Organic acid zirconium as well as preparation method and application thereof

Abstract

The invention relates to organic acid zirconium and a preparation method and application thereof.The preparation method of the organic acid zirconium comprises the steps that an ammonium zirconium carbonate aqueous solution and a first solvent are evenly mixed, first organic acid is dropwise added for a reaction, and a first intermediate product is obtained; adding a layering solvent into the first intermediate product, dropwise adding an alcohol solvent for reaction, adjusting the pH value to 6.5-7.5 by using a second organic acid, standing for layering, and separating to obtain a second intermediate product; and testing the content of the zirconium element in the second intermediate product, supplementing the first solvent until the content of the zirconium element is 4-6.2 wt%, and then adding or not adding the organic diamine to obtain the organic acid zirconium. Compared with the prior art, a one-step method is used for reaction, compared with a traditional two-step method, no waste residues are generated, the method belongs to a green and environment-friendly production process, and the prepared novel organic acid zirconium has more excellent hydrolysis resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and particularly relates to an organic acid zirconium, a preparation method thereof, and an application thereof. Background Art

[0002] Organic acid zirconiums such as zirconium isooctanoate and zirconium naphthenate are indispensable additives in various air-dried oxidation cross-linking coatings. Metallic zirconium belongs to a coordination type drier, which can form a large molecular weight coordination complex with hydroxyl groups or polar groups in the resin, and promote the dry-to-touch of the resin.

[0003] Currently in China, the two-step method is mainly used to synthesize organic acid zirconiums such as zirconium isooctanoate and zirconium naphthenate. The specific method is that an organic acid and sodium hydroxide undergo an acid-base neutralization reaction to form a sodium organic acid salt, and the sodium organic acid salt and zirconium oxychloride undergo a metathesis reaction to form an organic acid zirconium. With the wide application of organic acid zirconiums in polyurethane systems and waterborne coatings, the organic acid zirconiums synthesized by the above method are prone to hydrolysis, resulting in a significant reduction in the activity of metallic zirconium. Summary of the Invention

[0004] The purpose of the present invention is to provide an organic acid zirconium, a preparation method thereof, and an application thereof so as to overcome at least one of the defects existing in the above-mentioned prior art.

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

[0006] One of the purposes of the present invention lies in a preparation method of an organic acid zirconium, comprising the following steps:

[0007] (1) Mix an aqueous solution of ammonium zirconium carbonate uniformly with a first solvent, and dropwise add a first organic acid for reaction to obtain a first intermediate product;

[0008] (2) Add a layered solvent to the first intermediate product, then dropwise add an alcohol solvent for reaction, adjust the pH to 6.5 - 7.5 with a second organic acid, and let it stand for layering; drain the lower aqueous layer, and distill off the layered solvent and water from the oil layer to obtain a second intermediate product;

[0009] (3) Test the zirconium element content of the second intermediate product, add the first solvent as a supplement to make the zirconium element content 4 - 6.2 wt%, and then add or not add an organic diamine to obtain an organic acid zirconium. Preferably, the optimal content of the zirconium element is 5 - 6.2 wt%. If the zirconium element content is too high, the product stability will decrease.

[0010] Furthermore, in step (1),

[0011] the first organic acid is selected from one or more of isooctanoic acid, isononanoic acid, naphthenic acid, neodecanoic acid, or octodecanoic acid, and is preferably isooctanoic acid;

[0012] The first solvent is selected from one or more of 1500#, 1800#, D60 or D80.

[0013] Furthermore, in step (1),

[0014] The pH value of the aqueous solution of ammonium zirconium carbonate is 8 - 10, and the content of ZrO2 is greater than 15 wt%.

[0015] The molar ratio of the first organic acid to the zirconium element in the aqueous solution of ammonium zirconium carbonate is (1 - 3):1, preferably (1 - 2):1; the mass ratio of the first solvent to the first organic acid is (1 - 1.5):1, preferably (1.1 - 1.3):1.

[0016] The dropping time of the first organic acid is 0.5 - 2 h, the reaction temperature is 30 - 50 °C. After the dropping of the first organic acid is completed, react for another 1 - 3 h; preferably, the dropping time of the first organic acid is 40 - 60 min, the reaction temperature is 35 - 45 °C, and after the dropping of the first organic acid is completed, react for another 1.5 - 2 h.

[0017] Furthermore, in step (2),

[0018] The layered solvent is 120# solvent.

[0019] The alcohol solvent is selected from one or more of isooctanol, isohexanol, isononanol, octanol, n-nonanol, neopentyl alcohol or n-hexanol.

[0020] The second organic acid is selected from one or more of isooctanoic acid, isononanoic acid, naphthenic acid, neodecanoic acid or octodecanoic acid.

[0021] Furthermore, in step (2),

[0022] The mass ratio of the layered solvent to the second organic acid is (2 - 4):1, preferably (2 - 3):1.

[0023] The molar ratio of the alcohol solvent to the zirconium element in the aqueous solution of ammonium zirconium carbonate is (1 - 4):1, preferably (1 - 3):1; the dropping time of the alcohol solvent is 20 - 60 min, preferably 30 - 50 min.

[0024] The reaction temperature is 80 - 110 °C, preferably 90 - 100 °C, and the reaction time is 1 - 3 h, preferably 1.5 - 2.5 h.

[0025] Furthermore, in step (2), the oil layer is distilled until the flash point > 60 °C. Too low a flash point indicates the residue of 120# solvent in the system.

[0026] Further, in step (3), the organic diamine is selected from one or more of tetramethylpropylenediamine, trimethylhydroxyethylenediamine, (dimethylaminopropyl)diisopropanolamine, bis(dimethylaminoethyl)ether, diazabicyclo, p-phenylenediamine or triethylenediamine.

[0027] Further, in step (3), after adjusting the content of zirconium element, an organic diamine is added, and the mass ratio of the organic diamine to the zirconium element content of the second intermediate is (1-4):100, preferably (2-3.5):100.

[0028] The second object of the present invention is an organic acid zirconium obtained by using the preparation method of the organic acid zirconium as described above.

[0029] The third object of the present invention is an application of an organic acid zirconium. The organic acid zirconium is the organic acid zirconium as described above and is applied to a drier for air-dry resins. Compared with the prior art, it has more excellent hydrolysis resistance.

[0030] Compared with the prior art, the present invention has the following beneficial effects.

[0031] (1) In the ammonium zirconium carbonate of the present invention, zirconium exists in the form of an anionic hydroxylated zirconium polybody. Zirconium ions can have a complexing effect with a large bond energy with the carboxyl group in the organic acid. The hydroxyl group in the alcohol solvent can have a hydrogen bond effect with the carbonyl structure on the zirconium atom, and the binding force is stronger and it is not easy to undergo a hydrolysis reaction in water. Currently, the organic acid zirconium prepared by a double decomposition reaction has a weak binding force between the metal zirconium and the organic acid. In the presence of a large amount of water, the chemical bond is easily broken, resulting in the loss of the drying performance of the metal zirconium. Therefore, the novel organic acid zirconium prepared by the present invention has more excellent hydrolysis resistance.

[0032] (2) The present invention uses a one-step reaction. Compared with the traditional two-step method, no waste residue is generated, and it belongs to a green environmental protection production process.

[0033] (3) The present invention uses an organic diamine. The N atom in the organic amine and the metal zirconium share electron pairs, which improves the activity of the metal zirconium and further enhances the drying performance of the resin, thereby significantly improving the dry-to-touch performance of the coating film. Specific Embodiments

[0034] The following will give a detailed description of the embodiments of the present invention. The embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0035] Example 1

[0036] Add 100 g of zirconium ammonium carbonate aqueous solution (ZrO2 = 19.0 - 20.5%, pH = 8 - 10) and 56.3 g of 1500# into a four-necked flask, start stirring, heat up to 35 - 40 °C, and dropwise add 46.9 g of isooctanoic acid under the condition of 500 r / min. The dropping time is 45 min. After the dropping is completed, react for 1.5 h;

[0037] Add 93.8 g of 120# solvent, heat up to 90 - 95 °C, dropwise add 41.6 g of isooctanol. The dropping time is 40 min. After the dropping is completed, the reaction time is 2 h. Test the pH value of the system = 7.8, add 15 g of isooctanoic acid to adjust to 7.2, and let it stand for stratification;

[0038] Drain the lower water layer, heat up to distill out the stratifying solvent and water in the system, heat up to 130 - 135 °C, turn on the vacuum pump for 10 minutes, flash point = 62 °C;

[0039] Test the zirconium element content = 6.5 wt%, add 5.6 g of 1500# solvent as a supplement, zirconium element = 6.2 wt%, add 0.3 g of diazabicyclo, and prepare a new zirconium isooctanoate.

[0040] Example 2

[0041] Add 100 g of zirconium ammonium carbonate aqueous solution (ZrO2 = 19.0 - 20.5%, pH = 8 - 10) and 56.3 g of 1500# into a four-necked flask, start stirring, heat up to 35 - 40 °C, and dropwise add 46.9 g of isooctanoic acid under the condition of 500 r / min. The dropping time is 45 min. After the dropping is completed, react for 1.5 h;

[0042] Add 93.8 g of 120# solvent, heat up to 90 - 95 °C, dropwise add 41.6 g of isooctanol. The dropping time is 40 min. After the dropping is completed, the reaction time is 2 h. Test the pH value of the system = 7.8, add 15 g of isooctanoic acid to adjust to 7.2, and let it stand for stratification;

[0043] Drain the lower water layer, heat up to distill out the stratifying solvent and water in the system, heat up to 130 - 135 °C, turn on the vacuum pump for 10 minutes, flash point = 67 °C;

[0044] Test the zirconium element content = 6.5 wt%, add 5.6 g of 1500# solvent as a supplement, zirconium element = 6.2 wt%, and prepare a new zirconium isooctanoate.

[0045] Example 3

[0046] Add 100 g of zirconium ammonium carbonate aqueous solution (ZrO2 = 19.0 - 20.5%, pH = 8 - 10) and 60.5 g of D80 into a four-necked flask, start stirring, heat up to 40 - 45 °C, and dropwise add 55 g of neodecanoic acid under the condition of 500 r / min. The dropping time is 45 min. After the dropping is completed, react for 2 h;

[0047] Add 126 g of 120# solvent, heat up to 90 - 95 °C, dropwise add 28 g of neopentyl alcohol. The dropping time is 40 min. After the dropping is completed, the reaction time is 2 h. Test the pH value of the system = 7.7, add 10 g of neodecanoic acid to adjust to 7.5, and let it stand for liquid separation;

[0048] Drain the lower aqueous layer, heat up to distill out the separated solvent and water in the system, heat up to 130 - 135 °C, turn on the vacuum pump for 10 minutes, flash point = 65 °C;

[0049] Test the zirconium element content = 6.35%, add 5.5 g of D80 to make the zirconium element content = 6.2 wt%, add 0.4 g of triethylenediamine to prepare a novel zirconium neodecanoate.

[0050] Comparative example

[0051] Add 105.6 g of 32 wt% sodium hydroxide aqueous solution into a four-necked flask, heat up to 75 - 80 °C, add 98.4 g of isooctanoic acid, and react for 40 min under the condition of 500 r / min. Add 200 g of 1500# solvent, add 100 g of zirconium oxychloride, react for 1 h, add 50 g of 120# solvent, let it stand for liquid separation, drain the lower aqueous layer, then add 150 g of water, stir evenly, let it stand for liquid separation, drain the lower aqueous layer, heat up to remove the 120# solvent and water in the system, heat up to 130 °C, turn on the vacuum pump for 10 minutes, flash point = 65 °C, cool down to 80 °C, measure the zirconium element content = 6.5 wt%, add 73 g of 1500# solvent to adjust to the zirconium element content = 6.2 wt%, and prepare an organic acid zirconium.

[0052] After formulating the organic acid zirconium (zirconium element = 6.2 wt%) prepared in the above examples and comparative examples of the present invention, cobalt isooctanoate (cobalt element = 10 wt%, produced by Shanghai Huayi Coatings Co., Ltd.), and T-80 emulsifier into a composite drier, add it to the waterborne propylene-modified alcohol resin to compare the drying performance. The composite drier formula is shown in Table 1

[0053] Table 1 Composite driers formulated in Examples 1 - 3 and Comparative Example

[0054]

[0055] Add the composite driers formulated in the above examples and comparative examples of the present invention to Yuanbang 01W75 waterborne propylene-modified alcohol resin for performance testing. The specific testing method is as follows:

[0056] Add the prepared composite drier to Yuanbang 01W75 waterborne propylene-modified alcohol resin, with an addition amount of 3 wt% of the resin amount. Prepare a coating film on tinplate and air-dry it naturally under the conditions of 21 - 25 °C and 48 - 52% RH, and test the surface dryness and through dryness.

[0057] Surface dryness test method (blowing cotton ball method): Place a degreased cotton ball on the surface of the coating film, gently blow the cotton ball horizontally with the mouth. When the cotton ball can be blown away and no cotton filaments are left on the film surface, it can be judged that the surface is dry.

[0058] Through dryness test method (pressing filter paper method): Place a filter paper on the surface of the paint film, press a 200 g weight on it. After 30 seconds, remove the weight, and then turn the sample plate over. If the filter paper can fall freely, it can be considered that the paint film is through dry.

[0059] Prepare a coating film on a glass plate and air-dry it naturally for 7 days under the conditions of 21 - 25 °C and 48 - 52% RH, and test the hardness with a BYK pendulum hardness tester. The specific test results are shown in Table 2 below.

[0060] Table 2 Performance test data of the composite driers prepared in Examples 1 - 3 and the comparative example

[0061]

[0062] It can be seen from the data in Table 2 that for the composite driers 1 and 3 prepared in Examples 1 and 3, since a binary organic amine was added in Examples 1 and 3, the N atom in the organic amine and the metal zirconium shared an electron pair, improving the activity of the metal zirconium and further enhancing its drying performance for the resin, thus significantly improving the through dry performance of the coating film.

[0063] Put the above waterborne propylene-modified alcohol resin added with the drier into an oven at 50 °C, take it out after 15 days and retest the performance. The specific test results are shown in Table 3 below.

[0064] Table 3 Performance test data of the composite driers prepared in Examples 1 - 3 and the comparative example after being added to waterborne propylene-modified alcohol resin and placed at 50 °C for 15 days

[0065]

[0066] It can be seen from the data in Table 3 that the composite driers 1, 2, and 3 prepared from the novel zirconium organic acid based on the concept of the present invention have more excellent hydrolysis resistance. After the zirconium organic acid in the comparative example was placed in an aqueous environment for a period of time, the performance of the composite drier 4 prepared with it decreased significantly because the zirconium organic acid in the comparative example hydrolyzed and lost its activity.

[0067] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention in any other form. Any person skilled in the relevant art may use the technical content disclosed above to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution content of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for preparing zirconium organic acid, characterized in that, It includes the following steps: (1) Mix the ammonium zirconium carbonate aqueous solution evenly with the first solvent, and dropwise add the first organic acid for reaction to obtain a first intermediate product; (2) Add a layer-separating solvent to the first intermediate product, then dropwise add an alcohol solvent for reaction, adjust the pH to 6.5 - 7.5 with the second organic acid, let it stand for layer separation, and after separation, obtain a second intermediate product; (3) Test the zirconium element content of the second intermediate product, add the first solvent as a supplement to make the zirconium element content 4 - 6.2 wt%, and obtain zirconium organic acid.

2. The preparation method of an organic acid zirconium according to claim 1, wherein, In step (1), the first organic acid is selected from one or more of isooctanoic acid, isononanoic acid, naphthenic acid, neodecanoic acid, or octodecanoic acid; the first solvent is selected from one or more of 1500#, 1800#, D60, or D80.

3. The preparation method of an organic acid zirconium according to claim 1, characterized in that, In step (1), the pH value of the ammonium zirconium carbonate aqueous solution is 8 - 10, and the content of ZrO2 is greater than 15 wt%; the molar ratio of the first organic acid to the zirconium element in the ammonium zirconium carbonate aqueous solution is (1 - 3):1; the mass ratio of the first solvent to the first organic acid is (1 - 1.5):1; the dropping time of the first organic acid is 0.5 - 2 h, the reaction temperature is 30 - 50 °C, and after the first organic acid is completely dropped, react for another 1 - 3 h.

4. The preparation method of an organic acid zirconium according to claim 1, characterized in that, In step (2), the layer-separating solvent is 120# solvent; the alcohol solvent is selected from one or more of isooctanol, isohexanol, isononanol, octanol, n-nonanol, neopentyl alcohol, or n-hexanol; the second organic acid is selected from one or more of isooctanoic acid, isononanoic acid, naphthenic acid, neodecanoic acid, or octodecanoic acid.

5. The preparation method of an organic acid zirconium according to claim 1, characterized in that, In step (2), the mass ratio of the layer-separating solvent to the second organic acid is (2 - 4):1; the molar ratio of the alcohol solvent to the zirconium element in the ammonium zirconium carbonate aqueous solution is (1 - 4):1; the dropping time of the alcohol solvent is 20 - 60 min; the reaction temperature is 80 - 110 °C, and the reaction time is 1 - 3 h.

6. The preparation method of an organic acid zirconium according to claim 1, characterized in that, In step (2), the oil layer is distilled until the flash point > 60 °C.

7. A method for preparing zirconium organic acid according to claim 1, characterized in that, In step (3), the organic diamine is selected from one or more of tetramethylpropylenediamine, trimethylhydroxyethylenediamine, (dimethylaminopropyl)diisopropanolamine, bis(dimethylaminoethyl)ether, diazabicyclo, p-phenylenediamine, or triethylenediamine.

8. The preparation method of an organic acid zirconium according to claim 1, characterized in that, In step (3), after adjusting the zirconium element content, add the organic diamine, and the mass ratio of the organic diamine to the zirconium element content of the second intermediate product is (1 - 4):

100.

9. An organic acid zirconium, characterized in that, It is obtained by using the preparation method of zirconium organic acid as described in any one of claims 1 - 8.

10. Application of zirconium organic acid, characterized in that, This zirconium organic acid is the zirconium organic acid as described in claim 9 and is applied as a drier for air-drying resins.

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