Preparation method of chlorinated olefin modified waterborne alkyd resin

Abstract

The invention relates to the field of water-based paint, in particular to a preparation method of chlorinated olefin modified water-based alkyd resin, and various properties of the resin can be remarkably improved by modifying the water-based alkyd resin through chlorinated olefin. Due to the introduction of a chlorinated olefin molecular structure and a polar functional group, the improvement of a resin cross-linked network, the enhancement of chemical resistance and the optimization of rheological property and environmental protection property, the overall performance is improved; and meanwhile, the chlorinated olefin modified water-based alkyd resin shows a wider market prospect, and the development of green paint is promoted.

Description

Technical Field

[0001] The invention relates to the field of water-based coatings, and in particular to a method for preparing a chlorinated olefin modified water-based alkyd resin. Background Art

[0002] Alkyd resin is a linear resin formed by the condensation of polyols, polyacids and vegetable oils. From the perspective of molecular structure, alkyd resin is a linear resin with an ester bond generated by the reaction of polyols and polyacids as the main chain and vegetable oil as the side chain. By controlling the content of vegetable oil, alkyd resins of different oil contents can be synthesized and used in different fields.

[0003] Waterborne alkyd resin has a polar main chain and non-polar side chains, and has reactive groups such as hydroxyl, carboxyl, and double bonds in the molecule. However, waterborne alkyd resin has long-chain alkyl and hydrophilic groups, which causes its adhesion to decrease, limiting its application in water-soluble coatings. Summary of the invention

[0004] In view of the problems in the prior art, the present invention provides a method for preparing a fluorinated olefin modified waterborne alkyd resin, which utilizes the introduction of chlorinated olefin molecular structure and polar functional groups, the improvement of the resin cross-linking network, the enhancement of chemical resistance, and the optimization of rheological properties and environmental protection, thereby improving the overall performance; at the same time, it also ensures that the chlorinated olefin modified waterborne alkyd resin shows a broader market prospect and promotes the development of green coatings.

[0005] In order to achieve the above technical objectives, the technical solution of the present invention is:

[0006] A method for preparing a fluorinated olefin modified waterborne alkyd resin comprises the following steps:

[0007] Step 1, oleic acid, ethylene glycol, isophthalic acid, trimethylolpropane and xylene are added to a reaction kettle, heated to 80° C. for 2 hours and stirred, heated to 190° C. and refluxed for 7 hours to obtain a mixed solution;

[0008] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0009] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160-170°C, and nitrogen is introduced and allowed to stand;

[0010] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins, methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0011] Step 5, adding triethylamine and filtering to obtain a chlorinated olefin modified waterborne alkyd resin.

[0012] The mass ratio of the chlorinated olefin modified waterborne alkyd resin is: 32-45 parts of oleic acid, 3-8 parts of ethylene glycol, 25-35 parts of isophthalic acid, 14-16 parts of trimethylolpropane, and 1-3 parts of xylene in the step 1; 15-30 parts of ethylene glycol butyl ether in the step 2; 10-15 parts of chlorinated olefins, 1-3 parts of maleic anhydride, 5-10 parts of acrylic acid, and 0.4-0.7 parts of dibenzoyl peroxide in the mixed material in the step 4; 5 parts of isopropyl alcohol, 0.1 parts of dibenzoyl peroxide, and 5-8 parts of methyl methacrylate in the step 4; and 3-6 parts of triethylamine in the step 5.

[0013] The above method can significantly improve multiple properties of waterborne alkyd resin by modifying waterborne alkyd resin with chlorinated olefins. The introduction of the molecular structure and polar functional groups of the chlorinated olefins, the improvement of the cross-linking network of the resin, the enhancement of chemical resistance, and the optimization of rheological properties and environmental protection have brought about an improvement in overall performance; at the same time, it also ensures that the chlorinated olefin-modified waterborne alkyd resin has a broader market prospect and promotes the development of green coatings.

[0014] It can be seen from the above description that the present invention has the following advantages:

[0015] 1. The present invention uses chlorinated olefins as dopants and connects them to alkyd resins through acrylic monomers. Chlorinated olefins usually have polar functional groups. Introducing these functional groups into water-based alkyd resins can increase the polarity of the resin and improve the compatibility and adhesion with the substrate surface. This modification can effectively improve the adhesion of the coating, especially on low-energy surfaces such as metals and plastics.

[0016] 2. The present invention utilizes chlorinated olefins and acrylic monomers to improve the resin network structure in water-based alkyd resin. The molecular structure of chlorinated olefins can interact with alkyd resin through chemical reaction or physical cross-linking to promote the formation of a resin cross-linked network. The enhancement of this network structure helps to improve the mechanical properties of the coating, including hardness, impact resistance and wear resistance.

[0017] 3. The waterborne alkyd resin prepared by the present invention has improved chemical resistance. Chlorinated olefins have high chemical stability. By introducing chlorinated olefins, the acid resistance, alkali resistance and solvent resistance of the waterborne alkyd resin are improved, so that the service life of the coating in harsh environments is extended, and it is suitable for more industrial applications.

[0018] 4. In the preparation method provided by the present invention, during the polymerization reaction, when the BPO initiator is added once, the grafting rate of acrylic acid and alkyd resin is low, and a large amount of free acrylic acid is likely to remain in the system. Adding it twice can increase the degree of reaction between acrylic acid and alkyd resin, further ensuring the stability of the resin system and the cross-linking density. DETAILED DESCRIPTION

[0019] The present invention is described in detail with reference to the embodiments, but no limitation is imposed on the claims of the present invention.

[0020] Example 1

[0021] A method for preparing a chlorinated olefin modified alkyd resin comprises the following steps:

[0022] Step 1, oleic acid, ethylene glycol, isophthalic acid, trimethylolpropane and xylene are added to a reaction kettle, heated to 80° C. for 2 hours and stirred, heated to 190° C. and refluxed for 7 hours to obtain a mixed solution;

[0023] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0024] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160-170° C., and nitrogen is introduced;

[0025] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins, methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0026] Step 5, adding triethylamine and filtering to obtain chlorinated olefin modified waterborne alkyd resin

[0027] The mass ratio of the mixed liquid in step 1 is: 38 parts of oleic acid, 5 parts of ethylene glycol, 30 parts of isophthalic acid, 15 parts of trimethylolpropane, and 3 parts of xylene; 22 parts of ethylene glycol butyl ether in step 2; 10 parts of chlorinated olefins, 2 parts of maleic anhydride, 10 parts of acrylic acid, and 0.7 parts of dibenzoyl peroxide in the mixed material in step 4; 5 parts of isopropanol, 0.1 parts of dibenzoyl peroxide, and 5 parts of methyl methacrylate in step 4, and 5 parts of triethylamine in step 5.

[0028] Embodiment 2:

[0029] A method for preparing a chlorinated olefin modified alkyd resin comprises the following steps:

[0030] Step 1, oleic acid, ethylene glycol, isophthalic acid, trimethylolpropane and xylene are added to a reaction kettle, heated to 80° C. for 2 hours and stirred, heated to 190° C. and refluxed for 7 hours to obtain a mixed solution;

[0031] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0032] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160-170° C., and nitrogen is introduced;

[0033] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins, methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0034] Step 5, adding triethylamine and filtering to obtain chlorinated olefin modified waterborne alkyd resin

[0035] The mass ratio of the mixed liquid in step 1 is: 45 parts of oleic acid, 8 parts of ethylene glycol, 35 parts of isophthalic acid, 16 parts of trimethylolpropane, and 3 parts of xylene; 30 parts of ethylene glycol butyl ether in step 2; 15 parts of chlorinated olefins, 3 parts of maleic anhydride, 10 parts of acrylic acid, and 0.7 parts of dibenzoyl peroxide in the mixed material in step 4; 5 parts of isopropanol, 0.1 parts of dibenzoyl peroxide, and 8 parts of methyl methacrylate in step 4; and 6 parts of triethylamine in step 5.

[0036] Example 3

[0037] A method for preparing a chlorinated olefin modified alkyd resin comprises the following steps:

[0038] Step 1, adding oleic acid, ethylene glycol, isophthalic acid and trimethylolpropane into a reaction kettle, heating to 80° C. for 2 hours and starting stirring, heating to 190° C. and reflux for 7 hours to obtain a mixed solution;

[0039] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0040] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160-170° C., and nitrogen is introduced;

[0041] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins, methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0042] Step 5, adding triethylamine and filtering to obtain chlorinated olefin modified waterborne alkyd resin

[0043] The mass ratio of the mixed liquid in step 1 is: 32 parts of oleic acid, 3 parts of ethylene glycol, 25 parts of isophthalic acid, 14 parts of trimethylolpropane, and 3 parts of xylene; 15 parts of ethylene glycol butyl ether in step 2; 15 parts of chlorinated olefins in the mixed material in step 4, 1 part of maleic anhydride, 5 parts of acrylic acid, 0.4 parts of dibenzoyl peroxide, 5 parts of isopropanol in step 4, 0.1 parts of dibenzoyl peroxide, and 5 parts of methyl methacrylate; 3 parts of triethylamine in step 5.

[0044] Comparative Example 1

[0045] A method for preparing an acrylic acid-modified alkyd resin comprises the following steps:

[0046] Step 1, adding oleic acid, ethylene glycol, isophthalic acid and trimethylolpropane into a reaction kettle, heating to 80° C. for 2 hours and starting stirring, heating to 190° C. and reflux for 7 hours to obtain a mixed solution;

[0047] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0048] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160° C. to 170° C., and nitrogen is introduced;

[0049] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in a high-level tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0050] Step 5, adding triethylamine and filtering to obtain chlorinated olefin modified waterborne alkyd resin

[0051] The mass ratio of the mixed liquid in step 1 is: 32 parts of oleic acid, 3 parts of ethylene glycol, 25 parts of isophthalic acid, 14 parts of trimethylolpropane, and 3 parts of xylene; 15 parts of ethylene glycol butyl ether in step 2; 1 part of maleic anhydride, 20 parts of acrylic acid, 0.4 parts of dibenzoyl peroxide in the mixed material in step 4, 5 parts of isopropyl alcohol in step 4, 0.1 parts of dibenzoyl peroxide, and 5 parts of methyl methacrylate; 3 parts of triethylamine in step 5.

[0052] Comparative Example 2

[0053] A method for preparing a chlorinated olefin modified alkyd resin comprises the following steps:

[0054] Step 1, adding oleic acid, ethylene glycol, isophthalic acid and trimethylolpropane into a reaction kettle, heating to 80° C. for 2 hours and starting stirring, heating to 190° C. and reflux for 7 hours to obtain a mixed solution;

[0055] Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C;

[0056] Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160° C. to 170° C., and nitrogen is introduced;

[0057] Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour;

[0058] Step 5, adding triethylamine and filtering to obtain chlorinated olefin modified waterborne alkyd resin

[0059] The mass ratio of the mixed liquid in step 1 is: 32 parts of oleic acid, 3 parts of ethylene glycol, 25 parts of isophthalic acid, 14 parts of trimethylolpropane, and 3 parts of xylene; 20 parts of ethylene glycol butyl ether in step 2; 20 parts of chlorinated olefins, 1 part of maleic anhydride, 0.4 parts of dibenzoyl peroxide in the mixed material in step 4, 5 parts of isopropyl alcohol in step 4, and 0.1 parts of dibenzoyl peroxide; 3 parts of triethylamine in step 5.

[0060] Performance Testing

[0061] The alkyd resins of Examples 1-3 and Comparative Examples 1-2 and commercially available alkyd resins were used as test samples for testing, and the results are as follows:

[0062] Table 1 Test data of alkyd resins and commercially available alkyd resins in Examples 1-3 and Comparative Examples 1-2

[0063]

[0064] Comparison of the above examples and comparative examples shows that the water-based alkyd resin provided by the present invention forms a resin network structure in the alkyd resin through the synergistic effect of chlorinated olefins and acrylic monomers, effectively improving the viscosity and other properties of the resin, and also improving its protectiveness. At the same time, chlorinated olefins and alkyd resins cannot react directly, resulting in that although the comparative document 2 maintains good translucency and good dispersibility in the early stage, as the standing time increases, the chlorinated olefins themselves granulate, resulting in a more serious turbidity phenomenon.

[0065] Examples

[0066] Alkyd resins were applied to the paint films and the films were tested:

[0067] The mass ratio of the paint film is: 55 parts of alkyd resin, 0.2 parts of Tego670W, 0.1 parts of Tego270, 0.3 parts of BYK-333, 16 parts of medium chrome yellow, 2.6 parts of 3132 red powder, 1 part of fumed silica A200, 2 parts of ethylene glycol butyl ether, 3 parts of isopropyl alcohol, 19.3 parts of water, and 0.5 parts of polyurethane thickener.

[0068] In the test data, the modified alkyd resin and water-based alkyd resin of Example 1, Comparative Example 1 and Comparative Example 2 were used as raw materials to prepare paint films.

[0069] Table 2 Paint film data of modified alkyd resin and waterborne alkyd resin of Example 1, Comparative Example 1 and Comparative Example 2

[0070]

[0071]

[0072] By comparing the data, it can be concluded that the chlorinated olefin modified waterborne alkyd resin has significantly improved the drying speed, adhesion, mechanical properties and chemical resistance of low surface tension substrates compared to conventional waterborne alkyd resins. Compared with conventional waterborne alkyd resins and waterborne acrylic modified alkyd resins, the paint film prepared by the present invention has significantly improved adhesion and hardness on low surface tension substrates, and also significantly improved chemical resistance and weather resistance.

[0073] It is understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A method for preparing a fluorinated olefin modified waterborne alkyd resin, characterized in that: The steps include: Step 1, oleic acid, ethylene glycol, isophthalic acid, trimethylolpropane and xylene are added to a reaction kettle, heated to 80° C. for 2 hours and stirred, heated to 190° C. and refluxed for 7 hours to obtain a mixed solution; Step 2, heating the mixed solution and esterifying it at a temperature of 230°C to obtain an esterified solution, and then immediately sampling and testing the acid value, wherein the heating rate of the heating treatment is 10°C / min, and the temperature of the esterification at a temperature of 230°C; Step 3, when the acid value is ≤6 mgKOH / g, the temperature is lowered to 160-170°C, and nitrogen is introduced and allowed to stand; Step 4, dilute the esterification liquid in the reactor with ethylene glycol butyl ether and cool it to 130°C, then mix the chlorinated olefins, methyl methacrylate, acrylic acid and dibenzoyl peroxide evenly to obtain a mixture and place it in an overhead tank, add it dropwise to the reactor when the temperature drops to 80°C, and add it within 2 hours, and finally keep it at 80°C for 1 hour, then continue to add isopropyl alcohol and dibenzoyl peroxide dropwise, and continue to keep it warm for 1 hour; Step 5, adding triethylamine and filtering to obtain a chlorinated olefin modified waterborne alkyd resin.

2. The method for preparing a fluorinated olefin modified waterborne alkyd resin according to claim 1, characterized in that: The raw material mass ratio in step 1 is: 32-45 parts of oleic acid, 3-8 parts of ethylene glycol, 25-35 parts of isophthalic acid, 14-16 parts of trimethylolpropane, and 1-3 parts of xylene.

3. The method for preparing a fluorinated olefin modified waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of the raw materials to oleic acid in step 2 is: 15-30 parts of ethylene glycol butyl ether.

4. The method for preparing a fluorinated olefin modified waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of the raw materials in the mixture of step 4 to oleic acid is: 10-15 parts of chlorinated olefins, 1-3 parts of maleic anhydride, 5-10 parts of acrylic acid, and 0.4-0.7 parts of dibenzoyl peroxide.

5. The method for preparing a fluorinated olefin modified waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of the raw materials to oleic acid in step 4 is: 5 parts of isopropyl alcohol, 0.1 parts of dibenzoyl peroxide, and 5-8 parts of methyl methacrylate.

6. The method for preparing a fluorinated olefin modified waterborne alkyd resin according to claim 1, characterized in that: The mass ratio of the raw materials to oleic acid in step 5 is: 3-6 parts of triethylamine.

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