Metallic nickel suspension, method for its production, coating and adhesive tape

Abstract

The application provides a metal nickel suspension liquid and a preparation method, paint and adhesive tape thereof, and relates to the technical field of nickel suspension liquid. Raw materials of the metal nickel suspension liquid include, by weight, 100 parts of acrylate, 8-20 parts of nickel powder, 0.5-1 part of carboxyl aromatic acid compound and 0.5-1 part of halogenated alkyl bromide. The carboxyl aromatic acid compound and the halogenated alkyl bromide (organic halide) undergo electrophilic cross-coupling reaction under the action of nickel to prepare an amphoteric macromolecule, an electrophilic group extends to the metal nickel phase, and an electron-donating group extends to the acrylate solution, so that the surface tension of the nickel powder is reduced, meanwhile, different micelles are relatively stable and independent, which is beneficial to the dispersion of the whole to form small particle droplets, so that the nickel powder is stably suspended in the acrylate solution.

Description

Technical Field

[0001] This application relates to the field of nickel suspension technology, and more particularly to a metallic nickel suspension and its preparation method, coatings and tapes. Background Technology

[0002] With the rapid development of science and technology, various devices are evolving from ordinary braking systems to more intelligent ones. While mobile phones rely on screen interaction, cars are increasingly adopting screen interaction modes. The use of circuit modules is becoming more widespread, leading to growing demands for technologies related to conductivity and shielding. Even simple reductions in impedance can directly impact energy conservation, emission reduction, cost control, and weight and size reduction.

[0003] Currently, most conductive products rely on the addition of metallic nickel filler. On the one hand, due to the density difference—ordinary resin has a density of 0.9-1.4 g / cm³, while metallic nickel powder has a density of 7-10 g / cm³—it still agglomerates under gravity. On the other hand, the intermolecular forces between the powder particles easily cause agglomeration, resulting in uneven dispersion, reduced conductivity in some areas, and in severe cases, rendering the product unusable.

[0004] Therefore, how to solve the above problems and provide a new metal suspension is an urgent issue that needs to be addressed. Summary of the Invention

[0005] The purpose of this application is to provide a metallic nickel suspension and its preparation method, as well as coatings and tapes, to solve the above-mentioned problems.

[0006] To achieve the above objectives, the first aspect of this application provides a metallic nickel suspension, the raw materials of which, by weight, comprise: 100 parts acrylate, 8-20 parts nickel powder, 0.5-1 part carboxylic aromatic acid compound, and 0.5-1 part haloalkyl bromide.

[0007] Optionally, the nickel suspension satisfies at least one of the following conditions: A. The nickel powder includes modified nickel powder treated with a phenylsilane coupling agent; B. The nickel powder comprises pure metallic nickel and / or nickel-coated graphite; C. The particle size of the nickel powder is less than or equal to 100 μm.

[0008] Optionally, the phenylsilane coupling agent includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.

[0009] Optionally, the nickel suspension satisfies at least one of the following conditions: A. The chemical formula of the acrylate is CH2=CR1COOR2; Wherein, R1 includes a hydrogen group or an alkyl group, and R2 includes -(CH2). m -H, where m is a positive integer from 1 to 5; The alkyl group has 4 or fewer carbon atoms; B. The molecular weight of the acrylate is 86-198.

[0010] Optionally, the nickel suspension satisfies at least one of the following conditions: A. The general chemical formula of the carboxylic aromatic acid compound is: H-(CH2) n -C6H4-COOH; Where n is a positive integer from 4 to 9; B. The molecular weight of the carboxylic aromatic acid compound is 180-250.

[0011] Optionally, the general chemical formula of the haloalkyl bromide is: H-(CH2) y -Br; Where y is a positive integer between 4 and 9.

[0012] A second aspect of this application provides a method for preparing the aforementioned nickel suspension, comprising: Nickel powder and carboxylic aromatic acid compound are first mixed and then heated to obtain a mixture; The mixture, acrylate, and haloalkyl bromide are then mixed a second time to obtain a nickel suspension.

[0013] Optionally, the method for preparing the nickel suspension satisfies at least one of the following conditions: A. The heating temperature is 80℃-100℃, and the time is 2h-4h; B. Before performing the second mixing, the mixture is sieved; C. After the second mixing, vacuum degassing is performed; The vacuum degassing pressure is -0.1 MPa to -0.08 MPa.

[0014] A third aspect of this application provides a coating comprising the aforementioned nickel suspension or a nickel suspension prepared by the method for preparing the aforementioned nickel suspension.

[0015] The fourth aspect of this application provides an adhesive tape comprising the aforementioned nickel suspension or a nickel suspension prepared by the method for preparing the aforementioned nickel suspension.

[0016] Compared with the prior art, the beneficial effects of this application include: The nickel suspension provided in this application involves a carboxylic aromatic acid compound and a haloalkyl bromide (organohalogenated compound) undergoing an electrophilic cross-coupling reaction under the action of nickel to obtain an amphoteric macromolecule. The electrophilic group extends into the nickel phase, while the electron-donating group extends into the acrylate solution, which reduces the surface tension of the nickel powder. At the same time, the different micelles remain relatively stable and independent, which is conducive to the overall dispersion to form fine droplets, thereby making the nickel powder stably suspended in the acrylate solution.

[0017] The method for preparing a nickel suspension provided in this application involves first mixing nickel powder and a carboxylic aromatic acid compound evenly, then heating to form a nickel chelate, which is further reacted with a haloalkyl bromide. Throughout the process, the carboxylic aromatic acid compound and the haloalkyl bromide undergo an electrophilic cross-coupling reaction to obtain an amphoteric macromolecule. In the end, nickel is reduced to elemental nickel, which acts as a catalyst. This preparation method not only avoids the introduction of new catalyst impurities but also avoids the problems caused by ketone compounds prepared by the traditional Weinreb ketone synthesis strategy, such as the volatilization, residue, and reduced adhesion of these monomers in the later use. Furthermore, this preparation method is simple, has a short production cycle, and high production efficiency, making it suitable for large-scale production.

[0018] The coatings and tapes provided in this application do not easily cause the nickel powder to agglomerate. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0020] Figure 1 A schematic diagram of nickel distribution in the nickel suspension provided in this application; Figure 2 A photograph of the 72-hour precipitation test of the nickel suspension provided in Example 1; Figure 3 This is a photograph of the 72-hour precipitation test of the nickel suspension provided in Example 2. Figure 4 This is a photograph of the 72-hour precipitation test of the nickel suspension provided in Example 3. Figure 5 A photograph of the 72-hour precipitation test of the nickel suspension provided for Comparative Example 1; Figure 6 A photograph of the 72-hour precipitation test of the nickel suspension provided for Comparative Example 2; Figure 7 A photograph of the 72-hour precipitation test of the nickel suspension provided for Comparative Example 3; Figure 8A photograph of the 72-hour precipitation test of the nickel suspension provided for Comparative Example 4; Figure 9 A photograph of the 72-hour precipitation test of the nickel suspension provided in Comparative Example 5; Figure 10 Microscopic examination image of the nickel suspension provided in Example 1; Figure 11 Microscopic image of the nickel suspension provided in Example 2; Figure 12 Microscopic images of the nickel suspension provided in Comparative Example 1; Figure 13 Microscopic images of the nickel suspension provided in Comparative Example 2; Figure 14 Microscopic images of the nickel suspension provided in Comparative Example 3; Figure 15 Microscopic images of the nickel suspension provided in Comparative Example 4; Figure 16 Microscopic image of the nickel suspension provided in Comparative Example 5. Detailed Implementation

[0021] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0022] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0023] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0024] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0025] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0026] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0027] The first aspect of this application provides a nickel suspension, the raw materials of which, by weight, include: 100 parts acrylate, 8-20 parts nickel powder, 0.5-1 part carboxylic aromatic acid compound, and 0.5-1 part haloalkyl bromide.

[0028] Optionally, the raw materials for the nickel suspension, by weight, include 100 parts of acrylate, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, or any value between 8 and 20 parts of nickel powder, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, or any value between 0.5 and 1 part of carboxylic aromatic acid compound, and 0.5 parts to 1 part of haloalkyl bromide.

[0029] In some embodiments, the nickel suspension satisfies at least one of the following conditions: A. The nickel powder includes modified nickel powder treated with a phenylsilane coupling agent; It should be noted that in modified nickel powder treated with phenylsilane coupling agent, the phenylsilane coupling agent acts as a promoter in the entire reaction process, improving the encapsulation and dispersibility of the nickel powder. B. The nickel powder comprises pure metallic nickel and / or nickel-coated graphite; In some embodiments, the nickel powder is pure metallic nickel; In some embodiments, the nickel powder is nickel-coated graphite; In some embodiments, the nickel powder is a mixture of pure metallic nickel and nickel-coated graphite. Preferably, when the mass ratio of pure metallic nickel to nickel-coated graphite is 1:0.5, the effective component of the entire suspension, i.e., the conductivity, is optimal. C. The particle size of the nickel powder is less than or equal to 100 μm.

[0030] Optionally, the particle size of the nickel powder can be 1µm, 10µm, 20µm, 40µm, 60µm, 80µm, 100µm or any value less than or equal to 100µm.

[0031] It should be noted that when the particle size of nickel powder is less than or equal to 100 μm, the specific surface area is relatively large, so as to achieve a stable suspension effect.

[0032] In some embodiments, the phenylsilane coupling agent includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.

[0033] In some embodiments, the nickel suspension satisfies at least one of the following conditions: A. The chemical formula of the acrylate is CH2=CR1COOR2; Wherein, R1 includes a hydrogen group or an alkyl group, and R2 includes -(CH2). m -H, where m is a positive integer from 1 to 5; Optionally, m can be 1, 2, 3, 4, 5 or any positive integer between 1 and 5; The alkyl group has 4 or fewer carbon atoms; Optionally, the number of carbon atoms in the alkyl group can be 1, 2, 3, 4 or any positive integer less than or equal to 4; B. The molecular weight of the acrylate is 86-198.

[0034] In some embodiments, the nickel suspension satisfies at least one of the following conditions: A. The general chemical formula of the carboxylic aromatic acid compound is: H-(CH2) n -C6H4-COOH; Where n is a positive integer from 4 to 9; Optionally, n can be any positive integer between 4, 5, 6, 7, 8, 9, or 4-9; In some optional embodiments, a carboxyl aromatic acid compound refers to a compound having an aromatic acid group, i.e., a benzoic acid group obtained by directly attaching a carboxyl group to a benzene ring. For example, carboxyl aromatic acid compounds include, but are not limited to, one or more of CH3(CH2)4-C6H4-COOH, CH3(CH2)5-C6H4-COOH, CH3(CH2)6-C6H4-COOH, CH3(CH2)7-C6H4-COOH, CH3(CH2)8-C6H4-COOH, and CH3(CH2)9-C6H4-COOH. B. The molecular weight of the carboxylic aromatic acid compound is 180-250.

[0035] In some embodiments, the general chemical formula of the haloalkyl bromide is: H-(CH2) y -Br; Where y is a positive integer between 4 and 9.

[0036] Optionally, y can be any positive integer between 4, 5, 6, 7, 8, 9, or 4-9.

[0037] In some optional embodiments, the haloalkyl bromides include, but are not limited to, one or more of CH3(CH2)4-Br, CH3(CH2)5-Br, CH3(CH2)6-Br, CH3(CH2)7-Br, CH3(CH2)8-Br, and CH3(CH2)9-Br.

[0038] A second aspect of this application provides a method for preparing the aforementioned nickel metal suspension, comprising: Nickel powder and carboxylic aromatic acid compound are first mixed and then heated to obtain a mixture; The mixture, acrylate, and haloalkyl bromide are then mixed a second time to obtain a nickel suspension.

[0039] It is important to note that, such as Figure 1 As shown in the left figure, when nickel powder is only in a solvent, the nickel powder will agglomerate in large quantities, while... Figure 1 As shown in the right figure, after nickel powder and carboxylic aromatic acid compound are mixed evenly, the nickel chelate formed by heating is further reacted with haloalkyl bromide. In the whole process, the carboxylic aromatic acid compound and haloalkyl bromide undergo electrophilic cross-coupling reaction to obtain amphoteric macromolecules, thereby making the nickel powder stably suspended in acrylate solution.

[0040] In some embodiments, the method for preparing the nickel suspension satisfies at least one of the following conditions: A. The heating temperature is 80℃-100℃, and the time is 2h-4h; Optionally, the heating temperature can be any value between 80℃, 90℃, 100℃ or 80℃-100℃, and the time can be any value between 2h, 3h, 4h or 2h-4h. B. Before performing the second mixing, the mixture is sieved; C. After the second mixing, vacuum degassing is also performed; The vacuum degassing pressure is -0.1 MPa to -0.08 MPa.

[0041] Optionally, the pressure for vacuum degassing can be any value between -0.1 MPa, -0.09 MPa, -0.08 MPa, or -0.1 MPa and -0.08 MPa.

[0042] A third aspect of this application provides a coating comprising the aforementioned nickel suspension or a nickel suspension prepared by the method for preparing the aforementioned nickel suspension.

[0043] In some alternative embodiments, the application of the coating includes, but is not limited to, electromagnetic shielding, antistatic properties, and conductivity.

[0044] The fourth aspect of this application provides an adhesive tape comprising the aforementioned nickel suspension or a nickel suspension prepared by the method for preparing the aforementioned nickel suspension.

[0045] In some alternative embodiments, the tape is used as EMI shielding to prevent electromagnetic interference to electronic devices and as conductive bonding for flexible printed circuit boards.

[0046] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0047] Example 1 The first aspect of this embodiment provides a nickel suspension, the raw materials of which, by weight, include: 100g acrylate, 15g pure nickel powder, 0.8g carboxylic aromatic acid compound, 0.8g haloalkyl bromide; Among them, the nickel powder is modified pure metallic nickel treated with phenylsilane coupling agent, Dv(50)=25um, Dv(90)=80um; The phenylsilane coupling agent is phenyltrimethoxysilane; The chemical formula of acrylate is CH2=CCH3COOCH3, and the molecular weight of acrylate is 102. The carboxylic aromatic acid compound is CH3CH2C6H4COOH; The haloalkyl bromide is CH3CH2Br.

[0048] The second aspect of this embodiment provides a method for preparing a nickel metal suspension, the specific steps of which include: S1: Mix nickel powder and carboxyl-functionalized aromatic acid, sieve under ultrasonic vibration and 325 mesh screen, and bake the sieved material in an 80℃ oven for 2 hours. S2: The acrylate and the haloalkyl bromide are stirred and mixed at a speed of 800 r / min; S3: Mix the S1 and S2 products, stir dynamically at a stirring speed of 800-1000 r / min until homogeneous, and then degas under vacuum. The vacuum degassing pressure is -0.1 MPa to -0.08 MPa.

[0049] The third aspect of this embodiment provides an adhesive tape, including the above-mentioned nickel suspension. The method for preparing the adhesive tape includes: applying the above-mentioned nickel suspension to the surface of a copper foil using a doctor blade to form an adhesive tape product.

[0050] Example 2 The difference from Example 1 is that the amount of nickel powder is 20g.

[0051] Example 3 The difference from Example 1 is that the third aspect provides a coating whose raw materials, by weight, include: 30 parts of metallic nickel suspension and 70 parts of acrylic ester base coating.

[0052] Comparative Example 1 The difference from Example 1 is that no carboxyl-functionalized aromatic acid is added.

[0053] Comparative Example 2 The difference from Example 1 is that no haloalkyl bromide is added.

[0054] Comparative Example 3 The difference from Example 1 is that no haloalkyl bromide and carboxyl-functionalized aromatic acid are added.

[0055] Comparative Example 4 The difference from Example 1 is that the raw materials for the nickel metal suspension, by weight, include: 100 parts acrylate, 50 parts nickel powder, 5 parts carboxylic aromatic acid compound, and 5 parts haloalkyl bromide.

[0056] Comparative Example 5 The difference from Example 1 is that metallic nickel is replaced with iron powder.

[0057] The nickel suspensions prepared in the above examples and comparative examples were subjected to precipitation tests, and the precipitation was observed after 72 hours. The precipitation test results for Example 1 after 72 hours are as follows: Figure 2 As shown, the 72-hour precipitation test results of Example 2 are as follows: Figure 3 As shown, the 72-hour precipitation test results of Example 3 are as follows: Figure 4 As shown, the precipitation test results of Comparative Example 1 after 72 hours are as follows: Figure 5 As shown, the precipitation test results of Comparative Example 2 after 72 hours are as follows: Figure 6 As shown, the precipitation test results of Comparative Example 3 after 72 hours are as follows: Figure 7 As shown, the precipitation test results of Comparative Example 4 after 72 hours are as follows: Figure 8 As shown, the precipitation test results of Comparative Example 5 after 72 hours are as follows: Figure 9 As shown in Table 1, the specific test results are as follows.

[0058] Table 1 Sedimentation Test

[0059] The nickel suspensions prepared in the above examples and comparative examples were also subjected to microscopic examination to observe the uniformity of powder distribution. The microscopic test results of Example 1 are as follows: Figure 10 As shown, the microscope test results of Example 2 are as follows: Figure 12 As shown, the microscopic test results of Comparative Example 1 are as follows: Figure 13 As shown, the microscopic test results of Comparative Example 2 are as follows: Figure 14 As shown, the microscopic test results of Comparative Example 3 are as follows: Figure 14 As shown, the microscopic test results of Comparative Example 4 are as follows: Figure 15 As shown, the microscopic test results of Comparative Example 5 are as follows: Figure 16 As shown.

[0060] analyze: As can be seen from the above-mentioned precipitation test and microscopic observation, the nickel suspension prepared in this application has good stability and uniform dispersion, as can be seen from Examples 1-3; Comparative Examples 1, 3, and 5 essentially blocked the mechanism, so there was a large amount of precipitation; Comparative Example 2 also had serious defects, but it had some stability under the pretreatment; Comparative Example 4 exceeded the overall tolerance range.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0062] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A nickel suspension, characterized in that, Its raw materials, by weight, include: 100 parts acrylate, 8-20 parts nickel powder, 0.5-1 part carboxylic aromatic acid compound, and 0.5-1 part haloalkyl bromide.

2. The nickel suspension according to claim 1, characterized in that, At least one of the following conditions must be met: A. The nickel powder includes modified nickel powder treated with a phenylsilane coupling agent; B. The nickel powder comprises pure metallic nickel and / or nickel-coated graphite; C. The particle size of the nickel powder is less than or equal to 100 μm.

3. The nickel suspension according to claim 2, characterized in that, The phenylsilane coupling agent includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.

4. The nickel suspension according to claim 1, characterized in that, At least one of the following conditions must be met: A. The chemical formula of the acrylate is CH2=CR1COOR2; Wherein, R1 includes a hydrogen group or an alkyl group, and R2 includes -(CH2). m -H, where m is a positive integer from 1 to 5; The alkyl group has 4 or fewer carbon atoms; B. The molecular weight of the acrylate is 86-198.

5. The nickel suspension according to claim 1, characterized in that, At least one of the following conditions must be met: A. The general chemical formula of the carboxylic aromatic acid compound is: H-(CH2) n -C6H4-COOH; Where n is a positive integer from 4 to 9; B. The molecular weight of the carboxylic aromatic acid compound is 180-250.

6. The metallic nickel suspension according to any one of claims 1-5, characterized in that, The general chemical formula of the haloalkyl bromide is: H-(CH2) y -Br; Where y is a positive integer between 4 and 9.

7. A method for preparing a metallic nickel suspension according to any one of claims 1-6, characterized in that, include: Nickel powder and carboxylic aromatic acid compound are first mixed and then heated to obtain a mixture; The mixture, acrylate, and haloalkyl bromide are then mixed a second time to obtain a nickel suspension.

8. The method for preparing the metallic nickel suspension according to claim 7, characterized in that, At least one of the following conditions must be met: A. The heating temperature is 80℃-100℃, and the time is 2h-4h; B. Before performing the second mixing, the mixture is sieved; C. After the second mixing, vacuum degassing is performed; The vacuum degassing pressure is -0.1 MPa to -0.08 MPa.

9. A coating, characterized in that, Includes the metallic nickel suspension according to any one of claims 1-6 or the metallic nickel suspension prepared by the method for preparing the metallic nickel suspension according to claim 7 or 8.

10. A type of adhesive tape, characterized in that, Includes the metallic nickel suspension according to any one of claims 1-6 or the metallic nickel suspension prepared by the method for preparing the metallic nickel suspension according to claim 7 or 8.

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