separation was performed, and concentrated and crystallized to obtain the disulfide disubstituted aromatic hydrocarbon sulfonate compound of the present invention;

[0180] The structure of the substituted polyoxypropylene ether compound R1 substituent is -CH2CH(OH)CH2CH2OH, and the R2 substituent is The preparation method is as follows: 105 g of 2-chloro-butylene oxide and 150 g of 4-[ethyl(hexahydropyridin-4-ylmethyl)amino]butane-1,3-diol are dissolved in ethyl acetate, 1 g of boron trifluoride catalyst is added, the mixture is heated to 85° C., and stirred and refluxed for 10 hours to obtain a yellow liquid; DI water is added, the mixture is allowed to stand for stratification, a lower layer of water is sampled, and concentrated and separated to obtain the substituted polyoxypropylene ether compound of the present invention;

[0181] The above-mentioned disulfide disubstituted aromatic hydrocarbon sulfonate compound and substituted polyoxypropylene ether compound are placed in water and mixed, the content of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is 3.2 g / L, the content of the substituted polyoxypropylene ether compound is 20 g / L, and the balance is DI water.

[0182] The solution was implemented with a tank volume of 3mL / L, a kiloampere-hour addition of 45mL / L, and a copper plating current density of 5.5ASD.

[0183] Comparative Example

[0184] Sodium polydisulfide propane sulfonate (SPS) 3.5 g / L, polyethylene glycol 10000 (PEG-10000) 50 g / L, and the balance is DI water.

[0185] The solution has a tank volume of 6mL / L, a kiloampere-hour addition of 120mL / L, and a copper plating current density of 2.5ASD.

[0186] Table 1: Summary of the effects of additive-insoluble anode copper plating

[0187]

[0188]

[0189] The specific structures of the substances used in Examples 1 to 16 are shown in Figures 3 to 18 (The materials used in Examples 1 to 16 in the figure correspond to Figures 3 to 18 , Examples 1 to 16 are referred to as Examples 1 to 16 for short).

[0190] Table 2: Summary of TOC content data of additive insoluble anode copper plating

[0191]

[0192] The above embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A copper plating additive, characterized in that: Including disulfide disubstituted aromatic hydrocarbon sulfonate compounds and substituted polyoxypropylene ether compounds; The general structural formula of the disulfide disubstituted aromatic hydrocarbon sulfonate compound is shown in I: wherein R1 and R3 are independently selected from -OH, -CHO or -SH, and R2 and R4 are independently selected from -OH, -NH2 or -COONa; The general structural formula of the substituted polyoxypropylene ether compound is shown in II: Wherein, R1 is -CH2OH, -CH2CH2OH, -CH2CH(OH)CH3 or -CH2CH(OH)CH2CH2OH, and R2 is 2. The copper plating additive according to claim 1, characterized in that: The copper plating additive also includes a solvent.

3. The copper plating additive according to claim 2, characterized in that: The solvent is water.

4. The copper plating additive according to claim 1, characterized in that: The concentration of the disulfide disubstituted aromatic hydrocarbon sulfonate compound in the copper plating additive is 0.1 g / L to 10 g / L; and / or, The concentration of the substituted polyoxypropylene ether compound in the copper plating additive is 1 g / L to 50 g / L.

5. A method for preparing a copper plating additive, characterized in that: Used to prepare the copper plating additive according to any one of claims 1 to 4, the preparation method of the copper plating additive comprises the following steps: Obtaining disulfide disubstituted aromatic hydrocarbon sulfonate compounds and substituted polyoxypropylene ether compounds; The disulfide disubstituted aromatic hydrocarbon sulfonate compound and the substituted polyoxypropylene ether compound are subjected to solution preparation treatment to obtain a copper plating additive.

6. The method for preparing the copper plating additive according to claim 5, characterized in that: Obtaining a disulfide disubstituted aromatic hydrocarbon sulfonate compound comprises the following steps: Propylene glycol and methanesulfonyl chloride derivative are mixed and heated to 80°C to 90°C, and stirred and refluxed for 3.5h to 4.5h to obtain a yellow liquid; The yellow liquid is cooled to room temperature, and then n-butyl lithium is added to the yellow liquid and stirred for reaction for 2 h to 3 h to obtain a dark yellow liquid; Add sodium thioacetate and hydrogen peroxide to the dark yellow liquid, heat to 38° C. to 45° C., and stir to react for 1.8 h to 2.5 h to obtain a yellow-brown liquid; Adding water to the yellow-brown liquid, followed by chromatography, concentration and crystallization to obtain a disulfide disubstituted aromatic hydrocarbon sulfonate compound; 7. The method for preparing the copper plating additive according to claim 5, characterized in that: Obtaining a substituted polyoxypropylene ether compound comprises the following steps: Take 2-chloro-butylene oxide and an alcohol amine compound having a pyridine or piperidine group and dissolve them in ethyl acetate, then add boron trifluoride catalyst, heat to 80°C to 90°C, stir and reflux for 9h to 11h to obtain a yellow liquid; Add water to the yellow liquid, let it stand to separate into layers, take a water sample of the lower layer, concentrate and separate, and obtain a substituted polyoxypropylene ether compound; 8. The method for preparing the copper plating additive according to claim 6 or 7, characterized in that: The water is deionized water.

9. An application of a copper plating additive, characterized in that: The copper plating additive according to any one of claims 1 to 5 is applied to a copper plating solution.

10. The use of the copper plating additive according to claim 9, characterized in that: The copper plating solution further comprises 50 g / L to 100 g / L of copper sulfate pentahydrate, 200 g / L to 300 g / L of sulfuric acid and 40 mg / L to 100 mg / L of chloride ions; and / or, The amount of the copper plating additive added to the copper plating solution is 1 mL / L to 10 mL / L; and / or, During use of the copper plating solution, the amount of the copper plating additive added is 30 mL / kiloampere hour to 80 mL / kiloampere hour; and / or, The copper plating solution is used at a current density of 3.0 ASD to 8.0 ASD.

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