Chromium-nickel alloy electroplating additive, preparation method and application thereof

Abstract

The invention relates to the technical field of metal surface treatment, in particular to a chromium-nickel alloy electroplating additive and a preparation method and application thereof. The electroplating additive is selected from organic compounds with molecular structures meeting the following conditions: at least one aryl group, cycloalkyl group, heterocyclic group or heteroaryl group; the amino group contains at least one amino group, and the amino group is connected with the aryl group, the cycloalkyl group, the heterocyclic group or the heteroaryl group; the carboxyl group contains at least two carboxyl groups, and the carboxyl groups are connected with the aryl group, the cycloalkyl group, the heterocyclic group or the heteroaryl group. The present disclosure prepares a plating additive compound that facilitates deposition of chromium ions and nickel ions during plating.

Description

Technical Field

[0001] The present disclosure relates to the technical field of metal surface treatment, and in particular to an electroplating additive for chromium-nickel alloy, a preparation method and application thereof. Background Art

[0002] In recent years, with the rapid development of my country's economy, marine transportation, aquaculture, oil development and other marine-related activities have increased. The emergence of various transportation equipment, aquaculture equipment and oil development equipment has facilitated industrial activities. Due to the particularity of the offshore industrial environment, the surface of the equipment is easily corroded, so it requires a large maintenance cost and will also delay the production cycle.

[0003] Electroplating nickel-chromium alloy has attracted much attention for its excellent coating properties, such as corrosion resistance, wear resistance and good decorative effect. It has a wide range of applications, and some coatings can replace chrome-plated products, especially depositing a layer of nickel-chromium alloy on the surface of metal materials, which can improve the corrosion resistance of the substrate, thereby reducing the amount of stainless steel used and saving chromium resources. Summary of the invention

[0004] The present invention provides a chromium-nickel alloy electroplating additive, a preparation method and application thereof to solve the deficiencies in the related art.

[0005] According to a first aspect of an embodiment of the present disclosure, there is provided an electroplating additive for a chromium-nickel alloy, wherein the electroplating additive is selected from organic compounds whose molecular structures satisfy the following conditions: 1) contains at least one aryl, cycloalkyl, heterocyclyl or heteroaryl group; 2) comprising at least one amino group, wherein the amino group is connected to the aryl group, cycloalkyl group, heterocyclyl group or heteroaryl group; 3) contains at least two carboxyl groups, wherein the carboxyl groups are connected to the aryl group, cycloalkyl group, heterocyclic group or heteroaryl group.

[0006] In one aspect of the embodiments of the present disclosure, the electroplating additive is selected from organic compounds whose molecular structures satisfy the following conditions: 1) contains at least two aryl groups or heteroaryl groups; or, contains at least one aryl group and at least one heteroaryl group; 2) comprising at least one amide group, wherein the amide group is connected to the aryl or heteroaryl group; 3) comprising at least one amino group, wherein the amino group is connected to the aryl or heteroaryl group; 4) comprising at least two carboxyl groups, wherein the carboxyl groups are connected to the aryl or heteroaryl groups; 5) The amino group and the carboxyl group are not connected to the same aryl group or heteroaryl group.

[0007] In one aspect of the embodiments of the present disclosure, the electroplating additive is selected from an organic compound having the following structure of Formula I: wherein n is selected from an integer of 1-6; Ar1 ​​and Ar2 are each independently selected from C3-C15 cycloalkyl, C6-12 aryl, 5-15 membered heterocyclyl or 5-15 membered heteroaryl; wherein the C3-C15 cycloalkyl, C6-12 aryl, 5-15 membered heterocyclyl or 5-15 membered heteroaryl are optionally substituted with one or more hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy.

[0008] In one aspect of the embodiments of the present disclosure, Ar1 and Ar2 are each independently selected from phenyl and biphenyl, wherein the phenyl and biphenyl are optionally substituted by one or more hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy.

[0009] In one aspect of the embodiments of the present disclosure, the electroplating additive is selected from organic compounds having the following structures of Formula II-1 to Formula II-4: Wherein, n is selected from an integer of 1-6; n2 is selected from an integer of 0 to 3; R1 is selected from hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl or C1-C3 alkoxy.

[0010] In one aspect of the embodiments of the present disclosure, the electroplating additive is selected from any one of the following organic compounds: In one aspect of the embodiments of the present disclosure, preferably, the electroplating additive is selected from the following organic compounds: or .

[0011] According to a second aspect of the embodiment of the present disclosure, there is provided a method for preparing the aforementioned electroplating additive, the method comprising the following steps: In one aspect of the embodiments of the present disclosure, preferably, the raw material A is selected from 5-bromoisophthalic acid.

[0012] In one aspect of the embodiments of the present disclosure, preferably, the raw material B is selected from 2,3-diaminobenzamide, 3-aminobenzamide, 2-aminobenzamide or 4-aminobenzamide.

[0013] According to a third aspect of an embodiment of the present disclosure, a chromium-nickel alloy electroplating solution is provided, the electroplating solution comprising: water, chromium salt, nickel salt, conductive agent, surfactant, buffer, and the aforementioned electroplating additives.

[0014] In one aspect of the disclosed embodiment, in the electroplating solution, relative to 1000 parts by weight of water, the content of the chromium salt is 100-200 parts by weight, the content of the nickel salt is 40-100 parts by weight, the content of the conductive agent is 40-80 parts by weight, the content of the surfactant is 5-20 parts by weight, the content of the conductive agent is 10-50 parts by weight, and the content of the electroplating additive is 5-60 parts by weight.

[0015] In one aspect of the embodiments of the present disclosure, the chromium salt is selected from at least one of chromium nitrate, chromium chloride or chromium sulfate; the nickel salt is selected from at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate; the conductive agent is selected from at least one of ammonium chloride, sodium chloride or potassium chloride; the surfactant is selected from at least one of sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, OP-10 or polyvinylpyrrolidone; the buffer is selected from at least one of boric acid, tartaric acid or phosphoric acid.

[0016] In one aspect of the embodiments of the present disclosure, preferably, the chromium salt is selected from chromium nitrate, and the nickel salt is selected from nickel nitrate.

[0017] In one aspect of the embodiments of the present disclosure, preferably, the molar ratio of the chromium salt to the nickel salt is selected from 1:(1.8-2.2); more specifically, the molar ratio of the chromium salt to the nickel salt is selected from 1:2.

[0018] The technical solution provided by the embodiments of the present disclosure may have the following beneficial effects: As can be seen from the above examples, the present disclosure prepares an electroplating additive compound that helps to deposit chromium ions and nickel ions during the electroplating process.

[0019] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of the present application. The embodiments of the present application should not be interpreted as limiting the present application.

[0021] For simplicity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range. In addition, each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unspecified range.

[0022] In this article, the terms "comprises", "comprising" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device that includes a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of more restrictions, an element defined by the sentence "comprising a ..." does not exclude the presence of other identical elements in the process, method, article or device that includes the element.

[0023] In the description herein, unless otherwise specified, “above” and “below” include the number.

[0024] Unless otherwise specified, the terms used in this disclosure have the commonly known meanings generally understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this disclosure).

[0025] The term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in this article in a range format. It should be understood that such a range format is for convenience and simplicity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0026] A list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0027] In this disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl or propyl, attached to a linear alkyl chain. "Lower alkyl" refers to a group containing about 1 to about 6 carbon atoms in the chain, which can be straight or branched.

[0028] In the present disclosure, the term "amino" refers to a -NR'R" group. The amino group may be optionally substituted. In an unsubstituted amino group, R' and R" are hydrogen. In a substituted amino group, R' and R" may each independently be, but are not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl or heteroaryl, provided that R' and R" are not both hydrogen. In a substituted amino group, R' and R" may be cyclized to form a cyclic amino group, such as a pyrrolidinyl or piperidinyl group. Such cyclic amino groups may incorporate other heteroatoms, for example to form piperazine or morpholine groups. Such cyclic amino groups may be optionally substituted, for example, by amino, hydroxyl or oxo groups.

[0029] In the present disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight chain, branched or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy and pentoxy. Alkoxy can be optionally substituted with one or more alkoxy substituents ("substituted alkoxy").

[0030] In this disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. The aryl group may be optionally substituted with one or more "ring system substituents", which may be the same or different, and are as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0031] In the present disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system in which one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination, with preferred heteroaryls containing about 5 to about 6 ring atoms. The "heteroaryl" may be optionally substituted with one or more "ring system substituents", which may be the same or different, as defined herein. The prefix aza, oxa or thia before the heteroaryl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The nitrogen atom of the heteroaryl may be optionally oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl groups include pyridinyl, pyrazinyl, furanyl, thiophenyl, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-naphthyridinyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothiophenyl, quinolinyl, imidazolyl, thienopyridinyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridinyl, imidazopyridinyl, isoquinolinyl, benzazaindolyl, 1,2,4-triazinyl, benzothiazolyl, and the like.

[0032] In the present disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system containing about 3 to about 10 carbon atoms, preferably about 5 to about 10 carbon atoms, and the preferred cycloalkyl ring contains about 5 to about 7 ring atoms. The cycloalkyl group may be optionally substituted with one or more "ring system substituents", which may be the same or different and are defined as above. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Non-limiting examples of suitable polycyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl, etc.

[0033] In the present disclosure, the term "heterocyclyl" refers to a non-aromatic saturated monocyclic or polycyclic ring system containing about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more of the ring atoms in the ring system is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination. There are no adjacent oxygen and / or sulfur atoms in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heterocyclyl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The heterocyclyl may optionally be substituted with one or more "ring system substituents", which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclyl may optionally be oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, and the like.

[0034] In the present disclosure, the electroplating additives involved in the present disclosure can form coordination polymers with nickel elements and cobalt elements to form compounds. For example, it can form the following structure with nickel atoms and / or cobalt atoms: Among them, cobalt is connected to two carboxyl groups, and nickel is connected to four carboxyl groups.

[0035] The present invention is further described below by way of specific examples. The various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all weight contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0036] Examples and Comparative Examples Embodiment 1: Embodiment 1 comprises the following steps: (1) Preparation of the electrolyte additive of Example 1: 4.5 g of 5-bromoisophthalic acid (20 mmol) was added to 50 mL of butyronitrile, followed by 1.0 g of potassium phosphate, 400 μL of ethylenediamine (0.36 g, 6 mmol) and 0.5 g of catalyst CuI, and then 3.26 g of 4-aminobenzamide (24 mmol). The mixture was reacted at 165 °C for 4 h under nitrogen protection. After the reaction, the product was extracted, column chromatographed and dried to obtain the organic compound with a yield of 72%. 1 H NMR: δ 6.87 (2H, J = 8.6, 1.1, 0.4 Hz), 7.47 (2H, J =8.6, 1.7, 0.4 Hz), 7.60 (2H, t, J = 1.9 Hz), 8.44 (1H, t, J = 1.9 Hz). (2) Prepare the electroplating solution of Example 1: 6 g of sodium dodecyl sulfate was added to 500 mL of water, and the water was heated to 80° C. to completely dissolve the sodium dodecyl sulfate. Then, 80 g of cobalt nitrate, 40 g of nickel nitrate, 25 g of sodium chloride, 5 g of tartaric acid and 3 g of the electrolyte additive prepared above (10 mmol) were added to obtain the electroplating solution of Example 1.

[0037] Embodiment 2: Embodiment 2 comprises the following steps: (1) Preparation of the electrolyte additive of Example 2: Example 2 The steps for preparing the electrolyte additive are the same as those in Example 1, except that the raw material 4-aminobenzamide is replaced by 3-aminobenzamide: Product yield 65%, 1 H NMR: δ 7.26 (1H, J = 8.2, 1.4, 1.3 Hz), 7.34-7.51 (2H,7.42 (J = 8.4, 8.2, 0.4 Hz), 7.45 (J = 8.4, 1.8, 1.3 Hz)), 7.61 (2H, t, J =1.9 Hz), 8.07 (1H, J = 1.8, 1.4, 0.4 Hz), 8.44 (1H, t, J = 1.9 Hz).

[0038] (2) Prepare the electroplating solution of Example 2: The steps for preparing the electroplating solution in Example 2 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive (10 mmol) prepared in Example 2.

[0039] Embodiment 3: Embodiment 3 comprises the following steps: (1) Preparation of the electrolyte additive of Example 3: Example 3 The steps for preparing the electrolyte additive are the same as those in Example 1, except that the raw material 4-aminobenzamide is replaced by 2-aminobenzamide: Product yield 63%, 1 H NMR: δ 6.88 (1H, J = 8.1, 1.2, 0.5 Hz), 7.29 (1H, J =7.9, 7.4, 1.2 Hz), 7.42-7.65 (4H, 7.49 (J = 7.9, 1.4, 0.5 Hz), 7.58 (J = 8.1,7.4, 1.4 Hz), 7.60 (t, J = 1.9 Hz)), 8.44 (1H, t, J = 1.9 Hz). (2) Preparation of the electroplating solution of Example 3: The steps for preparing the electroplating solution in Example 3 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive (10 mmol) prepared in Example 3.

[0040] Embodiment 4: Embodiment 4 comprises the following steps: (1) Preparation of the electrolyte additive of Example 4: Example 4 The steps for preparing the electrolyte additive are the same as those in Example 1, except that the raw material 4-aminobenzamide is replaced by 2,3-diaminobenzamide: Product yield 67%, 1 H NMR: δ 6.63 (1H, dd, J = 8.3, 1.5 Hz), 6.98 (1H, dd, J= 8.5, 8.3 Hz), 7.16 (1H, dd, J = 8.5, 1.5 Hz), 7.60 (2H, t, J = 1.9 Hz), 8.44 (1H, t, J = 1.9 Hz). (2) Preparation of the electroplating solution of Example 4: The steps for preparing the electroplating solution in Example 4 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive (10 mmol) prepared in Example 4.

[0041] Embodiment 5: Embodiment 5 comprises the following steps: (1) Preparation of the electrolyte additive of Example 5: Example 5 The steps for preparing the electrolyte additive are the same as those in Example 1, except that the raw material 4-aminobenzamide is replaced by 3,4-diaminobenzamide: Product yield 70%, 1 H NMR: δ 6.84 (1H, dd, J = 8.8, 0.5 Hz), 7.23 (1H, dd, J= 8.8, 1.8 Hz), 7.60 (2H, t, J = 1.9 Hz), 8.12 (1H, dd, J = 1.8, 0.5 Hz), 8.44 (1H, t, J = 1.9 Hz). (2) Preparation of the electroplating solution of Example 5: The steps for preparing the electroplating solution in Example 5 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive (10 mmol) prepared in Example 5.

[0042] Comparative Example 1: (1) Select the electrolyte additive of Comparative Example 1: 5-Hydroxyisophthalic acid was selected as the electrolyte additive of Comparative Example 1.

[0043] (2) Preparation of the electroplating solution of Comparative Example 1: The steps for preparing the electroplating solution in Comparative Example 1 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive of Comparative Example 1 (10 mmol).

[0044] Comparative Example 2: (1) Select the electrolyte additive of Comparative Example 2: Diethylenetriamine was selected as the electrolyte additive in Comparative Example 2.

[0045] (2) Preparation of the plating solution of Comparative Example 2: The steps for preparing the electroplating solution in Comparative Example 2 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive of Comparative Example 2 (10 mmol).

[0046] Comparative Example 3: (1) Select the electrolyte additive of Comparative Example 3: Tetrahydroxyethylethylenediamine was selected as the electrolyte additive of Comparative Example 3.

[0047] (2) Preparation of the electroplating solution of Comparative Example 3: The steps for preparing the electroplating solution in Comparative Example 3 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive of Comparative Example 3 (10 mmol).

[0048] Comparative Example 4: (1) Select the electrolyte additive of Comparative Example 4: Sodium acetate was selected as the electrolyte additive for Comparative Example 4.

[0049] (2) Preparation of the plating solution of Comparative Example 4: The steps for preparing the electroplating solution in Comparative Example 4 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive (10 mmol) of Comparative Example 4.

[0050] Comparative Example 5: (1) Select the electrolyte additive of Comparative Example 5: Butanetetracarboxylic acid was selected as the electrolyte additive of Comparative Example 5.

[0051] (2) Preparation of the electroplating solution of Comparative Example 5: The steps for preparing the electroplating solution in Comparative Example 5 are the same as those in Example 1, except that the electrolyte additive prepared in Example 1 is replaced by the electrolyte additive of Comparative Example 5 (10 mmol).

[0052] Electroplating process: The electrolytes prepared in Examples 1-5 and Comparative Examples 1-5 were electroplated under the following conditions: substrate: iron plate, current value: 2.5 A, current density: 4 A / dm 2 , temperature is 25°C, current time is 20min, and electroplated plates of Examples 1-5 and Comparative Examples 1-5 are obtained.

[0053] Corrosion resistance test: The electroplated plates of Examples 1-5 and Comparative Examples 1-5 were placed in a sodium chloride salt solution at a temperature of 45°C, the pH was adjusted to 6.5, and the precipitation rate of the salt mist was adjusted to 2 ml / 80 cm ² .h, and then placed for 2.5h to detect the corrosion degree of the electroplated plate. The test results are shown in Table 1.

[0054] Table 1: By comparing Examples 1-5 and Comparative Examples 1-5, it can be seen that the electrolyte additive provided by the present disclosure can not only act as a complexing agent, but also form a coordination polymer with chromium ions and nickel ions, which is conducive to the precipitation of heavy metal ions, so that the heavy metal ions will not form a piled hydroxy bridge compound; and, since the electrolyte additive contains amino groups and amide groups in its molecular structure, it can further help precipitate heavy metal ions. In addition, by comparing Examples 1-5, it can be seen that in similar molecular structures, the position and number of amino groups will also affect the effect of the electrolyte additive. When the amino group is in the ortho position (Example 3), its performance as an electrolyte additive will be worse, because the ortho amino group will combine with the carboxylic acid of the electrolyte additive, which is not conducive to its complexation with heavy metal ions; while in Example 5, the amino group is not in the ortho position and the number of amino groups is larger, so the performance is the best.

[0055] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. The present disclosure is intended to cover any variations, uses or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary technical means in the art that are not disclosed in the present disclosure.

Claims

1. A chromium-nickel alloy electroplating additive, characterized in that: The electroplating additive is selected from organic compounds whose molecular structures meet the following conditions: contains at least one aryl, cycloalkyl, heterocyclyl or heteroaryl group; comprising at least one amino group, wherein the amino group is connected to the aryl group, cycloalkyl group, heterocyclyl group or heteroaryl group; The compound comprises at least two carboxyl groups, wherein the carboxyl groups are connected to the aryl group, cycloalkyl group, heterocyclic group or heteroaryl group.

2. The electroplating additive according to claim 1, characterized in that: The electroplating additive is selected from organic compounds whose molecular structures meet the following conditions: 1) contains at least two aryl groups or heteroaryl groups; or, contains at least one aryl group and at least one heteroaryl group; 2) comprising at least one amide group, wherein the amide group is connected to the aryl or heteroaryl group; 3) comprising at least one amino group, wherein the amino group is connected to the aryl or heteroaryl group; 4) comprising at least two carboxyl groups, wherein the carboxyl groups are connected to the aryl or heteroaryl groups; 5) The amino group and the carboxyl group are not connected to the same aryl group or heteroaryl group.

3. The electroplating additive according to claim 1, characterized in that: The electroplating additive is selected from organic compounds having the following formula I structure: wherein n is selected from an integer of 1-6; Ar1 ​​and Ar2 are each independently selected from C3-C15 cycloalkyl, C6-12 aryl, 5-15 membered heterocyclyl or 5-15 membered heteroaryl; wherein the C3-C15 cycloalkyl, C6-12 aryl, 5-15 membered heterocyclyl or 5-15 membered heteroaryl are optionally substituted with one or more hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy.

4. The electroplating additive according to claim 3, characterized in that: Ar1 and Ar2 are each independently selected from phenyl and biphenyl, wherein the phenyl and biphenyl are optionally substituted by one or more hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl, C1-C3 alkoxy.

5. The electroplating additive according to claim 4, characterized in that: The electroplating additive is selected from organic compounds having the following structures of Formula II-1 to Formula II-4: Wherein, n is selected from an integer of 1-6; n2 is selected from an integer of 0 to 3; R1 is selected from hydrogen, hydroxyl, nitro, cyano, C1-C3 alkyl or C1-C3 alkoxy.

6. The electroplating additive according to claim 4, characterized in that: The electroplating additive is selected from any one of the following organic compounds: 。 7. A method for preparing the electroplating additive according to any one of claims 3 to 6, characterized in that: The method comprises the following steps: 。 8. A chromium-nickel alloy electroplating solution, characterized in that: The electroplating solution comprises: water, chromium salt, nickel salt, conductive agent, surfactant, buffer, and the electroplating additive according to any one of claims 1 to 6.

9. The electroplating solution according to claim 8, characterized in that In the electroplating solution, relative to 1000 parts by weight of water, the content of the chromium salt is 100-200 parts by weight, the content of the nickel salt is 40-100 parts by weight, the content of the conductive agent is 40-80 parts by weight, the content of the surfactant is 5-20 parts by weight, the content of the buffer is 10-50 parts by weight, and the content of the electroplating additive is 5-60 parts by weight.

10. The electroplating solution according to claim 8, characterized in that The chromium salt is selected from at least one of chromium nitrate, chromium chloride or chromium sulfate; the nickel salt is selected from at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate; the conductive agent is selected from at least one of ammonium chloride, sodium chloride or potassium chloride; the surfactant is selected from at least one of sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, OP-10 or polyvinyl pyrrolidone; the buffer is selected from at least one of boric acid, tartaric acid or phosphoric acid.

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