4, 5-thiazoline-3-onium sulfonate series electroplating additive as well as preparation method and application thereof

Abstract

The invention provides a 4, 5-thiazoline-3-onium sulfonate series electroplating additive as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The electroplating additive of 4, 5-thiazolidine-3-onium sulfonate series is designed and synthesized by grafting a short carbon chain with a sulfonic acid group on a carbon heterocyclic ring containing sulfur atoms and nitrogen atoms at the same time, and the additive can have the functions of a brightener and a leveling agent at the same time without being compatible with other compounds in an electroplating copper plating process; the formula difficulty is reduced, and the process control flow is simplified; the synergistic effect of heteroatoms in molecules of the additive reduces the sensitivity of the plating solution to the temperature, cooling equipment does not need to be additionally arranged, and the preparation cost is remarkably reduced. According to the electroplating additive provided by the invention, the brightness of a plating layer can be improved by 35% in acidic copper plating, and the service life of a plating solution is doubled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a 4,5-dihydrothiazolium-3-yl sulfonate series of electroplating additives and a preparation method and application thereof. BACKGROUND

[0002] Traditional copper plating additives are usually composed of multiple components such as main brightener (which can refine grains), leveler (which can inhibit deposition in the convex region), wetting agent, dispersant, etc. The main brightener is usually sodium polydithiopropyl sulfonate (SPS), which can control grain refinement by adsorption, but SPS is easy to oxidize and decompose (it will fail when the current capacity is more than 15 Ah / L), so it needs to be frequently supplemented and combined with activated carbon treatment during electroplating. The leveler is usually sodium thiazoline dithiopropyl sulfonate (SH110) or N-ethyl thiourea, which can achieve filling by enhancing cathode polarization, but the aforementioned two levelers are easy to produce turbidity with imine levelers, which has limitations in compatibility.

[0003] There are three core problems in the existing copper plating additive system: (1) different additives (such as SPS and SH110, AESS and HP) need to be used in coordination, but after mixing, they are easy to cause side reactions (such as precipitation and plating solution turbidity), which limits the flexibility of formula design; (2) activated carbon adsorption is needed when SPS decomposes, and continuous filtration (≥5 times the tank volume / hour) is needed for dye-type additives, which requires frequent operation and adjustment during electroplating to ensure process stability, resulting in high maintenance costs; (3) most additives will fail in a high temperature (>35℃) environment, which requires additional cooling equipment, resulting in increased energy consumption.

[0004] Therefore, it is necessary to design a 4,5-dihydrothiazolium-3-yl sulfonate series of electroplating additives and a preparation method and application thereof to solve the above problems. SUMMARY

[0005] In view of the technical problems in the background art, the present application provides a 4,5-dihydrothiazolium-3-yl sulfonate series of electroplating additives and a preparation method and application thereof. By grafting a short carbon chain with a sulfonic acid group on a carbon heterocycle containing both sulfur and nitrogen atoms, a 4,5-dihydrothiazolium-3-yl sulfonate series of electroplating additives is designed and synthesized. On the one hand, the obtained additive molecules can simultaneously have the functions of brightener and leveler without the need for compatibility with other compounds, reducing the difficulty of formula design and simplifying the process control process. On the other hand, the synergistic effect of heteroatoms in the additive molecules reduces the sensitivity of the plating solution to temperature, eliminating the need for additional cooling equipment and significantly reducing the preparation cost. The 4,5-dihydrothiazolium-3-yl sulfonate series of electroplating additives provided by the present application can improve the brightness of the plating layer by 35% and prolong the life of the plating solution by 100% in acid copper plating.

[0006] In a first aspect, the embodiments of the present application provide a series of 4,5-dihydrothiazolium-3-yl sulfonate as electroplating additives, the electroplating additives have a structural formula of one of A, B, C, D, wherein,

[0007] A is B is

[0008] C is D is

[0009] X1, X2, X3, X4, X5, X6, X7, X8 in the structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X10 in the structural formula B, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 haloalkoxy, C3-C12 cycloalkyl, C2-C12 alkenyl, C2-C12 alkynyl, 4-12 membered heterocyclyl, or 5-10 membered heteroaryl. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen.

[0010] Further, X1, X2, X3, X4, X5, X6, X7, X8 in the structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X10 in the structural formula B, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen.

[0011] Further, X1, X2, X3, X4, X5, X6, X7, X8 in the structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X10 in the structural formula B, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen. 10 , and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in the structural formula D are each independently selected from -H, -OH, or halogen.

[0012] In a second aspect, the embodiments of the present application provide a preparation method of a series of 4,5-dihydrothiazolium sulfonate plating additives, comprising the following steps:

[0013] S1, mixing compound a and compound b with water, and performing a first reaction after heating to obtain a zwitterionic intermediate solution;

[0014] S2, adding NaOH aqueous solution to the zwitterionic intermediate solution obtained in step S1, then heating to 40℃, and then slowly adding compound c, controlling the temperature of the reaction system between 40-80℃, and then performing a second reaction, and finally concentrating, removing water, salting out, and drying to obtain a series of 4,5-dihydrothiazolium sulfonate plating additives;

[0015] wherein the structural formula of the compound a is or Y1, Y2 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, C1-C 10 alkyl, C1-C 10 alkoxy, C1-C 10 alkoxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl, C2-C 10 alkenyl, 4-12 membered heterocyclyl, or 5-10 membered heteroaryl; the structural formula of the compound b and / or the compound c is or Y3, Y4, Y5, Y6 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, C1-C 10 alkyl, C1-C 10 alkoxy, C1-C 10 alkoxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl, C2-C 10 alkenyl, 4-12 membered heterocyclyl, or 5-10 membered heteroaryl.

[0016] Further, Y1, Y2, Y3, Y4, Y5, Y6 are each independently selected from -H, -OH, or halogen.

[0017] Further, compound a is thiazolidin-2-thione or 5-chloro-2-mercapto-4,5-dihydrothiazolidin-4-ol; compound b and / or compound c are each independently selected from 1,3-propanesulfonyl lactone, 1,4-butyrate lactone, 4-hydroxy-1,2-oxathiazide-2,2-dioxide or 4-hydroxy-1,2-oxothiophene-2,2-dioxide.

[0018] Furthermore, the equivalent ratio of compound a to compound b and compound c is 1:(1-1.1):(1-1.1).

[0019] Furthermore, in step S1, the mass-to-volume ratio of compound a to water is 0.5-1 g / mL; in step S1, the temperature of the first reaction is 60-65℃, and the reaction time is 8-8.5 h.

[0020] Furthermore, in step S2, the mass concentration of the NaOH aqueous solution is 25-35%, and the equivalent ratio of NaOH to compound c is 1:(1-1.2); in step S2, the temperature of the second reaction is 80-85℃, and the reaction time is 2-2.5h; in step S2, the concentration and dehydration refers to concentrating the reaction material to a theoretical water content of 110%; in step S2, the salting-out process involves cooling the concentrated reaction material to 0-5℃, adding methanol, stirring, allowing it to stand, filtering, and finally washing the filter cake with methanol.

[0021] Thirdly, embodiments of this application provide an application of a 4,5-dihydrothiazole-3-onium sulfonate series of electroplating additives, wherein the 4,5-dihydrothiazole-3-onium sulfonate series of electroplating additives is used for copper electroplating.

[0022] The beneficial effects of this application are as follows:

[0023] This application provides a series of electroplating additives of 4,5-dihydrothiazole-3-onium sulfonate, their preparation method and application. A short carbon chain with sulfonic acid group is grafted onto a carbon heterocycle containing both sulfur and nitrogen atoms to design and synthesize a series of electroplating additives of 4,5-dihydrothiazole-3-onium sulfonate.

[0024] (1) The additive prepared in this application can simultaneously function as a brightener and a leveling agent without needing to be combined with other compounds, which reduces the difficulty of formulation and simplifies the process control process.

[0025] (2) The synergistic effect of heteroatoms within the additive molecule reduces the temperature sensitivity of the plating solution, eliminating the need for additional cooling equipment and significantly reducing preparation costs.

[0026] (3) The additive prepared in this application is added in less amount than traditional electroplating additives when used for electroplating, and can increase the brightness of the coating by 35% and double the life of the plating solution in acidic copper plating.

[0027] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0029] Figure 1 The molecular structural formula of the 4,5-dihydrothiazol-3-onium sulfonate series of electroplating additives provided in this application;

[0030] Figure 2 This is a reaction route diagram of sodium 4-((3-(4-sulfonyl)-4,5-dihydrothiazolyl-3-onthion-2-yl)thio)but-1-sulfonate in Example 1 of this application;

[0031] Figure 3 This is a reaction route diagram of sodium 4-((3-(3-sulfonylpropyl)-4,5-dihydrothiazolyl-3-onthion-2-yl)thio)but-1-sulfonate in Example 2 of this application;

[0032] Figure 4 This is a reaction route diagram of sodium 4-(2-((3-sulfonylpropyl)thio)-4,5-dihydrothiazolyl-3-onthiol-3-yl)but-1-sulfonate in Example 2 of this application;

[0033] Figure 5 This is a reaction route diagram of sodium 3-((3-(3-sulfonylpropyl)-4,5-dihydrothiazolyl-3-onthion-2-yl)thio)propane-1-sulfonate in Example 2 of this application;

[0034] Figure 6 This is a reaction route diagram of sodium 4-(5-chloro-4-hydroxy-2-((4-sulfonyl)thio)-4,5-dihydrothiazolyl-3-onthiol-3-yl)-2-hydroxybutane-1-sulfonate in Example 2 of this application;

[0035] Figure 7This is a reaction route diagram of sodium 2-hydroxy-3-((3-(2-hydroxy-3-sulfonylpropyl)-4,5-dihydrothiazo-3-onthion-2-yl)thio)propane-1-sulfonate in Example 2 of this application; Detailed Implementation

[0036] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0038] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0039] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0040] In the description of the embodiments of this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship. Those skilled in the art can understand the specific meaning of the above terms in the embodiments of this application according to the specific circumstances.

[0041] The existing copper plating additive system has the following three core problems: (1) Different additives (such as SPS and SH110, AESS and HP) need to be used in combination, but after mixing, side reactions (such as precipitation and turbidity of the plating solution) are easily triggered, which limits the flexibility of the formulation design; (2) SPS needs to be adsorbed by activated carbon when it decomposes, while dye-type additives need to be continuously filtered (≥5 times the tank volume / hour). Frequent operation and adjustment are required during the electroplating process to ensure process stability, resulting in high maintenance costs; (3) Most additives will fail in high temperature (>35℃) environments, requiring additional cooling equipment, which increases energy consumption.

[0042] To address the aforementioned technical problems, this application provides a series of 4,5-dihydrothiazole-3-onium sulfonate electroplating additives, their preparation methods, and applications. By grafting short carbon chains with sulfonic acid groups onto carbon heterocycles containing both sulfur and nitrogen atoms, the resulting additive molecule can simultaneously function as a brightener and leveling agent without the need for compatibility with other compounds, reducing formulation complexity and simplifying process control. Furthermore, the synergistic effect of heteroatoms within the additive molecule reduces the temperature sensitivity of the plating bath, eliminating the need for additional cooling equipment and significantly reducing preparation costs. The 4,5-dihydrothiazole-3-onium sulfonate electroplating additives provided in this application can increase the brightness of the plating layer by 35% and double the lifespan of the plating bath in acidic copper plating.

[0043] Please see Figure 1 As shown, in a first aspect, embodiments of this application provide an electroplating additive in the series of 4,5-dihydrothiazole-3-onium sulfonate, with a structural formula of one of A, B, C, and D, wherein...

[0044] A is B is

[0045] C is D is

[0046] In the embodiments of this application, X1, X2, X3, X4, X5, X6, X7, X8 in structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X... 10 And / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in structural formula D, are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C10 cycloalkyl, C2-C 10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic or 5-10 membered heteroaryl.

[0047] Preferably, X1, X2, X3, X4, X5, X6, X7, X8 in structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X8 in structural formula B. 10 The X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula C and the X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula D are each independently selected from -H, -OH, or halogens.

[0048] More preferably, in structural formula A, X1, X3, X4, X5, X6, and X8 are -H, and X2 and X3 are each independently selected from -H or -OH; in structural formula B, X1, X2, X3, X4, X7, X8, and X... 10 X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula C are -H; X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula D are -H.

[0049] Secondly, embodiments of this application provide a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0050] S1, Compound a and Compound b are mixed with water, heated to carry out the first reaction, and an amphoteric intermediate solution is obtained;

[0051] S2, add NaOH aqueous solution to the zwitterionic intermediate solution obtained in step S1, then heat to 40°C and slowly add compound c dropwise, controlling the temperature of the reaction system between 40-80°C, and then carry out a second reaction. Finally, concentrate to remove water, salt out, and dry to obtain 4,5-dihydrothiazol-3-onium sulfonate series electroplating additives.

[0052] In the embodiments of this application, the structural formula of compound a is as follows: or Among them, Y1 and Y2 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C 10 cycloalkyl, C2-C10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic, or 5-10 membered heteroaryl. Preferably, Y1 and Y2 are each independently selected from -H, -OH, or halogen. More preferably, compound a is thiazolyl-2-thione or 5-chloro-2-mercapto-4,5-dihydrothiazolyl-4-ol.

[0053] In the embodiments of this application, the structural formulas of compound b and / or compound c are as follows: or Among them, Y3, Y4, Y5, and Y6 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic, or 5-10 membered heteroaryl. Preferably, Y3, Y4, Y5, and Y6 are each independently selected from -H, -OH, or halogens. More preferably, compound b and / or compound c are each independently selected from 1,3-propanesulfonyl lactone, 1,4-butyrate lactone, 4-hydroxy-1,2-oxathiazide-2,2-dioxide, or 4-hydroxy-1,2-oxothiophene-2,2-dioxide.

[0054] In the embodiments of this application, the equivalent ratio of compound a to compound b and compound c is 1:(1-1.1):(1-1.1).

[0055] In the embodiments of this application, in step S1, the mass-to-volume ratio of compound a to water is 0.5-1 g / mL.

[0056] In the embodiments of this application, in step S1, the temperature of the first reaction is 60-65°C, and the reaction time is 8-8.5h.

[0057] In the embodiments of this application, in step S2, the mass concentration of the NaOH aqueous solution is 25-35%, and the equivalent ratio of NaOH to compound c is 1:(1-1.2).

[0058] In the embodiments of this application, in step S2, the temperature of the second reaction is 80-85°C, and the reaction time is 2-2.5h.

[0059] In this embodiment of the application, in step S2, concentration and dehydration refers to concentrating the reactants to a theoretical water content of 110%.

[0060] In this embodiment, step S2, the salting-out process involves cooling the concentrated reaction material to 0-5°C, adding methanol, stirring, allowing it to stand, filtering, and washing the filter cake with methanol. The dried filter cake yields the 4,5-dihydrothiazol-3-onium sulfonate series of electroplating additives.

[0061] Thirdly, embodiments of this application provide an application of a 4,5-dihydrothiazol-3-onium sulfonate series of electroplating additives for copper electroplating.

[0062] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0063] Example 1

[0064] Example 1 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazole-3-onium sulfonate series, comprising the following steps:

[0065] S1, 11.9g thiazolidin-2-thione, 14.98g 1,4-butyryl lactone, and 20ml water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0066] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. Then, the mixture was heated to 40°C, and 14.98g of 1,4-butyric acid lactone was slowly added dropwise. The temperature of the reaction system was controlled between 40-80°C, and then maintained at 80°C for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0°C, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20mL of methanol, and dried to obtain 38.01g of a white solid product. The product name was sodium 4-((3-(4-sulfonyl)-4,5-dihydrothiazol-3-onthionyl-2-yl)thio)but-1-sulfonate, i.e., an electroplating additive in the 4,5-dihydrothiazol-3-onthionyl sulfonate series. The yield in Example 1 was 91.93%.

[0067] See the reaction route diagram of Example 1. Figure 2 As shown.

[0068] Example 2

[0069] Example 2 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0070] S1, 11.9g thiazolidin-2-thione, 14.98g 1,4-butyryl lactone, and 20ml water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0071] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. The mixture was then heated to 40°C, and 13.4g of 1,3-propanesulfonyl lactone was slowly added dropwise. The temperature of the reaction system was controlled between 40-80°C, and then maintained at 80°C for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0°C, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20mL of methanol, and dried to obtain 36.14g of solid product. The product name was sodium 4-((3-(3-sulfonylpropyl)-4,5-dihydrothiazol-3-onium-2-yl)thio)but-1-sulfonate, i.e., an electroplating additive in the 4,5-dihydrothiazol-3-onium sulfonate series. The yield in Example 2 was 90.47%.

[0072] See the reaction route diagram for Example 2. Figure 3 As shown.

[0073] Example 3

[0074] Example 3 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0075] S1, 11.9g of thiazolidin-2-thione, 13.4g of 1,3-propanesulfonyl lactone, and 20ml of water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0076] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. Then, the mixture was heated to 40°C, and 14.98g of 1,4-butyric acid lactone was slowly added dropwise. The temperature of the reaction system was controlled between 40-80°C, and then maintained at 80°C for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0°C, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20mL of methanol, and dried to obtain 35.72g of solid product. The product name was sodium 4-(2-((3-sulfonylpropyl)thio)-4,5-dihydrothiazol-3-onthium-3-yl)but-1-sulfonate, i.e., an electroplating additive in the 4,5-dihydrothiazol-3-onthium sulfonate series. The yield in Example 3 was 89.42%.

[0077] See the reaction route diagram for Example 3. Figure 4 As shown.

[0078] Example 4

[0079] Example 4 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0080] S1, 11.9g of thiazolidin-2-thione, 13.4g of 1,3-propanesulfonyl lactone, and 20ml of water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0081] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. The mixture was then heated to 40°C, and 13.4g of 1,3-propanesulfonyl lactone was slowly added dropwise. The temperature of the reaction system was controlled between 40-80°C, and then maintained at 80°C for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0°C, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20mL of methanol, and dried to obtain 34.18g of solid product. The product name was sodium 3-((3-(3-sulfonylpropyl)-4,5-dihydrothiazol-3-onium-2-yl)thio)propane-1-sulfonate, i.e., an electroplating additive in the 4,5-dihydrothiazol-3-onium sulfonate series. The yield in Example 4 was 88.67%.

[0082] See the reaction route diagram for Example 4. Figure 5 As shown.

[0083] Example 5

[0084] Example 5 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0085] S1, 16.96g of 5-chloro-2-mercapto-4,5-dihydrothiazol-4-ol, 16.74g of 4-hydroxy-1,2-oxathiazide 2,2-dioxide, and 20ml of water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0086] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. Then, the mixture was heated to 40°C, and 14.98g of 1,4-butyric acid lactone was slowly added dropwise. The temperature of the reaction system was controlled between 40-80°C, and then maintained at 80°C for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0°C, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20mL of methanol, and dried to obtain 41.67g of a white solid product. The product was named sodium 4-(5-chloro-4-hydroxy-2-((4-sulfonyl)thio)-4,5-dihydrothiazol-3-onthium-3-yl)-2-hydroxybutane-1-sulfonate, i.e., an electroplating additive in the 4,5-dihydrothiazol-3-onthium sulfonate series. The yield in Example 5 was 86.82%.

[0087] See the reaction route diagram for Example 5. Figure 6 As shown.

[0088] Example 6

[0089] Example 6 provides a method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series, comprising the following steps:

[0090] S1, 11.9g of thiazolidin-2-thione, 15.2g of 4-hydroxy-1,2-oxothiophene-2,2-dioxide, and 20ml of water were added to a reactor and mixed. The mixture was heated to 60℃ and reacted at a constant temperature for 8 hours (first reaction) to obtain a zwitterionic intermediate solution.

[0091] S2, 15g of 30% NaOH aqueous solution was added to the zwitterionic intermediate solution obtained in step S1. The mixture was then heated to 40℃, and 15.2g of 4-hydroxy-1,2-oxothiophene-2,2-dioxide was slowly added dropwise. The temperature of the reaction system was controlled between 40-80℃, and then maintained at 80℃ for 2 hours (second reaction). After the reaction was complete, the mixture was concentrated to remove water, reducing the water content to 110%. The mixture was then cooled to 0℃, and 30mL of methanol was added and stirred thoroughly to precipitate crystals. Finally, the mixture was filtered, washed twice with 20 mL of methanol, and dried to obtain 34.11 g of a white solid product. The product was named sodium 2-hydroxy-3-((3-(2-hydroxy-3-sulfonylpropyl)-4,5-dihydrothiazol-3-onthion-2-yl)thio)propane-1-sulfonate, which is an electroplating additive in the 4,5-dihydrothiazol-3-onthionate series. The yield in Example 6 was 81.71%.

[0092] See the reaction route diagram of Example 6. Figure 7 As shown.

[0093] Electroplating tests were conducted using the 4,5-dihydrothiazolium-3-onium sulfonate series of electroplating additives prepared in Examples 1-6, with an additive formulated with sodium dithiopropane sulfonate (SPS) and diallyl dimethyl ammonium chloride-sulfur dioxide alternating block copolymer (PAS-A-5) serving as a control group. The specific steps of the electroplating tests are as follows:

[0094] An electrolyte solution was prepared by mixing copper sulfate pentahydrate, concentrated sulfuric acid, deionized water, and dilute hydrochloric acid. This electrolyte solution was then introduced into an electrolytic cell equipped with heating and temperature control. An additive solution was added and stirred until homogeneous. Electroplating began after the mixed solution was heated to 55°C, with a current density of 50 A / dm³. 2 After electrolysis of the copper foil, the copper foil is passivated with a chromic anhydride passivation solution to obtain a 6μm finished copper foil. The electrolyte contains a copper ion concentration of 90 g / L, an acid content of 110 g / L, a chloride ion concentration of 15 mg / L, and an additive solution including additives and polyethylene glycol 1000.

[0095] The concentrations of each component in the additive are shown in Table 1:

[0096] Table 1. Concentration of each component in the additive

[0097]

[0098]

[0099] Finally, the finished copper foil obtained by electroplating was subjected to a copper plating bath life test under acidic high-temperature conditions, with the following test conditions:

[0100] Accelerated aging conditions: 60℃ constant temperature bath, 3A / dm 2 Continuous electroplating;

[0101] Monitoring cycles: 0, 24, 48, 72, 96 hours (corresponding to actual usage cycles of 1-4 months);

[0102] Test piece specifications: 150mm×100mm copper clad laminate (substrate roughness Ra≤0.1μm);

[0103] Termination condition: gloss ≤ 50Gs.

[0104] The data on gloss, arithmetic mean roughness (Ra), ten-point mean roughness (Rz), and plating solution life obtained from electroplating tests and acidic copper plating solution life tests are shown in Table 2. (Where N4 and N3 represent that the N atom is attached to a C3 carbon chain and a C4 carbon chain, respectively, and N4(-OH) represents that the C4 carbon chain also contains -OH; the same applies to S4, S3, N4(-OH), and S3(-OH).)

[0105] Table 2. Test Data

[0106]

[0107]

[0108] As shown in Table 2, the gloss, Ra, and Rz of the additives prepared in Examples 1-6 are significantly better than those of the mixed additives of SPS and PAS-A-5. Compared with ordinary mixed additives, the additives prepared in Examples 1-6 have better brightening and leveling effects, longer plating bath life, and lower overall addition amount.

[0109] In summary, this application provides a series of 4,5-dihydrothiazole-3-onium sulfonate electroplating additives, their preparation methods, and applications. A series of 4,5-dihydrothiazole-3-onium sulfonate electroplating additives was designed and synthesized, and successfully applied to acidic copper electroplating. Compared with a mixed additive of SPS and PAS-A-5, the electroplating additive provided in this application increases the brightness of the plating layer by about 35% and extends the plating bath life by about 100%.

[0110] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. An electroplating additive in the series of 4,5-dihydrothiazol-3-onium sulfonate, characterized in that, The electroplating additive has a structural formula of one of A, B, C, and D, wherein... A is B is C is D is X1, X2, X3, X4, X5, X6, X7, X8 in structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X in structural formula B 10 And / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in structural formula C, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9 in structural formula D, are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic or 5-10 membered heteroaryl.

2. The electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series according to claim 1, characterized in that, X1, X2, X3, X4, X5, X6, X7, X8 in structural formula A, and / or X1, X2, X3, X4, X5, X6, X7, X8, X9, X in structural formula B 10 The X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula C and the X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula D are each independently selected from -H, -OH, or halogens.

3. The electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series according to claim 2, characterized in that, In structural formula A, X1, X3, X4, X5, X6, and X8 are -H, while X2 and X3 are each independently selected from -H or -OH; in structural formula B, X1, X2, X3, X4, X7, X8, X... 10 X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula C are -H; X1, X2, X3, X4, X5, X6, X7, X8, and X9 in structural formula D are -H.

4. A method for preparing an electroplating additive of the 4,5-dihydrothiazol-3-onium sulfonate series according to any one of claims 1-3, characterized in that, Includes the following steps: S1, Compound a and Compound b are mixed with water, heated to carry out the first reaction, and an amphoteric intermediate solution is obtained; S2, add NaOH aqueous solution to the zwitterionic intermediate solution obtained in step S1, then heat to 40°C and slowly add compound c dropwise, control the temperature of the reaction system between 40-80°C, then carry out the second reaction, finally concentrate to remove water, salt out, dry, and obtain 4,5-dihydrothiazol-3-onium sulfonate series electroplating additives. Wherein, the structural formula of compound a is or Y1 and Y2 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic, or 5-10 membered heteroaryl; the structural formulas of compound b and / or compound c are as follows: or Y3, Y4, Y5, and Y6 are each independently selected from -H, halogen, -OH, -NRR, cyano, -COOH, =O, -C(=O)NRR, Cl-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkyl oxyacyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl group, C2-C 10 Alkenyl, 4-12 membered heterocyclic or 5-10 membered heteroaryl.

5. The method for preparing the 4,5-dihydrothiazol-3-onium sulfonate series electroplating additives according to claim 4, characterized in that, Y1, Y2, Y3, Y4, Y5, and Y6 are each independently selected from -H, -OH, or halogens.

6. The method for preparing the 4,5-dihydrothiazol-3-onium sulfonate series electroplating additives according to claim 5, characterized in that, Compound a is thiazolidin-2-thione or 5-chloro-2-mercapto-4,5-dihydrothiazolidin-4-ol; compound b and / or compound c are each independently selected from 1,3-propanesulfonyl lactone, 1,4-butyrate lactone, 4-hydroxy-1,2-oxathiazide-2,2-dioxide or 4-hydroxy-1,2-oxothiophene-2,2-dioxide.

7. The method for preparing the 4,5-dihydrothiazol-3-onium sulfonate series electroplating additive according to claim 4, characterized in that, The equivalent ratio of compound a to compound b and compound c is 1:(1-1.1):(1-1.1).

8. The method for preparing the 4,5-dihydrothiazol-3-onium sulfonate series electroplating additives according to claim 4, characterized in that, In step S1, the mass-to-volume ratio of compound a to water is 0.5-1 g / mL; in step S1, the temperature of the first reaction is 60-65℃, and the reaction time is 8-8.5 h.

9. The method for preparing the 4,5-dihydrothiazol-3-onium sulfonate series electroplating additive according to claim 4, characterized in that, In step S2, the mass concentration of the NaOH aqueous solution is 25-35%, and the equivalent ratio of NaOH to compound c is 1:(1-1.2); in step S2, the temperature of the second reaction is 80-85℃, and the reaction time is 2-2.5h; in step S2, the concentration and dehydration refers to concentrating the reaction material to a theoretical water content of 110%; in step S2, the salting-out treatment step is to cool the concentrated reaction material to 0-5℃, add methanol, stir and let it stand, and finally filter and wash the filter cake with methanol.

10. The application of an electroplating additive of the 4,5-dihydrothiazole-3-onium sulfonate series according to any one of claims 1-3, or an electroplating additive of the 4,5-dihydrothiazole-3-onium sulfonate series prepared by any one of claims 4-9, characterized in that, The 4,5-dihydrothiazole-3-onium sulfonate series of electroplating additives are used for copper electroplating.

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