An environment-friendly paint and a preparation method thereof

Abstract

The application relates to the field of paint technology and discloses an environment-friendly paint and a preparation method thereof, the environment-friendly paint comprising the following raw materials: phenyl acrylate, styrene, lauryl methacrylate, tert-butyl acrylate, antifouling and anticorrosion cellulose, coumalic acid modified polyether, anhydrous ethanol, an initiator, dimethyl silicone oil defoaming agent and polyurethane leveling agent; the antifouling and anticorrosion cellulose and the coumalic acid modified polyether are prepared and involved in the preparation process of the paint matrix, so that the prepared environment-friendly paint has excellent antifouling and anticorrosion capacity, high toughness and is not easy to be damaged, and has excellent antioxidant effect, can meet the use requirements in various environments, does not need to be frequently replaced even when being used for a long time, saves cost, and has a long service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of paint technology, and in particular to an environmentally friendly paint and a preparation method thereof. BACKGROUND

[0002] As an important part of the paint industry, paint is widely used in many fields such as building, furniture, automobile, mechanical engineering, etc., and plays a protective and aesthetic effect. However, with the development of science and technology, the drawbacks of traditional paint gradually appear. In actual use, the anti-fouling and anti-corrosion ability of traditional paint is obviously insufficient, especially in harsh environments such as high humidity, high salt content and high pollution environment. The protective ability of traditional paint is weak, and the problem of coating peeling and rusting easily occurs, which loses the protection effect on the base material. Moreover, the traditional paint has poor oxidation resistance and is easy to oxidize, and has poor durability. Therefore, when using traditional paint, the paint coating needs to be replaced frequently, which not only increases the use cost, but also easily damages the base material during frequent replacement and polishing, causing unnecessary loss. Especially in recent years, with the proposal of the environmental protection concept, the use of traditional paint with environmentally unfriendly solvents such as benzene has been difficult to meet the needs of green development at the present stage.

[0003] Therefore, the patent with publication number CN110218497B discloses a kind of corrosion-resistant water-based paint and its preparation process, which solves the problem that the overall application effect is poor due to the poor salt water corrosion resistance of water-based paint. The corrosion-resistant water-based paint prepared by the invention has good corrosion resistance and toughness, is friendly to the environment and has little pollution, and has good overall application effect. However, the corrosion-resistant water-based paint prepared by the patent has general antioxidant capacity, and the coating may need to be replaced frequently in actual use, which is not conducive to the protection of the base material and increases the use cost. SUMMARY

[0004] The present application aims to provide an environmentally friendly paint and a preparation method thereof, which solves the following technical problems: (1) the problem that the anti-fouling and anti-corrosion performance of ordinary paint needs to be improved; (2) the problem that the ordinary paint has general antioxidant capacity and short service life; (3) the problem that the ordinary paint uses environmentally unfriendly solvents as dispersants, which is not friendly to the environment.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] The environment-friendly paint comprises the following raw materials in parts by weight: 25-30 parts of phenyl acrylate, 20-25 parts of styrene, 15-20 parts of lauryl methacrylate, 10-15 parts of tert-butyl acrylate, 12-15 parts of anti-fouling and anti-corrosion cellulose, 8-10 parts of coumaric acid modified polyether, 100-150 parts of anhydrous ethanol, 8-10 parts of initiator, 3-5 parts of dimethyl silicone oil defoaming agent, and 2-3 parts of polyurethane leveling agent; the anti-fouling and anti-corrosion cellulose is prepared by reacting organic fluorine modified bacterial cellulose with pentaerythritol triacrylate; the organic fluorine modified bacterial cellulose is prepared by reacting bacterial cellulose with tetrafluoro-phthalic anhydride; and the coumaric acid modified polyether is prepared by reacting allyl alcohol polyether with coumaric acid.

[0007] Further, the initiator is any one of benzoyl peroxide, dicumyl peroxide and tert-butyl peroxybenzoate.

[0008] Further, the preparation method of the anti-fouling and anti-corrosion cellulose comprises the following steps:

[0009] S1: mixing bacterial cellulose with butanone, introducing nitrogen, adding tetrafluoro-phthalic anhydride, and heating to 65-70 DEG C for 5-8 h; after the reaction is completed, removing the solvent by distillation under reduced pressure to obtain the organic fluorine modified bacterial cellulose;

[0010] S2: placing the organic fluorine modified bacterial cellulose in N-methyl pyrrolidone, mixing and stirring, adding pentaerythritol triacrylate and a catalyst, and heating to 90-100 DEG C for 6-8 h; after the reaction is completed, removing the solvent by distillation under reduced pressure to obtain the anti-fouling and anti-corrosion cellulose.

[0011] In the scheme, the hydroxyl groups in the structure of the bacterial cellulose react with the acid anhydride groups in the structure of the tetrafluoro-phthalic anhydride under a nitrogen atmosphere to obtain the organic fluorine modified bacterial cellulose; and under the action of the catalyst, the carboxyl groups in the structure of the organic fluorine modified bacterial cellulose esterify with the hydroxyl groups in the structure of the pentaerythritol triacrylate to obtain the anti-fouling and anti-corrosion cellulose. The anti-fouling and anti-corrosion cellulose uses the bacterial cellulose as a high molecular skeleton, can effectively enhance the toughness of the paint film of the environment-friendly paint, makes it not easy to crack, introduces the organic fluorine with low surface energy into the structure, can effectively enhance the anti-fouling and anti-corrosion ability of the environment-friendly paint, makes it keep clean even in the environment surrounded by oil stains, is easy to clean, and can block the invasion of corrosive media, so that it can be used in the environment where corrosive media exist, greatly expands the use field of the paint, and meanwhile, the anti-fouling and anti-corrosion cellulose structure also has multiple alkenyl groups, which can participate in the preparation process of the paint base material, crosslink with the base material, form a three-dimensional network structure, and further enhance the toughness and anti-corrosion and anti-fouling ability of the paint film.

[0012] Further, in step S2, the catalyst is any one of p-toluenesulfonic acid, aminobenzenesulfonic acid.

[0013] Further, the preparation method of the coumaric acid modified polyether comprises the following steps:

[0014] The allyl alcohol polyether and the coumaric acid are placed in N,N-dimethylformamide, after sufficient mixing and stirring, p-toluenesulfonic acid is added, the reaction is carried out by heating, the solvent is removed by distillation under reduced pressure, and the product is collected to obtain the coumaric acid modified polyether.

[0015] In the scheme, under the action of p-toluenesulfonic acid, the hydroxyl in the structure of the allyl alcohol polyether reacts with the carboxyl in the structure of the coumaric acid to obtain the coumaric acid modified polyether, the coumaric acid modified polyether takes the allyl alcohol polyether as a high molecular skeleton, a plurality of ether bonds in the structure can effectively enhance the adhesion between the paint and the base material, the coumaric acid as a phenolic antioxidant can scavenge free radicals and inhibit the activity of enzymes that produce free radicals, has excellent antioxidant capacity, is chemically connected to the high molecular skeleton of the allyl alcohol polyether, can protect the coumaric acid, prevent the migration of the coumaric acid small molecules during long-term use, and the alkene in the structure of the coumaric acid modified polyether can participate in the free radical polymerization process of the paint base material, further protects the small molecule active ingredients in the structure, so that the excellent antioxidant effect can be long-term, and the service life of the paint is significantly prolonged.

[0016] Further, the temperature of the heating reaction is 95-105 DEG C, and the time is 5-6 h.

[0017] A preparation method of an environment-friendly paint comprises the following steps:

[0018] Step one, the phenyl acrylate, styrene, lauryl methacrylate, tert-butyl acrylate, antifouling anticorrosive cellulose and coumaric acid modified polyether are placed in anhydrous ethanol, an initiator is added, the temperature is increased to 50-55 DEG C, and sufficient stirring is carried out to obtain an environment-friendly paint base material.

[0019] Step two, the dimethyl silicone oil defoaming agent and the polyurethane leveling agent are added into the environment-friendly paint base material and uniformly mixed to obtain the environment-friendly paint.

[0020] Further, in step one, the rotation speed of the sufficient stirring is 200-300 r / min, and the time is 6-8 h.

[0021] The beneficial effects of the present application are:

[0022] The cellulose with antifouling and anticorrosion is prepared, and the cellulose with antifouling and anticorrosion is modified by coumaric acid to participate in the preparation process of the environment-friendly paint, so that the prepared environment-friendly paint has excellent antifouling and anticorrosion capacity, is not easy to break and has excellent antioxidant effect, can meet the use requirements in various environments and has a long service life.

[0023] Of course, implementing any product of the present application does not necessarily require achieving all the advantages described above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0025] Figure 1 The preparation process of the environment-friendly paint of the present application. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0027] The preparation methods of the coumaric acid modified polyether and the antifouling and anticorrosion cellulose in the following embodiments and comparative examples of the present application are as follows:

[0028] I. Preparation of coumaric acid modified polyether

[0029] 4g of allyl alcohol polyether and 3.8g of coumaric acid were taken into 60ml of N,N-dimethylformamide, and after fully mixed and stirred, 0.6g of p-toluenesulfonic acid was added, and the temperature was raised to 95℃ for reaction for 5h, and the solvent was removed by distillation under reduced pressure, and the product was collected to obtain the coumaric acid modified polyether.

[0030] II. Preparation of antifouling and anticorrosion cellulose

[0031] S1: 3.5g of bacterial cellulose was mixed with 80ml of butanone, nitrogen was introduced, 3.2g of tetrafluoro phthalic anhydride was added, the temperature was raised to 65℃ for reaction for 5h, and after the reaction was completed, the solvent was removed by distillation under reduced pressure, and the product was collected to obtain the organic fluorine modified bacterial cellulose;

[0032] S2: 3.8 g of organic fluorine-modified bacterial cellulose was placed in 100 ml of N-methyl pyrrolidone, after sufficient mixing and stirring, 2.5 g of pentaerythritol triacrylate and 0.5 g of p-toluene sulfonic acid were added, and the temperature was raised to 90℃ and reacted for 6 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the product was collected to obtain the antifouling and anticorrosion cellulose. Example 1

[0033] Preparation method of environment-friendly paint

[0034] Step one, 25 parts of phenyl acrylate, 20 parts of styrene, 15 parts of lauryl methacrylate, 10 parts of tert-butyl acrylate, 12 parts of antifouling and anticorrosion cellulose, 8 parts of coumaric acid modified polyether were placed in 100 parts of anhydrous ethanol, 8 parts of benzoyl peroxide was added, the temperature was raised to 50℃, and stirred at 200 r / min for 6 h to obtain the environment-friendly paint base material;

[0035] Step two, 3 parts of dimethyl silicone oil defoaming agent and 2 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain the environment-friendly paint. Example 2

[0036] Preparation method of environment-friendly paint

[0037] Step one, 28 parts of phenyl acrylate, 23 parts of styrene, 18 parts of lauryl methacrylate, 13 parts of tert-butyl acrylate, 13 parts of antifouling and anticorrosion cellulose, 9 parts of coumaric acid modified polyether were placed in 120 parts of anhydrous ethanol, 9 parts of dicumyl peroxide was added, the temperature was raised to 53℃, and stirred at 250 r / min for 7 h to obtain the environment-friendly paint base material;

[0038] Step two, 4 parts of dimethyl silicone oil defoaming agent and 2.5 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain the environment-friendly paint. Example 3

[0039] Preparation method of environment-friendly paint

[0040] Step one, 30 parts of phenyl acrylate, 25 parts of styrene, 20 parts of lauryl methacrylate, 15 parts of tert-butyl acrylate, 15 parts of antifouling and anticorrosion cellulose, 10 parts of coumaric acid modified polyether were placed in 150 parts of anhydrous ethanol, 10 parts of tert-butyl benzoyl peroxide was added, the temperature was raised to 55℃, and stirred at 300 r / min for 8 h to obtain the environment-friendly paint base material;

[0041] Step two, 5 parts of dimethyl silicone oil defoaming agent and 3 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain the environment-friendly paint.

[0042] Comparative example 1

[0043] Preparation method of environment-friendly paint

[0044] Step one, 28 parts of phenyl acrylate, 23 parts of styrene, 18 parts of lauryl methacrylate, 13 parts of tert-butyl acrylate, 9 parts of coumaric acid modified polyether were placed in 120 parts of anhydrous ethanol, 9 parts of dicumyl peroxide was added, the temperature was raised to 53℃, and stirred at 250r / min for 7h, to obtain an environment-friendly paint base material;

[0045] Step two, 4 parts of dimethyl silicone oil defoaming agent, 2.5 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain an environment-friendly paint.

[0046] Comparative example 2

[0047] Preparation method of environment-friendly paint

[0048] Step one, 28 parts of phenyl acrylate, 23 parts of styrene, 18 parts of lauryl methacrylate, 13 parts of tert-butyl acrylate, 13 parts of antifouling and corrosion-resistant cellulose were placed in 120 parts of anhydrous ethanol, 9 parts of dicumyl peroxide was added, the temperature was raised to 53℃, and stirred at 250r / min for 7h, to obtain an environment-friendly paint base material;

[0049] Step two, 4 parts of dimethyl silicone oil defoaming agent, 2.5 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain an environment-friendly paint.

[0050] Comparative example 3

[0051] Preparation method of environment-friendly paint

[0052] Step one, 28 parts of phenyl acrylate, 23 parts of styrene, 18 parts of lauryl methacrylate, 13 parts of tert-butyl acrylate were placed in 120 parts of anhydrous ethanol, 9 parts of dicumyl peroxide was added, the temperature was raised to 53℃, and stirred at 250r / min for 7h, to obtain an environment-friendly paint base material;

[0053] Step two, 4 parts of dimethyl silicone oil defoaming agent, 2.5 parts of polyurethane leveling agent were added to the environment-friendly paint base material and mixed uniformly to obtain an environment-friendly paint.

[0054] Comparative example 4

[0055] Preparation method of environment-friendly paint

[0056] Step one, 28 parts of phenyl acrylate, 23 parts of styrene, 18 parts of lauryl methacrylate, 13 parts of tert-butyl acrylate, 13 parts of organic fluorine modified bacterial cellulose, 9 parts of coumaric acid modified polyether were placed in 120 parts of anhydrous ethanol, 9 parts of dicumyl peroxide was added, the temperature was raised to 53℃, and stirred at 250r / min for 7h, to obtain an environment-friendly paint base material;

[0057] Step two, add 4 parts of dimethyl silicone oil defoaming agent, 2.5 parts of polyurethane leveling agent to the environmentally friendly paint base material and mix uniformly to obtain the environmentally friendly paint.

[0058] Performance detection

[0059] The environmentally friendly paints prepared by example 1 to example 3, comparative example 1 to comparative example 4 were coated on the steel plate meeting the specifications, and after curing, the samples were prepared. The adhesion grade test of the samples was carried out according to the standard GB / T1727-2021; the salt spray test of the samples was carried out according to the standard GB / T1771-2007 to judge the corrosion resistance of the samples; the water contact angle test of the samples was carried out using PZ-200SD type contact angle tester to judge the antifouling ability of the samples; the samples were placed in 80℃ aging oven for 72h, and the phenomenon of bubbling, edge lifting or even falling off of the samples was observed to judge the antioxidant ability of the samples. The specific detection results are shown in the following table:

[0060]

[0061] From the above table, it can be seen that the samples prepared by example 1 to example 3 all have excellent adhesion, corrosion and antifouling ability and antioxidant effect. The sample prepared by comparative example 1 does not add antifouling and corrosion cellulose, and the antifouling and corrosion resistance is poor, but it adds coumaric acid modified polyether, so the antioxidant ability of the sample is excellent. The sample prepared by comparative example 2 does not add coumaric acid modified polyether, and the antioxidant ability is poor, but it adds antifouling and corrosion cellulose, so the antifouling and corrosion resistance is strong. The sample prepared by comparative example 3 does not add antifouling and corrosion cellulose and does not add coumaric acid modified polyether, so the adhesion, antifouling and corrosion resistance and antioxidant ability of the sample are poor. The sample prepared by comparative example 4 directly adds organic fluorine modified cellulose and coumaric acid modified polyether, and the adhesion, antifouling and corrosion resistance and antioxidant ability are good, but they are not as good as examples, because the structure of the directly added organic fluorine modified cellulose does not have multiple alkenyl groups, which cannot form crosslinked structure with the paint matrix to enhance the density.

[0062] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction.

[0063] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or adopt similar ways to replace them, as long as they do not deviate from the scope defined by the concept of the application.

Claims

1. An environmentally friendly paint, characterized by, The raw materials include the following weight parts: 25-30 parts of phenyl acrylate, 20-25 parts of styrene, 15-20 parts of lauryl methacrylate, 10-15 parts of tert-butyl acrylate, 12-15 parts of anti-fouling and anti-corrosion cellulose, 8-10 parts of coumaric acid modified polyether, 100-150 parts of anhydrous ethanol, 8-10 parts of initiator, 3-5 parts of dimethyl silicone oil defoaming agent, and 2-3 parts of polyurethane leveling agent; the anti-fouling and anti-corrosion cellulose is prepared by reacting organic fluorine modified bacterial cellulose with pentaerythritol triacrylate; the organic fluorine modified bacterial cellulose is prepared by reacting bacterial cellulose with tetrafluoro phthalic anhydride; and the coumaric acid modified polyether is prepared by reacting allyl alcohol polyether with coumaric acid.

2. An environmentally friendly paint according to claim 1, characterized in that, The initiator is any one of benzoyl peroxide, dicumyl peroxide, and tert-butyl peroxybenzoate.

3. The environmentally friendly paint according to claim 1, characterized in that, The preparation method of the anti-fouling and anti-corrosion cellulose comprises the following steps: S1: mixing bacterial cellulose with butanone, passing nitrogen, adding tetrafluoro phthalic anhydride, and heating to 65-70 DEG C for 5-8 h; after the reaction is completed, the solvent is removed by distillation under reduced pressure, and the product is collected to obtain organic fluorine modified bacterial cellulose; S2: placing the organic fluorine modified bacterial cellulose in N-methyl pyrrolidone, fully mixing and stirring, then adding pentaerythritol triacrylate and a catalyst, heating to 90-100 DEG C for 6-8 h, and removing the solvent by distillation under reduced pressure after the reaction is completed to collect the product to obtain the anti-fouling and anti-corrosion cellulose.

4. An environmentally friendly paint according to claim 3, characterized in that, In step S2, the catalyst is any one of p-toluenesulfonic acid and aminobenzenesulfonic acid.

5. The environmentally friendly paint according to claim 1, wherein The preparation method of the coumaric acid modified polyether comprises the following steps: placing allyl alcohol polyether and coumaric acid in N,N-dimethylformamide, fully mixing and stirring, then adding p-toluenesulfonic acid, heating, removing the solvent by distillation under reduced pressure, and collecting the product to obtain the coumaric acid modified polyether.

6. An environmentally friendly paint according to claim 5, wherein The heating temperature is 95-105 DEG C, and the heating time is 5-6 h.

7. A method of preparing an eco-friendly paint as claimed in claim 1, characterized in that, The method comprises the following steps: Step one: placing phenyl acrylate, styrene, lauryl methacrylate, tert-butyl acrylate, anti-fouling and anti-corrosion cellulose, and coumaric acid modified polyether in anhydrous ethanol, adding an initiator, heating to 50-55 DEG C, and fully stirring to obtain an environmentally friendly paint base material; Step two: adding dimethyl silicone oil defoaming agent and polyurethane leveling agent to the environmentally friendly paint base material, and mixing uniformly to obtain an environmentally friendly paint.

8. The method of claim 7, wherein the paint is an environmentally friendly paint. In step one, the stirring speed is 200-300 r / min, and the stirring time is 6-8 h.

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