A polyphosphate polymer, a method for preparing the same, and an application thereof

Abstract

The application provides a polyphosphate polymer, a preparation method and application thereof, and raw materials for preparing the polyphosphate polymer include mono-amino polyether, a cyclic acid anhydride containing a carbon-carbon double bond, a conjugated diene containing a single hydroxyl group, and a phosphoric acid ester reagent. The polyphosphate polymer provided by the application can effectively disperse various pigments including water-based titanium dioxide, and has the advantages of good dispersibility and good stability.

Description

Technical Field

[0001] This invention belongs to the field of pigment dispersant technology, specifically relating to a polyphosphate polymer, its preparation method, and its application. Background Technology

[0002] Dispersants, as pigment dispersing aids, possess properties such as reducing pigment particle size, increasing coating gloss, improving leveling, and enhancing the coloring and hiding power of coatings. They are an indispensable raw material in coating production. Traditional dispersants are usually low-molecular-weight surfactants with relatively simple molecular structures and few anchoring groups. This structure makes it difficult to provide stable adsorption capacity on the pigment particle surface and address steric hindrance effects. Superdispersants, on the other hand, are high-molecular-weight dispersants with more complex molecular structures, containing multiple and various types of anchoring groups and abundant solvation segments. They can provide stable adsorption capacity on the pigment particle surface and corresponding steric protection effects, forming stable protective groups and effectively preventing pigment particle aggregation and sedimentation.

[0003] Phosphate ester groups, as ionic groups with a unique structure, possess both hydrophilic and hydrophobic properties. When phosphate ester groups come into contact with a solid surface, their hydrophilic groups adhere to the solid surface, while the hydrophobic groups extend outwards into the liquid, thereby reducing the surface tension of the liquid and making it easier for the liquid to spread on the solid surface, forming a uniform coating. As a polymer dispersant containing phosphate groups, its unique structure can give polymers excellent wetting, emulsifying, and solubilizing properties, effectively improving pigment dispersibility, increasing material uniformity, preventing particle aggregation, and enhancing material stability.

[0004] Therefore, a polymer dispersant containing phosphate ester groups has been developed, which has broad application prospects in the coatings field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a polyphosphate polymer, its preparation method, and its applications. The polyphosphate polymer provided by this invention can effectively disperse various pigments, including aqueous titanium dioxide, and has the advantages of good dispersibility and stability.

[0006] To achieve this objective, the present invention employs the following technical solution: In a first aspect, the present invention provides a polyphosphate polymer, wherein the raw materials for preparing the polyphosphate polymer include a monoamino polyether, a cyclic anhydride containing a carbon-carbon double bond, a conjugated diene containing a monohydroxyl group, and a phosphorylation reagent.

[0007] The polyphosphate polymer prepared from the above-mentioned specific raw materials can effectively disperse various pigments, including water-based titanium dioxide, and has the advantages of good dispersibility and good stability.

[0008] Preferably, the structure of the monoamino polyether is as follows: ; In the formula, R1 is C a H 2a+1 R2 is H or CH3, a is an integer from 1 to 4 (1, 2, 3 or 4), m and n are integers greater than 0, and the sum of m and n is greater than 10 and less than 100.

[0009] Preferably, the cyclic anhydride containing a carbon-carbon double bond is selected from any one or a combination of at least two of the compounds shown in Formula 1 or Formula 2: ; In the formula, R3, R4, R5, R6, and R7 are independently selected from hydrogen or C1-C3 alkyl groups (e.g., methyl, ethyl, n-propyl, or isopropyl).

[0010] Preferably, the structure of the monohydroxyl-containing conjugated diene is as follows: ; In the formula, R8, R9, R 10 Independently selected from hydrogen or C1-C10 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, etc.), R 11 For having C b H 2b Alkylene in general formula, where b is an integer from 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10).

[0011] Preferably, the phosphorylation reagent comprises phosphorus pentoxide.

[0012] Preferably, the monoamino polyether includes any one or a combination of at least two of SURFONAMINE® L100, SURFONAMINE® L207, SURFONAMINE® L300, SURFONAMINE® B60, SURFONAMINE® B100 or SURFONAMINE® B200, with SURFONAMINE® L207 and SURFONAMINE® L300 being more preferred.

[0013] Preferably, the cyclic anhydride containing carbon-carbon double bonds includes any one or a combination of at least two of maleic anhydride, itaconic anhydride, dimethylmaleic anhydride, or citraconic anhydride, with maleic anhydride and dimethylmaleic anhydride being more preferred.

[0014] Preferably, the monohydroxyl-containing conjugated diene includes any one or a combination of at least two of 2,4-hexadien-1-ol, 2,4-heptadien-1-ol, dodecadienol, 2,4-decadien-1-ol, or 2,4-nonadien-1-ol, with 2,4-hexadien-1-ol and 2,4-heptadien-1-ol being the most preferred.

[0015] The selection of these specific raw materials can further improve the dispersibility and stability of the pigments, thereby enhancing the product's performance.

[0016] Preferably, the phosphorylation reagent comprises phosphorus pentoxide.

[0017] Secondly, the present invention provides a method for preparing the polyphosphate polymer as described above, the method comprising the following steps: (1) The monoamino polyether is mixed with a cyclic anhydride containing carbon-carbon double bonds to obtain the first intermediate; (2) The first intermediate is mixed with a conjugated diene containing a single hydroxyl group and reacted to obtain the second intermediate; (3) The second intermediate is mixed with a phosphoric acid esterification agent to obtain the polyphosphate polymer.

[0018] Preferably, the molar ratio of the monoamino polyether to the cyclic anhydride containing carbon-carbon double bonds in step (1) is 1:(1-3), such as 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, but not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0019] Preferably, the molar ratio of the monohydroxyl-containing conjugated diene to the first intermediate in step (2) is (2-5):1, such as 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0020] Preferably, the molar ratio of the phosphorylation reagent to the second intermediate in step (3) is 1:(2-3), such as 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3, but not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0021] Preferably, the reaction temperature in step (1) is 120-160℃ and the time is 2-10 h. The temperature can be 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃ or 160℃, etc., and the time can be 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., but is not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0022] Preferably, the reaction temperature in step (2) is 80-120℃ and the time is 5-20 h. The temperature can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃, etc., and the time can be 5 h, 10 h, 15 h or 20 h, etc., but is not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0023] Preferably, the reaction temperature in step (3) is 50-100℃ and the time is 1-10 h. The temperature can be 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, etc., and the time can be 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., but is not limited to the values ​​listed above. Other unlisted values ​​within the above range are also applicable.

[0024] Thirdly, the present invention also provides the application of the polyphosphate polymer as described above in the preparation of pigment pastes.

[0025] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a polyphosphate polymer. By selecting specific raw materials, the prepared polyphosphate polymer can effectively disperse various pigments, including aqueous titanium dioxide, and has the advantages of good dispersibility and good stability. Detailed Implementation

[0026] To further illustrate the technical means and effects of the present invention, the following describes the technical solution of the present invention in conjunction with preferred embodiments of the present invention. However, the present invention is not limited to the scope of the embodiments.

[0027] Example 1 This embodiment provides a polyphosphate polymer, prepared from the following raw materials: Monoamino polyethers (SURFONAMINE® L207, SURFONAMINE® L300, molar ratio 1:1), cyclic anhydrides containing carbon-carbon double bonds (maleic anhydride, dimethylmaleic anhydride, molar ratio 1:1.2), conjugated dienes containing monohydroxyl groups (2,4-hexadien-1-ol, 2,4-heptadien-1-ol, molar ratio 1:1), and phosphoric acid esterification reagents (phosphorus pentoxide).

[0028] The preparation method is as follows: Step 1: Monoamino polyether was added to a reaction vessel, and the mixture was heated to 145°C under nitrogen protection. Then, a cyclic anhydride containing carbon-carbon double bonds was added and the reaction was maintained at this temperature for 6 hours to induce imidization until anhydrous product was obtained. Unreacted cyclic anhydride containing carbon-carbon double bonds was removed under reduced pressure to obtain intermediate 1. The molar ratio of monoamino polyether to cyclic anhydride containing carbon-carbon double bonds was 1:2.

[0029] Step 2: Intermediate 1 is added to the reaction vessel, heated to 100°C under nitrogen protection, and an excess of monohydroxyl-containing conjugated diene is added. The reaction is maintained at this temperature for 12 hours until complete, undergoing a cycloaddition reaction. Unreacted monohydroxyl-containing conjugated diene is removed under reduced pressure to obtain intermediate 2. The molar ratio of monohydroxyl-containing conjugated diene to intermediate 2 is 4:1. Step 3: Add intermediate 2 to the reaction flask, heat to 80°C, add phosphorus pentoxide and react for 5 hours to carry out the esterification reaction, obtaining the polyphosphate polymer. The molar ratio of phosphorus pentoxide to intermediate 2 is 1:2.5.

[0030] Example 2 This embodiment provides a polyphosphate polymer, prepared from the following raw materials: Monoamino polyethers (SURFONAMINE® L207, SURFONAMINE® L300, molar ratio 1:2), cyclic anhydrides containing carbon-carbon double bonds (maleic anhydride, dimethylmaleic anhydride, molar ratio 1:3), conjugated dienes containing monohydroxyl groups (2,4-hexadien-1-ol, 2,4-heptadien-1-ol, molar ratio 1:1.5), and phosphoric acid esterification reagents (phosphorus pentoxide).

[0031] The preparation method is as follows: Step 1: Monoamino polyether was added to a reaction vessel, and the mixture was heated to 120°C under nitrogen protection. Then, a cyclic anhydride containing carbon-carbon double bonds was added and the reaction was maintained at this temperature for 10 hours to induce imidization until anhydrous product was obtained. Unreacted cyclic anhydride containing carbon-carbon double bonds was removed under reduced pressure to obtain intermediate 1. The molar ratio of monoamino polyether to cyclic anhydride containing carbon-carbon double bonds was 1:1.

[0032] Step 2: Intermediate 1 is added to the reaction vessel, and the mixture is heated to 80°C under nitrogen protection. An excess of a monohydroxyl-containing conjugated diene is added, and the reaction is maintained at this temperature for 20 hours until complete, undergoing a cycloaddition reaction. Unreacted monohydroxyl-containing conjugated diene is removed under reduced pressure to obtain intermediate 2. The molar ratio of the monohydroxyl-containing conjugated diene to intermediate 2 is 2:1. Step 3: Add intermediate 2 to the reaction flask, heat to 50°C, add phosphorus pentoxide and react for 10 hours to carry out the esterification reaction, obtaining the polyphosphate polymer. The molar ratio of phosphorus pentoxide to intermediate 2 is 1:3.

[0033] Example 3 This embodiment provides a polyphosphate polymer, prepared from the following raw materials: Monoamino polyethers (SURFONAMINE® L207, SURFONAMINE® L300, molar ratio 2:1), cyclic anhydrides containing carbon-carbon double bonds (maleic anhydride, dimethylmaleic anhydride, molar ratio 1.5:1), conjugated dienes containing monohydroxyl groups (2,4-hexadien-1-ol, 2,4-heptadien-1-ol, molar ratio 1.5:1), and phosphoric acid esterification reagents (phosphorus pentoxide).

[0034] The preparation method is as follows: Step 1: Monoamino polyether was added to a reaction vessel, and the mixture was heated to 160°C under nitrogen protection. Then, a cyclic anhydride containing carbon-carbon double bonds was added and the reaction was maintained at this temperature for 2 hours to induce imidization until anhydrous product was obtained. Unreacted cyclic anhydride containing carbon-carbon double bonds was removed under reduced pressure to obtain intermediate 1. The molar ratio of monoamino polyether to cyclic anhydride containing carbon-carbon double bonds was 1:3.

[0035] Step 2: Intermediate 1 is added to the reaction vessel, and the temperature is raised to 120°C under nitrogen protection. An excess of a monohydroxyl-containing conjugated diene is added, and the reaction is maintained at this temperature for 5 hours until complete, undergoing a cycloaddition reaction. Unreacted monohydroxyl-containing conjugated diene is removed under reduced pressure to obtain intermediate 2. The molar ratio of the monohydroxyl-containing conjugated diene to intermediate 2 is 5:1. Step 3: Add intermediate 2 to the reaction flask, heat to 100°C, add phosphorus pentoxide and react for 1 hour to carry out the esterification reaction, obtaining the polyphosphate polymer. The molar ratio of phosphorus pentoxide to intermediate 2 is 1:2.

[0036] Example 4 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that SURFONAMINE® L207 is replaced with an equimolar amount of SURFONAMINE® L300.

[0037] The preparation method is the same as in Example 1.

[0038] Example 5 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that SURFONAMINE® L300 is replaced with an equimolar amount of SURFONAMINE® L207.

[0039] The preparation method is the same as in Example 1.

[0040] Example 6 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that maleic anhydride is replaced with an equimolar amount of dimethylmaleic anhydride.

[0041] The preparation method is the same as in Example 1.

[0042] Example 7 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that dimethyl maleic anhydride is replaced with an equimolar amount of maleic anhydride.

[0043] The preparation method is the same as in Example 1.

[0044] Example 8 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that 2,4-hexadien-1-ol is replaced with an equimolar amount of 2,4-heptadien-1-ol.

[0045] The preparation method is the same as in Example 1.

[0046] Example 9 This embodiment provides a polyphosphate polymer. The raw materials used in its preparation are the same as in Example 1, except that 2,4-heptadien-1-ol is replaced with an equimolar amount of 2,4-hexadien-1-ol.

[0047] The preparation method is the same as in Example 1.

[0048] Effect test: The polyphosphate polymers obtained in Examples 1-9 were used for the dispersion of aqueous titanium dioxide.

[0049] Using a laboratory sand mill, 5g of the polyphosphate polymer prepared in Examples 1-9, 0.5g of pH stabilizer sodium hydroxide, 70g of R258 titanium dioxide, and the balance water were added sequentially according to a total slurry formulation of 100g. After stirring evenly, 200g of zirconium beads with a particle size of 1-1.2mm were added and sealed in a glass jar. The mixture was shaken for 10 hours and then filtered to obtain the color paste. The particle size and storage stability of the color paste were tested.

[0050] 1. Particle size: Tested using a BT90 laser particle size analyzer, Dandong Better Instruments Co., Ltd.

[0051] 2. Viscosity: Measured using an NDJ-1B rotational viscometer, Shanghai Changji Geological Instrument Co., Ltd.

[0052] 3. Storage stability: After storing at 55℃ for 7 days, the changes in particle size and viscosity were detected.

[0053] The specific test results are shown in the table below: As can be seen from the test results above, the polyphosphate polymer prepared by the present invention, when used as a pigment dispersant, can produce a dispersion with low particle size, narrow distribution, and good stability. Comparing Examples 1 and 4-9, it can be found that by selecting specific reagents, the present invention results in smaller variations in product particle size and viscosity, better dispersibility and stability, and can further improve the product's effectiveness.

[0054] The applicant declares that the present invention illustrates the polyphosphate polymer, its preparation method, and its application through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0055] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0056] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. A polyphosphate polymer, characterized in that, The raw materials for preparing the polyphosphate polymer include monoamino polyether, cyclic anhydride containing carbon-carbon double bonds, conjugated diene containing monohydroxyl groups, and phosphorylation reagent. The preparation method of the polyphosphate polymer includes the following steps: (1) The monoamino polyether is mixed with a cyclic acid anhydride containing a carbon-carbon double bond and subjected to an imidization reaction to obtain the first intermediate; (2) The first intermediate is mixed with a conjugated diene containing a single hydroxyl group and subjected to a cycloaddition reaction to obtain the second intermediate; (3) The second intermediate is mixed with a phosphoric acid esterification agent to carry out an esterification reaction to obtain the polyphosphate polymer; The molar ratio of the monoamino polyether to the cyclic anhydride containing carbon-carbon double bonds in step (1) is 1:(1-3); The molar ratio of the monohydroxyl-containing conjugated diene to the first intermediate in step (2) is (2-5):1; The molar ratio of the phosphorylation reagent to the second intermediate in step (3) is 1:(2-3).

2. The polyphosphate polymer according to claim 1, characterized in that, The structure of the monoamino polyether is shown below: ； In the formula, R1 is C a H 2a+1 R2 is H or CH3, a is an integer from 1 to 4, m and n are integers greater than 0, and the sum of m and n is greater than 10 and less than 100; The cyclic anhydride containing a carbon-carbon double bond is selected from any one or a combination of at least two of the compounds shown in Formula 1 or Formula 2: ； In the formula, R3, R4, R5, R6, and R7 are independently selected from hydrogen or C1-C3 alkyl groups; The structure of the conjugated diene containing a single hydroxyl group is shown below: ； In the formula, R8, R9, R 10 Independently selected from hydrogen or C1-C10 alkyl, R 11 For having C b H 2b Alkyl groups of the general formula, where b is an integer from 1 to 10; The phosphorylation reagent includes phosphorus pentoxide.

3. The polyphosphate polymer according to claim 2, characterized in that, The monoamino polyether includes any one or a combination of at least two of SURFONAMINE® L100, SURFONAMINE® L207, SURFONAMINE® L300, SURFONAMINE® B60, SURFONAMINE® B100 or SURFONAMINE® B200.

4. The polyphosphate polymer according to claim 3, characterized in that, The monoamino polyethers include SURFONAMINE® L207 and SURFONAMINE® L300.

5. The polyphosphate polymer according to claim 2, characterized in that, The cyclic anhydrides containing carbon-carbon double bonds include any one or a combination of at least two of maleic anhydride, itaconic anhydride, dimethylmaleic anhydride, or citraconic anhydride. The monohydroxyl-containing conjugated diene includes any one or a combination of at least two of 2,4-hexadien-1-ol, 2,4-heptadien-1-ol, dodecadienol, 2,4-decadien-1-ol, or 2,4-nonadien-1-ol.

6. The polyphosphate polymer according to claim 5, characterized in that, The cyclic anhydrides containing carbon-carbon double bonds include maleic anhydride and dimethylmaleic anhydride.

7. The polyphosphate polymer according to claim 5, characterized in that, The monohydroxyl-containing conjugated dienes include 2,4-hexadien-1-ol and 2,4-heptadien-1-ol.

8. A method for preparing a polyphosphate polymer according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: (1) The monoamino polyether is mixed with a cyclic acid anhydride containing a carbon-carbon double bond and subjected to an imidization reaction to obtain the first intermediate; (2) The first intermediate is mixed with a conjugated diene containing a single hydroxyl group and subjected to a cycloaddition reaction to obtain the second intermediate; (3) The second intermediate is mixed with a phosphoric acid esterification agent to carry out an esterification reaction to obtain the polyphosphate polymer; The molar ratio of the monoamino polyether to the cyclic anhydride containing carbon-carbon double bonds in step (1) is 1:(1-3); The molar ratio of the monohydroxyl-containing conjugated diene to the first intermediate in step (2) is (2-5):1; The molar ratio of the phosphorylation reagent to the second intermediate in step (3) is 1:(2-3).

9. The use of a polyphosphate polymer according to any one of claims 1-7 in the preparation of pigment pastes.

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