A plating-resistant chemical liquid-resistant polypropylene composition, a method for preparing the same, and use thereof

Abstract

The application belongs to the technical field of high polymer materials, and discloses a polypropylene composition resistant to electroplating chemical liquid, and a preparation method and application thereof. The polypropylene composition comprises a polypropylene resin, a polyethylene wax, an amide lubricant, a glyceride lubricant, a nucleating agent and glass fiber. The isotacticity of the polypropylene resin is greater than or equal to 97.5%, and the nucleating agent is at least one of a carboxylic acid metal salt or an organic phosphoric acid metal salt. The polypropylene composition provided by the application is comprehensively modified by adding a lubricant, a specific type of nucleating agent and optional glass fiber in a polypropylene with a specific isotacticity, so that the obtained polypropylene composition not only maintains good mechanical properties, but also has the advantage of being resistant to electroplating chemical liquid.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a polypropylene composition resistant to electroplating chemical solution, a preparation method and application thereof. BACKGROUND

[0002] Polypropylene (PP) has the advantages of low density, easy processing, excellent mechanical properties, etc., and has been widely used in the automotive industry, household appliances and mechanical fields.

[0003] In the electroplating industry, when electroplating aluminum alloy, magnesium alloy, copper alloy, titanium alloy and the like, in order to increase the electroplating efficiency, a large number of original pieces are usually concentrated together, fixed by using a support or a tray, and then put into an electroplating tank for batch continuous production, and finally the support or the tray is opened to take out the electroplated parts. In this process, the support or the tray cannot damage the parts, cannot participate in the electroplating reaction, and cannot affect the electroplating effect of the parts. If a metal support or a tray is selected, the poor chemical resistance of the metal will result in a short service life, and the parts are easily scratched, affecting the electroplating effect. If a plastic support or a tray is selected, the chemical resistance of the material also needs to be considered, as well as the influence on the electroplating effect in the electroplating process. The tray made of ordinary polypropylene material also has problems of whitening, delamination and color spots on the surface of the electroplated parts after the chemical electroplating process in actual use.

[0004] The prior art discloses a glass fiber reinforced polypropylene material resistant to corrosion, which uses glass fiber and sorbitol nucleating agent to improve the impact strength, tensile strength, mechanical properties and heat resistance of the product, but does not improve the bending modulus data, only studies the corrosion resistance of polypropylene material in ethylene glycol, and covers a small number of substances, limiting the application range of the material.

[0005] Therefore, it is of important research significance and application value to develop a polypropylene composition with good mechanical properties and electroplating chemical solution resistance. SUMMARY

[0006] In order to solve the technical problem that the polypropylene material in the prior art cannot have good mechanical properties and electroplating chemical solution resistance, the present application provides a polypropylene composition resistant to electroplating chemical solution. The polypropylene composition resistant to electroplating chemical solution provided by the present application is comprehensively modified by adding PE wax, amide lubricant, glyceride lubricant and a specific type of nucleating agent in a polypropylene matrix material with a specific isotacticity, so that the obtained polypropylene composite material not only maintains good mechanical properties, but also has good electroplating chemical solution resistance.

[0007] Another purpose of the present application is to provide a preparation method of the above-mentioned polypropylene composition resistant to electroplating chemical solution.

[0008] Another object of the present application is to provide the use of the above-mentioned polypropylene composition resistant to electroplating chemical solution in the preparation of electroplating tank accessories and hangers.

[0009] Another object of the present application is to provide an electroplating tank accessory part prepared from the above-mentioned polypropylene composition.

[0010] To achieve the above-mentioned objects, the present application adopts the following technical solutions:

[0011] A polypropylene composition resistant to electroplating chemical solution comprises the following components in parts by weight: 90-100 parts of polypropylene resin, 0.3-1 part of PE wax, 0.3-0.6 part of amide lubricant, 0.3-0.6 part of glyceride lubricant, 0.1-0.5 part of nucleating agent, and 0-5 parts of glass fiber.

[0012] Preferably, the isotacticity of the polypropylene resin is selected from one of 97.5%, 98%, 98.5%, and 99%.

[0013] The polyethylene wax (PE wax) is also known as high molecular wax and is abbreviated as polyethylene wax. It is widely used due to its excellent cold resistance, heat resistance, chemical resistance, and wear resistance. In normal production, this part of wax can be directly added to polyolefin processing as an additive, which can increase the gloss and processing performance of the product. As a lubricant, it has stable chemical properties and good electrical properties. The addition of PE wax can improve the lubricity, hydrophobicity, and point insulation of the surface of the polypropylene material; the addition of the nucleating agent can promote the crystallinity and surface density of the polypropylene, which is beneficial to prevent small molecular substances such as acids, bases, copper salts, and soaps in the electroplating chemical solution from entering the material from the outside. During the crystallization of PE wax and PP, the amide lubricant will gradually precipitate to the surface, thereby forming a protective film that can block small molecular substances in the chemical solution.

[0014] The glyceride lubricant reduces the adsorption of bubbles on the surface of the part. Glyceride belongs to a polyol type non-ionic surfactant and has good surface activity. When the part enters the aqueous solution, the bubbles are quickly detached from the surface of the part.

[0015] Preferably, the isotacticity of the polypropylene resin is selected from one of 97.5%, 98%, 98.5%, and 99%.

[0016] The polypropylene of the present application is used as the basic raw material of the polypropylene composition resistant to electroplating chemical solution, and the isotacticity of the polypropylene itself is crucial. The higher the isotacticity of the polypropylene, the better the crystallinity and the higher the density, and accordingly, the better the resistance to electroplating chemical solution. The present application selects polypropylene with an isotacticity of ≥97.5%, thereby obtaining a composition with good resistance to electroplating chemical solution.

[0017] Preferably, the polypropylene resin has a melt mass flow rate of 3 to 80 g / 10 min, preferably 10 to 60 g / 10 min, at 230°C under a load of 2.16 kg.

[0018] Preferably, the PE wax has a melt mass flow rate of 0.2 to 10 g / 10 min, at 190°C under a load of 2.16 kg.

[0019] Preferably, the PE wax has a melting point of 135 to 155°C and a density of 0.955 to 0.960 g / cm 3 .

[0020] The PE wax in the present application includes conventional polyethylene wax, and also includes ethylene acrylic acid copolymer wax powder.

[0021] Preferably, the amide lubricant is selected from at least one of erucic acid amide, stearyl erucic acid amide, oleic acid amide or docosyl fatty amide.

[0022] Specifically, the carboxylic acid metal salt is selected from at least one of sodium benzoate, potassium benzoate or sodium p-toluenesulfonate, and the organic phosphoric acid metal salt is selected from at least one of 2,2'-methylenebis(2.4-di-tert-butylphenoxy) sodium phosphate, 2.2'-methylenebis(4.6-di-tert-butylphenoxy) aluminum basic salt or sodium p-tert-butylphenoxyphosphate.

[0023] Preferably, the glyceride lubricant is selected from at least one of glycerol monostearate, glycerol laurate or fatty acid diglyceride.

[0024] Preferably, the glass fiber is selected from at least one of ESC-13-03-508C GURITE glass fiber or ESC 3F-03-508A GURITE glass fiber.

[0025] More preferably, the average diameter of the glass fiber is 10 to 15 μm.

[0026] More preferably, the average diameter of the glass fiber is 13 μm.

[0027] Preferably, the electroplating chemical liquid resistant polypropylene composition further comprises other auxiliary agents in an amount of 0.4 to 1.6 parts.

[0028] More preferably, the other auxiliary agent is selected from at least one of an antioxidant, a light stabilizer or white mineral oil.

[0029] Specifically, the antioxidant is 0.1 to 0.6 parts, the light stabilizer is 0.1 to 0.5 parts, and the white mineral oil is 0.2 to 0.5 parts.

[0030] Specifically, the antioxidant is a compounded antioxidant composed of hindered phenolic antioxidants and phosphite antioxidants, more preferably, the compounded antioxidant is composed of antioxidant 1010 and antioxidant 168, wherein the mass ratio of antioxidant 1010 and antioxidant 168 is 1-2:1.

[0031] Specifically, the light stabilizer is a hindered amine light stabilizer, selected from at least one of UV3808PP5, LA-402AF or UV770. More preferably, the relative molecular weight of the hindered amine light stabilizer is ≥800, and the melting point thereof is 120-140℃.

[0032] The preparation method of the polypropylene composition resistant to electroplating chemical liquid comprises the following steps:

[0033] S1. uniformly mixing polypropylene resin, PE wax, amide lubricant, glyceride lubricant, nucleating agent, optional glass fiber and other additives to obtain a mixture;

[0034] S2. melt mixing the mixture, extruding and granulating to obtain the polypropylene composition.

[0035] Preferably, the melt mixing is carried out in a twin-screw extruder.

[0036] Preferably, the mixing temperature is 170-220℃, and the screw rotation speed is 350-450rpm.

[0037] The application of the polypropylene composition resistant to electroplating chemical liquid in the preparation of electroplating tank inner and peripheral accessories is also within the protection scope of the present application.

[0038] The present application also protects an electroplating tank inner and peripheral accessory part prepared from the above-mentioned polypropylene composition.

[0039] Preferably, the polypropylene part resistant to electroplating chemical liquid comprises at least one of a tray, a support or a hook.

[0040] Compared with the prior art, the present application has the following beneficial effects:

[0041] The polypropylene composition resistant to electroplating chemical liquid provided by the present application is comprehensively modified by adding PE wax, amide lubricant, glyceride lubricant, phosphoric acid metal salt or carboxylic acid metal salt nucleating agent to polypropylene resin, and the obtained polypropylene composition maintains good mechanical properties and good electroplating chemical liquid resistance, and can be used to prepare electroplating tank inner and peripheral accessory parts, such as trays, supports, hooks, etc.

[0042] The polypropylene composition provided by the application has good mechanical properties, and after being soaked in electroplating chemical liquid, no distortion, delamination, melting, cracking, whitening, discoloration or dirt phenomenon occurs, the discoloration level is 4-5 levels, and the electroplating chemical liquid resistance and mechanical properties are good. DETAILED DESCRIPTION

[0043] The application will be further described below in conjunction with examples. These examples are only used to illustrate the application and not used to limit the scope of the application. The experimental methods in the following examples are not specified, which are generally according to the conventional conditions in the art or according to the conditions suggested by the manufacturers; the raw materials, reagents and the like used are commercially available raw materials and reagents, unless otherwise specified. Any non-essential changes and substitutions made by those skilled in the art on the basis of the application shall fall within the scope of the application.

[0044] Some reagents selected by the examples and comparative examples of the application are described as follows:

[0045] Polypropylene 1: brand PP 225 (STL), manufacturer is Satellite Petrochemical, the isotacticity is 98.8 according to GB / T 2412-2008 standard, and the melt mass flow rate is 29 g / 10 min at 230℃, 2.16 kg according to ISO1133-2022 standard;

[0046] Polypropylene 2: brand K1118, manufacturer is Sinopec, the isotacticity is 96.5 according to GB / T 2412-2008 standard, and the melt flow rate (under the same test conditions) is 17 g / 10 min at 230℃, 2.16 kg according to ISO1133-2022 standard;

[0047] Polypropylene 3: brand CJS700H, manufacturer is Sinopec, the isotacticity is 98.3 according to GB / T 2412-2008 standard, and the melt mass flow rate is 10 g / 10 min at 230℃, 2.16 kg according to ISO1133-2022 standard;

[0048] Polypropylene 4: brand P901, manufacturer is SCG, the isotacticity is 98.5 according to GB / T 2412-2008 standard, and the melt mass flow rate is 60 g / 10 min at 230℃, 2.16 kg according to ISO1133-2022 standard;

[0049] Polypropylene 5: brand P401S, manufacturer is SCG, the isotacticity is 98.1 according to GB / T 2412-2008 standard, and the melt mass flow rate is 3 g / 10 min at 230℃, 2.16 kg according to ISO1133-2022 standard;

[0050] Polypropylene 6: grade K7100, manufacturer Sinopec, according to GB / T 2412-2008 standard, isotacticity is 98.1; according to ISO1133-2022 standard, the melt mass flow rate is 80 g / 10 min at 230℃, 2.16 kg;

[0051] Polypropylene 7: grade CS820, manufacturer Sinopec, according to GB / T 2412-2008 standard, isotacticity is 97.5; according to ISO1133-2022 standard, the melt flow rate is 24 g / 10 min at 230℃, 2.16 kg;

[0052] PE wax 1: grade AC-504A, manufacturer Honeywell;

[0053] PE wax 2: grade LP1040P, manufacturer SGC, Thailand;

[0054] Amide lubricant 1: oleic acid amide, commercially available;

[0055] Amide lubricant 2: erucic acid amide, commercially available;

[0056] Amide lubricant 3: stearyl erucic acid amide, commercially available;

[0057] Non-amide lubricant 1: stearic acid, commercially available;

[0058] Glyceride lubricant 1: glycerol monostearate, commercially available;

[0059] Glyceride lubricant 2: fatty acid diglyceride, commercially available;

[0060] Nucleating agent 1: carboxylic acid metal salt, sodium benzoate, manufacturer Chenghe Technology;

[0061] Nucleating agent 2: phosphoric acid metal salt, 2,2'-methylenebis(2.4-di-tert-butylphenoxy) sodium phosphate, grade NA-11, manufacturer Aidik;

[0062] Nucleating agent 3: sorbitol, grade Millad 3988, manufacturer Milliken;

[0063] Nucleating agent 4: sorbitol acetal, 1,2,3,4-dibenzylidene sorbitol, grade Millad 3905, manufacturer Milliken;

[0064] Glass fiber: grade ESC3F-03-508A, manufacturer Jushi Fiberglass;

[0065] Antioxidant 1: hindered phenolic antioxidant, antioxidant 1010, commercially available;

[0066] Antioxidant 2: Phosphite antioxidant, antioxidant 168, commercially available;

[0067] Light stabilizer: Hindered amine light stabilizer, brand LA-402AF, manufacturer Adic;

[0068] White mineral oil: 10# white mineral oil, Shanghai Daliang Chemical Industry;

[0069] The polypropylene composition of each embodiment and the comparative example of the present application is prepared by the following process:

[0070] S1. Mix each component in the formula of each embodiment and the comparative example to obtain a mixture;

[0071] S2. Add the mixture into a twin-screw extruder, melt and mix, set the temperature of the extruder at 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, the die temperature at 210℃, the feeding amount at 30 kg, the vacuum degree at -0.08, the screw rotation speed at 380 rpm, extrude and granulate to obtain the polypropylene composition.

[0072] The performance test method and standard of the polypropylene composition of each embodiment and the comparative example of the present application are as follows:

[0073] The electroplating chemical liquid resistance performance test: immerse the test plate in 20% concentration of citric acid, glacial acetic acid, malic acid, hydrogen peroxide, polyethylene glycol, sodium phytate, glycerol, triethanolamine, sulfamide, chromium oxidant, imidazoline, fatty alcohol surfactant, respectively, for 24 hours, drain the surface, and then clean the surface of the test plate with pure water. Judgment method: whether there are phenomena such as distortion, delamination, melting, cracking, whitening, discoloration, dirt, etc. after the test; observe whether there are crack or delamination phenomena on the surface with 30 times microscope.

[0074] Discoloration grade: test according to GB / T 250-2008, and grade according to color difference change.

[0075] Table 1 Color difference grade GB / T 250-2008

[0076] fastness rating CIELAB color difference tolerance 5 0 0.2 (4-5) 0.8 ±0.2 4 1.7 ±0.3 (3-4) 2.5 ±0.35 3 3.4 ±0.4 (2-3) 4.8 ±0.5 2 6.8 ±0.6 (1-2) 9.6 ±0.7 1 13.6 ±1.0

[0077] Determination of impact property: test based on ISO 179, test pendulum energy at 23℃, which can be selected as 2J.

[0078] Determination of flexural modulus: test based on ISO 178, loading speed: 2mm / min.

[0079] Examples 1-22

[0080] The present examples provide a series of polypropylene compositions, the weight fraction of each component in the formula, the chemical resistance to electroplating, impact properties and flexural modulus are shown in Table 2 and Table 3.

[0081] Table 2 Formulation of Examples 1-14 (parts)

[0082]

[0083] Table 3 Formulation of Examples 15-22 (parts)

[0084]

[0085]

[0086] Comparative Examples 1-10

[0087] The present comparative examples provide a series of polypropylene compositions, the weight fraction of each component in the formula, the chemical resistance to electroplating, impact properties and flexural modulus are shown in Table 4.

[0088] Table 4 Formulation of Comparative Examples 1-10 (parts)

[0089]

[0090]

[0091] As can be seen from Table 2 and Table 3, the polypropylene compositions prepared in Examples 1-22 of the present application all have the characteristics of chemical resistance to electroplating, the impact strength can reach 3.1 KJ / m 2 The above, the flexural modulus can reach 1765 MPa or more, wherein the comprehensive performance of Example 1 is the best, the mechanical properties and the resistance to electroplating are maintained. As can be seen from Table 4, in Comparative Example 1, the polypropylene with a degree of isotacticity less than 97.5% is used as the matrix, and micro-cracks appear after chemical resistance; in Comparative Examples 2 and 3, the weight fraction of PE wax is not within the range set by the present application, and the polypropylene material appears micro-cracks, whitening, deformation, cracks or delamination after chemical resistance; in Comparative Example 4, the amount of amide lubricant exceeds the range set by the present application, and delamination occurs; in Comparative Example 5, a non-amide lubricant is used for modification, and micro-cracks appear after chemical resistance; in Comparative Example 6, the amount of nucleating agent is too much, resulting in warping deformation and color grade rising, indicating that the amount of nucleating agent needs to be within a certain range; in Comparative Examples 7-8, a non-carboxylic acid metal salt or a non-phosphoric acid metal salt is used as a nucleating agent for modification, and white precipitates appear after chemical resistance; in Comparative Example 9, the amount of amide lubricant added is 0, and the surface appears whitening after chemical resistance; in Comparative Example 10, the amount of nucleating agent added is 0, and the surface appears swelling after chemical resistance.

[0092] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A plating chemical resistant polypropylene composition comprising the following components in parts by weight: polypropylene resin 90-100 parts, PE wax 0.3-1 part, amide lubricant 0.3-0.6 part, glyceride lubricant 0.3-0.6 part, nucleating agent 0.1-0.5 part, glass fiber 0-5 parts; wherein the polypropylene resin has an isotacticity of ≥ 97.5%, and the nucleating agent is at least one of carboxylic acid metal salt or organic phosphoric acid metal salt. wherein The polypropylene resin has a melt mass flow rate of 10-60 g / 10 min at 230℃ under a load of 2.16 kg.

2. The polypropylene composition according to claim 1, characterized in that The amide lubricant is at least one of erucamide, stearyl erucamide, oleamide or behenyl fatty amide.

3. The polypropylene composition according to claim 1, characterized in that The glyceride lubricant is at least one of glycerol monostearate, glycerol laurate or fatty acid diglyceride.

4. The polypropylene composition according to claim 1, characterized in that The carboxylic acid metal salt is at least one of sodium benzoate, potassium benzoate or sodium p-toluenesulfonate.

5. The polypropylene composition according to claim 1, characterized in that The organic phosphoric acid metal salt is at least one of sodium 2,2'-methylenebis(2.4-di-tert-butylphenoxy)phosphate, 2.2'-methylenebis(4.6-di-tert-butylphenoxy)phosphate, aluminum basic salt or sodium p-tert-butylphenoxyphosphate.

6. The polypropylene composition according to claim 1, characterized in that The plating chemical resistant polypropylene composition further comprises other auxiliary agents 0.4-1.6 parts.

7. The polypropylene composition according to claim 1, characterized in that 8. A method for preparing the polypropylene composition of any one of claims 1-7, comprising the following steps: S1. mixing polypropylene resin, amide lubricant, glyceride lubricant, PE wax, nucleating agent, optional glass fiber and other auxiliary agents uniformly to obtain a mixture; S2. melt mixing the mixture, extruding and granulating to obtain the polypropylene composition.

9. Use of the polypropylene composition of any one of claims 1-7 in the preparation of parts for electroplating tank and hanger.

10. A part for electroplating tank and hanger prepared from the polypropylene composition of any one of claims 1-7. ​

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