Wear-resistant antistatic paint and preparation method thereof

Abstract

The application relates to the field of paint technology and discloses a wear-resistant and antistatic paint and a preparation method thereof.The wear-resistant and antistatic paint comprises the following raw materials: cyclohexyl methacrylate, isopropyl methacrylate, pentafluorophenyl methacrylate, alcohol acid resin surface modified cerium dioxide, antistatic and antibacterial additive, an initiator, acetone, a fatty alcohol polyoxyethylene ether defoaming agent and a polyurethane leveling agent.The alcohol acid resin surface modified cerium dioxide and the antistatic and antibacterial additive are involved in the preparation process of the paint binder, so that the prepared paint has excellent wear resistance, antistatic capacity and antibacterial effect, can meet the use requirements in various environments, has a great application field and a long service life.

Description

Technical Field

[0001] This invention relates to the field of paint technology, specifically to a wear-resistant and antistatic paint and its preparation method. Background Technology

[0002] In modern industrial production and daily life, paint, as a common coating, not only gives objects a beautiful appearance but also protects them and extends their service life. It is widely used in various fields such as machinery, construction, furniture, and transportation. With the advancement of technology and industrial development, people's requirements for paint are also getting higher and higher. Especially in fields such as coal mines and petrochemicals, ordinary paint does not have anti-static capabilities. When a large amount of dust, gas, or liquid is present, static electricity is easily generated. Static electricity accumulation can form electric sparks, which can easily cause fires or even explosions, posing a great safety hazard. In fields such as machinery and construction, ordinary paint generally has poor adhesion and lacks wear resistance, making it easy to break and peel off, losing its protective function on the substrate. In cool and humid environments or environments requiring sterility, ordinary paint does not have antibacterial effects, and bacteria can easily multiply, thus limiting the application areas of ordinary paint.

[0003] Patent CN104744988B discloses a nano-alumina dispersion for improving the wear resistance of polyurethane paint and a method for preparing ultra-wear-resistant polyurethane paint. Although the paint prepared by this patent has excellent wear resistance, its antibacterial and antistatic capabilities need to be improved, making it difficult to meet the needs of use in various environments and greatly limiting the application areas of this type of paint. Summary of the Invention

[0004] The purpose of this invention is to provide a wear-resistant and antistatic paint and its preparation method, which solves the following technical problems: (1) Ordinary paint has general wear resistance, is easy to break, has weak adhesion and is easy to fall off; (2) Ordinary paint does not have antistatic and antibacterial capabilities, which limits its application field.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A wear-resistant and antistatic paint comprises the following raw materials in parts by weight: 30-40 parts cyclohexyl methacrylate, 25-35 parts isopropyl methacrylate, 12-15 parts pentafluorophenyl methacrylate, 10-15 parts alkyd resin surface-modified cerium dioxide, 8-12 parts antistatic and antibacterial additives, 3-6 parts initiator, 120-150 parts acetone, 2-3 parts fatty alcohol polyoxyethylene ether defoamer, and 1.5-2.5 parts polyurethane leveling agent; wherein the alkyd resin surface... Modified cerium dioxide is prepared by modifying the surface of nano-cerium dioxide with norbornene-modified alkyd resin; the norbornene-modified alkyd resin is prepared by reacting terminal hydroxyl alkyd resin with methyl-5-norbornene-2,3-dianhydride; the antistatic and antibacterial additive is prepared by reacting quaternized poly(4-vinyl)pyridine with ursolic acid under the action of a catalyst; the quaternized poly(4-vinyl)pyridine is prepared by reacting poly(4-vinyl)pyridine with chloroacetic acid.

[0007] Furthermore, the initiator is either benzoyl peroxide or dicumyl peroxide.

[0008] Furthermore, the preparation method of the alkyd resin modified cerium dioxide includes the following steps:

[0009] S1: Hydroxyl-terminated alkyd resin and methyl-5-norbornene-2,3-dianhydride are placed in toluene, nitrogen gas is introduced, and the mixture is stirred and mixed thoroughly. The mixture is heated to 70-75℃ and reacted for 6-8 hours. After removing the solvent by vacuum distillation, the product is collected to obtain norbornene-modified alkyd resin.

[0010] S2: Place nano-cerium dioxide in deionized water, ultrasonically disperse for 10-15 min, add norbornene-modified alkyd resin, heat and stir, filter, wash and dry to obtain alkyd resin surface-modified cerium dioxide.

[0011] In this scheme, under a nitrogen atmosphere, the hydroxyl groups in the terminal hydroxyl alkyd resin structure react with the anhydride structure in the methyl-5-norbornene-2,3-dianhydride structure to obtain norbornene-modified alkyd resin. Through the interaction between the carboxyl groups in the norbornene-modified alkyd resin structure and the hydroxyl groups on the surface of nano-cerium dioxide, cerium dioxide modified on the surface of the alkyd resin is obtained. This alkyd resin surface-modified cerium dioxide has a norbornene structure and alkyd resin polymer segments coated on the surface of nano-cerium dioxide. This effectively enhances the dispersibility of nano-cerium dioxide in the paint matrix. At the same time, the active alkenyl groups in the norbornene structure on its surface can participate in the preparation process of the paint base material, forming an organic-inorganic wear-resistant component with nano-cerium dioxide, producing a synergistic effect and effectively enhancing the wear resistance of the paint base material. In addition, the alkyd resin on its surface can effectively enhance the adhesion of the paint base material, so that the prepared paint not only has excellent wear resistance, but also enhances the adhesion between the paint and the substrate material, making it less likely to fall off after use and curing, and effectively extending the service life of the paint.

[0012] Further, in step S1, the mass ratio of the terminal hydroxyl alkyd resin to methyl-5-norbornene-2,3-dianhydride is 3-5:2.6-4.

[0013] Furthermore, in step S2, the temperature for heating and stirring is 95-105℃, and the time is 5-6 hours.

[0014] Furthermore, the preparation method of the antistatic and antibacterial additive includes the following steps:

[0015] SS1: Poly(4-vinyl)pyridine was placed in toluene, mixed and stirred thoroughly, then chloroacetic acid was added, and the mixture was heated under reflux. After cooling to room temperature, the product was collected to obtain quaternized poly(4-vinyl)pyridine.

[0016] SS2: Quaternized poly(4-vinyl)pyridine is placed in N,N-dimethylformamide, thoroughly mixed and stirred, then ursolic acid and catalyst are added, and the mixture is heated to 100-105℃ and reacted for 3-5 hours to obtain an antistatic and antibacterial additive.

[0017] In this scheme, the tertiary amine in the pyridine ring of the poly(4-vinyl)pyridine structure undergoes a quaternization reaction with the active chlorine in the chloroacetic acid structure to obtain quaternized poly(4-vinyl)pyridine. Then, under the action of a catalyst, the carboxyl group in the quaternized poly(4-vinyl)pyridine structure undergoes an esterification reaction with the hydroxyl group in the ursolic acid structure to obtain an antistatic and antibacterial additive. This antistatic and antibacterial additive structure contains multiple quaternary ammonium groups, which can effectively enhance the antistatic ability of the paint and also effectively enhance its antibacterial effect. It works synergistically with the ursolic acid introduced into its structure to jointly enhance the antibacterial ability of the paint. Simultaneously, the alkenyl group in the ursolic acid structure can participate in the preparation process of the paint matrix material, producing cross-linking, effectively enhancing the density and wear resistance of the paint matrix, and effectively expanding the application fields of the paint to meet the needs of various environments.

[0018] Furthermore, in step SS1, the heating reflux reaction time is 8-12 hours.

[0019] Furthermore, in step SS2, the catalyst is either p-toluenesulfonic acid or aminobenzenesulfonic acid.

[0020] A method for preparing a wear-resistant and antistatic paint includes the following steps:

[0021] Step 1: Place cyclohexyl methacrylate, isopropyl methacrylate, pentafluorophenyl methacrylate, alkyd resin surface-modified cerium dioxide, antistatic and antibacterial additives and initiator in acetone, heat to 50-55℃ and stir thoroughly for 3-5 hours to obtain paint base material;

[0022] Step 2: Add fatty alcohol polyoxyethylene ether defoamer and polyurethane leveling agent to the paint base, and stir thoroughly at a speed of 200-300 r / min for 1-1.5 h to obtain wear-resistant and antistatic paint.

[0023] The beneficial effects of this invention are:

[0024] This invention incorporates surface-modified cerium dioxide and antistatic / antibacterial additives into the preparation process of paint base materials, resulting in paints with excellent wear resistance, antistatic properties, and antibacterial effects, meeting the needs of various environments and having a long service life.

[0025] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a flowchart illustrating the preparation process of the wear-resistant and antistatic paint of this invention. Detailed Implementation

[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] The preparation methods of alkyd resin surface-modified cerium dioxide and antistatic antibacterial additives in the following embodiments and comparative examples of the present invention are as follows:

[0030] I. Preparation of Cerium Dioxide Surface Modification on Alkyd Resin

[0031] S1: 3g of terminal hydroxyl alkyd resin and 2.6g of methyl-5-norbornene-2,3-dianhydride were placed in 60ml of toluene, nitrogen gas was introduced, and the mixture was stirred and mixed thoroughly. The mixture was heated to 70℃ and reacted for 6h. After removing the solvent by vacuum distillation, the product was collected to obtain norbornene modified alkyd resin.

[0032] S2: Place 3g of nano-cerium dioxide in 100ml of deionized water, ultrasonically disperse for 10min, add 2.8g of norbornene-modified alkyd resin, heat to 95℃ and stir thoroughly for 5h, filter, wash and dry to obtain alkyd resin surface-modified cerium dioxide.

[0033] II. Preparation of Antistatic and Antibacterial Additives

[0034] SS1: 3.2 g of poly(4-vinyl)pyridine was placed in 80 ml of toluene, mixed and stirred thoroughly, and then 2.8 g of chloroacetic acid was added. The mixture was heated under reflux for 8 h, and the product was collected after cooling to room temperature to obtain quaternized poly(4-vinyl)pyridine.

[0035] SS2: Place 3.5g of quaternized poly(4-vinyl)pyridine in 100ml of N,N-dimethylformamide, mix and stir thoroughly, then add 3g of ursolic acid and 0.3g of p-toluenesulfonic acid, heat to 100℃ and react for 3h to obtain an antistatic and antibacterial additive. Example 1

[0036] Preparation of wear-resistant and antistatic paint

[0037] Step 1: Place 30 parts of cyclohexyl methacrylate, 25 parts of isopropyl methacrylate, 12 parts of pentafluorophenyl methacrylate, 10 parts of alkyd resin surface-modified cerium dioxide, 8 parts of antistatic and antibacterial additives and 3 parts of benzoyl peroxide into 120 parts of acetone, heat to 50°C and stir thoroughly for 3 hours to obtain paint base material.

[0038] Step 2: Add 2 parts of fatty alcohol polyoxyethylene ether defoamer and 1.5 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 200 r / min for 1 hour to obtain wear-resistant and antistatic paint. Example 2

[0039] Preparation of wear-resistant and antistatic paint

[0040] Step 1: Place 35 parts of cyclohexyl methacrylate, 30 parts of isopropyl methacrylate, 13 parts of pentafluorophenyl methacrylate, 12 parts of alkyd resin surface-modified cerium dioxide, 10 parts of antistatic and antibacterial additives and 4 parts of dicumyl peroxide into 130 parts of acetone, heat to 52°C and stir thoroughly for 4 hours to obtain paint base material.

[0041] Step 2: Add 2.5 parts of fatty alcohol polyoxyethylene ether defoamer and 2 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 250 r / min for 1.2 h to obtain wear-resistant and antistatic paint. Example 3

[0042] Preparation of wear-resistant and antistatic paint

[0043] Step 1: Place 40 parts of cyclohexyl methacrylate, 35 parts of isopropyl methacrylate, 15 parts of pentafluorophenyl methacrylate, 15 parts of alkyd resin surface-modified cerium dioxide, 12 parts of antistatic and antibacterial additives and 6 parts of benzoyl peroxide into 150 parts of acetone, heat to 55°C and stir thoroughly for 5 hours to obtain paint base material.

[0044] Step 2: Add 3 parts of fatty alcohol polyoxyethylene ether defoamer and 2.5 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 300 r / min for 1.5 h to obtain wear-resistant and antistatic paint.

[0045] Comparative Example 1

[0046] Paint preparation

[0047] Step 1: Place 35 parts of cyclohexyl methacrylate, 30 parts of isopropyl methacrylate, 13 parts of pentafluorophenyl methacrylate, 10 parts of antistatic and antibacterial additives and 4 parts of dicumyl peroxide into 130 parts of acetone, heat to 52°C and stir thoroughly for 4 hours to obtain paint base material.

[0048] Step 2: Add 2.5 parts of fatty alcohol polyoxyethylene ether defoamer and 2 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 250 r / min for 1.2 h to obtain the paint.

[0049] Comparative Example 2

[0050] Paint preparation

[0051] Step 1: Place 35 parts of cyclohexyl methacrylate, 30 parts of isopropyl methacrylate, 13 parts of pentafluorophenyl methacrylate, 12 parts of alkyd resin surface-modified cerium dioxide, and 4 parts of dicumyl peroxide into 130 parts of acetone, heat to 52°C and stir thoroughly for 4 hours to obtain paint base material.

[0052] Step 2: Add 2.5 parts of fatty alcohol polyoxyethylene ether defoamer and 2 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 250 r / min for 1.2 h to obtain the paint.

[0053] Comparative Example 3

[0054] Paint preparation

[0055] Step 1: Place 35 parts of cyclohexyl methacrylate, 30 parts of isopropyl methacrylate, 13 parts of pentafluorophenyl methacrylate, 12 parts of nano-cerium dioxide, 10 parts of antistatic and antibacterial additives and 4 parts of dicumyl peroxide into 130 parts of acetone, heat to 52°C and stir thoroughly for 4 hours to obtain paint base material.

[0056] Step 2: Add 2.5 parts of fatty alcohol polyoxyethylene ether defoamer and 2 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 250 r / min for 1.2 h to obtain the paint.

[0057] Comparative Example 4

[0058] Paint preparation

[0059] Step 1: Place 35 parts of cyclohexyl methacrylate, 30 parts of isopropyl methacrylate, 13 parts of pentafluorophenyl methacrylate, 12 parts of alkyd resin surface-modified cerium dioxide, 10 parts of quaternized poly(4-vinyl)pyridine and 4 parts of dicumyl peroxide into 130 parts of acetone, heat to 52°C and stir thoroughly for 4 hours to obtain paint base material;

[0060] Step 2: Add 2.5 parts of fatty alcohol polyoxyethylene ether defoamer and 2 parts of polyurethane leveling agent to the paint base, and stir thoroughly at 250 r / min for 1.2 h to obtain the paint.

[0061] Performance testing

[0062] The paints prepared in Examples 1-3 and Comparative Examples 1-4 were applied to steel plates and cured to form samples that met specifications. An MMW-1G universal friction and wear testing machine was used to conduct a wear test on the samples for 8 minutes under a load of 100 N and a rotation speed of 100 r / min. The mass of the samples before and after wear was measured, and the wear value was calculated according to the following formula: Wear value = Mass before wear - Mass after wear. The smaller the wear value, the stronger the wear resistance of the sample. The resistivity of the sample surface was tested using a DRK321B-II surface resistivity tester to determine its antistatic ability. The adhesion level of the samples was tested according to standard GB / T1727-2021 to determine the sample adhesion. The antibacterial rate of the samples was calculated according to standard GB / T21866-2008 to test the antibacterial performance of the samples. Specific test results are shown in the table below:

[0063]

[0064] As shown in the table above, the samples prepared in Examples 1-3 all exhibit excellent wear resistance, antistatic properties, adhesion, and antibacterial effects. The sample prepared in Comparative Example 1 did not contain alkyd resin surface-modified cerium dioxide, the sample prepared in Comparative Example 2 did not contain antistatic and antibacterial additives, the sample prepared in Comparative Example 3 directly contained nano-cerium dioxide and antistatic and antibacterial additives, and the sample prepared in Comparative Example 4 directly contained alkyd resin surface-modified cerium dioxide and quaternized poly(4-vinyl)pyridine. Compared with the samples prepared in the examples, the samples prepared in the comparative examples do not have the same wear resistance, antistatic properties, adhesion, and antibacterial effects.

[0065] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0066] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the inventive concept, they should all fall within the protection scope of the present invention.

Claims

1. A wear-resistant and antistatic paint, characterized in that, The raw materials include the following parts by weight: 30-40 parts cyclohexyl methacrylate, 25-35 parts isopropyl methacrylate, 12-15 parts pentafluorophenyl methacrylate, 10-15 parts alkyd resin surface-modified cerium dioxide, 8-12 parts antistatic and antibacterial additive, 3-6 parts initiator, 120-150 parts acetone, 2-3 parts fatty alcohol polyoxyethylene ether defoamer, and 1.5-2.5 parts polyurethane leveling agent; the alkyd resin surface-modified cerium dioxide is obtained by modifying the surface of nano-cerium dioxide with norbornene-modified alkyd resin; the norbornene-modified alkyd resin is obtained by reacting terminal hydroxyl alkyd resin with methyl-5-norbornene-2,3-dianhydride; the antistatic and antibacterial additive is obtained by reacting quaternized poly(4-vinyl)pyridine with ursolic acid under the action of a catalyst; the quaternized poly(4-vinyl)pyridine is obtained by reacting poly(4-vinyl)pyridine with chloroacetic acid.

2. The wear-resistant and antistatic paint according to claim 1, characterized in that, The initiator is either benzoyl peroxide or dicumyl peroxide.

3. The wear-resistant and antistatic paint according to claim 1, characterized in that, The preparation method of the alkyd resin modified cerium dioxide includes the following steps: S1: Hydroxyl-terminated alkyd resin and methyl-5-norbornene-2,3-dianhydride are placed in toluene, nitrogen gas is introduced, and the mixture is stirred and mixed thoroughly. The mixture is heated to 70-75℃ and reacted for 6-8 hours. After removing the solvent by vacuum distillation, the product is collected to obtain norbornene-modified alkyd resin. S2: Place nano-cerium dioxide in deionized water, ultrasonically disperse for 10-15 min, add norbornene-modified alkyd resin, heat and stir, filter, wash and dry to obtain alkyd resin surface-modified cerium dioxide.

4. The wear-resistant and antistatic paint according to claim 3, characterized in that, In step S1, the mass ratio of the terminal hydroxyl alkyd resin to methyl-5-norbornene-2,3-dianhydride is 3-5:2.6-4.

5. The wear-resistant and antistatic paint according to claim 3, characterized in that, In step S2, the temperature for heating and stirring is 95-105℃, and the time is 5-6 hours.

6. The wear-resistant and antistatic paint according to claim 1, characterized in that, The preparation method of the antistatic and antibacterial additive includes the following steps: SS1: Poly(4-vinyl)pyridine was placed in toluene, mixed and stirred thoroughly, then chloroacetic acid was added, and the mixture was heated under reflux. After cooling to room temperature, the product was collected to obtain quaternized poly(4-vinyl)pyridine. SS2: Quaternized poly(4-vinyl)pyridine is placed in N,N-dimethylformamide, thoroughly mixed and stirred, then ursolic acid and catalyst are added, and the mixture is heated to 100-105℃ and reacted for 3-5 hours to obtain an antistatic and antibacterial additive.

7. The wear-resistant and antistatic paint according to claim 6, characterized in that, In step SS1, the heating reflux reaction takes 8-12 hours.

8. The wear-resistant and antistatic paint according to claim 6, characterized in that, In step SS2, the catalyst is either p-toluenesulfonic acid or aminobenzenesulfonic acid.

9. A method for preparing the wear-resistant and antistatic paint as described in claim 1, characterized in that, Includes the following steps: Step 1: Place cyclohexyl methacrylate, isopropyl methacrylate, pentafluorophenyl methacrylate, alkyd resin surface-modified cerium dioxide, antistatic and antibacterial additives and initiator in acetone, heat to 50-55℃ and stir thoroughly for 3-5 hours to obtain paint base material; Step 2: Add fatty alcohol polyoxyethylene ether defoamer and polyurethane leveling agent to the paint base, and stir thoroughly at a speed of 200-300 r / min for 1-1.5 h to obtain wear-resistant and antistatic paint.

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