阅读说明：本技术 一种哑光粉用磷酸酯分散剂的制备方法 (Preparation method of phosphate ester dispersing agent for matte powder ) 是由 陈鹏 于 2021-11-16 设计创作，主要内容包括：本发明涉及一种哑光粉用磷酸酯分散剂的制备方法。首先使用甲基丙烯酸、马来酸酐和烯丙基聚醚在无氧环境中制备聚合物,有机胺中和,然后再加入低含氢硅油,制备聚二甲基硅氧烷改性的有机聚合物,将聚二甲基硅氧烷改性的有机聚合物进行磷酸酯化即可得到磷酸酯分散剂。本发明方法制备的哑光粉用磷酸酯分散剂,分散性强,色泽更好,并且能够有效地防止产生沉淀、消光和斑点的现象。(The invention relates to a preparation method of a phosphate ester dispersing agent for matte powder. Firstly, methacrylic acid, maleic anhydride and allyl polyether are used for preparing a polymer in an oxygen-free environment, organic amine is neutralized, then low-hydrogen silicone oil is added to prepare a polydimethylsiloxane modified organic polymer, and the polydimethylsiloxane modified organic polymer is subjected to phosphorylation esterification to obtain the phosphate dispersing agent. The phosphate ester dispersing agent for the matte powder prepared by the method has strong dispersibility and better color, and can effectively prevent the phenomena of precipitation, extinction and spots.)

1. A preparation method of a phosphate ester dispersing agent for matte powder is characterized by comprising the following preparation steps:

s1: preparation before preparation: heating the reaction kettle, and fully drying the reaction kettle; continuously filling inert gas into the reaction kettle, exhausting air in the reaction kettle, exhausting air and various impurities in the reaction kettle, and enabling the interior of the reaction kettle to be in an oxygen-free environment; adding an organic solvent into the reaction kettle, then adding an initiator, and stirring to obtain an initiator solution;

s2: preparation of polyether polymer: sequentially adding half part of methacrylic acid, half part of anhydride and half part of straight-chain alkenyl ether into an initiator solution of S1, heating to 60-70 ℃, and stirring at the rotating speed of 100 r/min; then adding graphene, continuously stirring for 10-15min, then adding the other half part of methacrylic acid, the half part of anhydride and the half part of allyl polyether into the reaction kettle, and continuously stirring for reaction; reacting for 5 hours, refluxing at 100-110 ℃ for the first 1-2 hours, then heating to 110-125 ℃, continuing refluxing, and after the reaction is finished, continuously introducing nitrogen until the temperature of the reaction liquid polymer is reduced to room temperature;

adding a neutralizer into the reaction liquid polymer, and treating for 3-5min by ultrasonic waves; then standing for 2 hours to obtain a polyether polymer;

s3: preparation of polydimethylsiloxane-modified organic polymers: continuously filling nitrogen into the reaction kettle, adding a small amount of platinum catalyst into the polyether polymer obtained in S2 in a nitrogen environment, slowly adding low-hydrogen silicone oil, reacting for 12-14 h at 60-70 ℃, and distilling under reduced pressure at low temperature to remove the organic solvent to obtain a light yellow viscous polydimethylsiloxane modified organic polymer;

s4: and (3) phosphorylation: the polydimethylsiloxane-modified organic polymer obtained in step S4 is subjected to phosphorylation at a temperature of 65 ℃ or lower. Cooling to room temperature to obtain a phosphated product;

s5: and (4) adjusting the pH value of the salt in the step S4 to 6.5-7.5 to obtain a final product, namely the phosphate ester dispersing agent.

2. The preparation method of the phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step S1, the initiator solvent is an organic solvent, and the organic solvent is one or more of xylene, chlorobenzene, n-butanol, sec-butanol, n-propanol, isopropanol, ethanol and methanol.

3. The method for preparing the phosphate ester dispersant for matte powder according to claim 1, wherein in the step S2, the neutralizer is an organic amine, and the organic amine is one or more of isopropylamine, n-butylamine, triethylamine, ethylenediamine, diphenylamine, tripropylamine and triethanolamine.

4. The method for preparing the phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step S2, the allyl polyether is a linear alkene ether containing 2-12 carbon atoms, and the molecular weight of the allyl polyether is 102-300.

5. The method for preparing the phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step S2, the weight ratio of methacrylic acid, anhydride and allyl polyether is 1.5:1.0-1.25: 1.5.

6. The method for preparing a phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step of S3, the low hydrogen silicone oil is added in a dropping manner to ensure that the reaction is fully performed.

7. The method for preparing the phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step S3, the platinum catalyst is potassium hexachloroplatinate; the amount of the added potassium hexachloroplatinate catalyst accounts for 0.06-0.08 wt% of the total amount of all the compounds.

8. The method for preparing the phosphate ester dispersing agent for matte powder according to claim 1, wherein in the step of S5, the pH value of the compound is adjusted to 7 to obtain the phosphate ester dispersing agent.

Technical Field

The invention relates to the technical field of industrial phosphate ester dispersing agents, and particularly relates to a preparation method of a phosphate ester dispersing agent for matte powder.

Background

Phosphate ester dispersants are chemicals that are clear yellow liquids, primarily used in aqueous coatings and printing inks. The phosphate ester dispersing agent has the main function of uniformly dispersing solid pigment particles in a liquid medium in the production process of coatings and printing ink; the establishment of a uniform and stable pigment dispersion system not only can improve the production efficiency and reduce the energy consumption, but also can enable the final product to exert excellent performances, such as high gloss, low viscosity, high coloring strength, prevention of flooding, blooming, flocculation and the like.

The phosphate end group in the phosphate dispersant plays a role of anchoring, and the monohydric alcohol precursor serves as a solvation chain segment for adjusting the polarity and enhancing the compatibility with the surrounding medium. In many cases, good results are obtained with the phosphate ester dispersants disclosed above, but the existing phosphate ester dispersants are generally highly polar and selective to the resin system used. Particularly, when the phosphate ester dispersing agent is applied to solvent-free epoxy resin paint, the existing phosphate ester dispersing agent has the defects of insufficient viscosity reduction capability, cracking and the like of a coating under the condition of high-temperature baking, and the dispersing force is insufficient, so that adverse phenomena of precipitation, extinction, spots, thickening and the like can be caused.

Disclosure of Invention

In order to solve the problems, the dispersing effect of the phosphate dispersing agent is better, and the adverse phenomena of precipitation, extinction, spots, thickening and the like are reduced when the phosphate dispersing agent is used, the invention provides the preparation method of the phosphate dispersing agent with good dispersing performance and good wetting performance on a base material.

A preparation method of a phosphate ester dispersing agent for matte powder comprises the following preparation steps:

s1: preparation before preparation: heating the reaction kettle, and fully drying the reaction kettle; continuously filling inert gas into the reaction kettle, exhausting air in the reaction kettle, exhausting air and various impurities in the reaction kettle, and enabling the interior of the reaction kettle to be in an oxygen-free environment; adding an organic solvent into the reaction kettle, then adding an initiator, and stirring to obtain an initiator solution;

s2: preparation of polyether polymer: sequentially adding half part of methacrylic acid, half part of anhydride and half part of straight-chain alkenyl ether into an initiator solution of S1, heating to 60-70 ℃, and stirring at the rotating speed of 100 r/min; then adding graphene, continuously stirring for 10-15min, then adding the other half part of methacrylic acid, the half part of anhydride and the half part of allyl polyether into the reaction kettle, and continuously stirring for reaction; reacting for 5 hours, refluxing at 100-110 ℃ for the first 1-2 hours, then heating to 110-125 ℃, continuing refluxing, and after the reaction is finished, continuously introducing nitrogen until the temperature of the reaction liquid polymer is reduced to room temperature;

adding a neutralizer into the reaction liquid polymer, and treating for 3-5min by ultrasonic waves; then standing for 2 hours to obtain a polyether polymer;

s3: preparation of polydimethylsiloxane-modified organic polymers: continuously filling nitrogen into the reaction kettle, adding a small amount of platinum catalyst into the polyether polymer obtained in S2 in a nitrogen environment, slowly adding low-hydrogen silicone oil, reacting at 60-70 ℃ for 12-14 h, and distilling at low temperature under reduced pressure to remove the organic solvent to obtain a light yellow viscous polyether modified organic silicon polymer;

s4: and (3) phosphorylation: the polydimethylsiloxane-modified organic polymer obtained in step S4 is subjected to phosphorylation at a temperature of 65 ℃ or lower. Cooling to room temperature to obtain a phosphated product;

s5: and (4) adjusting the pH value of the salt in the step S4 to 6.5-7.5 to obtain a final product, namely the phosphate ester dispersing agent.

Further, in the step S1, the initiator solvent is an organic solvent, and the organic solvent is one or more of xylene, chlorobenzene, n-butanol, sec-butanol, n-propanol, isopropanol, ethanol, and methanol.

Further, in the step S2, the neutralizer is an organic amine, and the organic amine is one or more of isopropylamine, n-butylamine, triethylamine, ethylenediamine, diphenylamine, tripropylamine, and triethanolamine.

Further, in the step S2, the linear alkenyl ether is an ether of a linear alkene containing 2 to 12 carbon atoms, and the molecular weight of the linear alkenyl ether is 58 to 300.

Furthermore, in the step S2, the weight ratio of the organic amine, the methacrylic acid, the anhydride and the linear alkenyl ether is 1: 1.5:1.0-1.25:1.5.

Further, in the step S2, the low hydrogen silicone oil is added in a dropping manner to ensure that the reaction is sufficiently performed.

Further, in the step S3, the platinum catalyst is potassium hexachloroplatinate; the amount of the added potassium hexachloroplatinate catalyst accounts for 0.06-0.08 wt% of the total amount of all the compounds.

Further, in the step S5, the pH of the compound is adjusted to 7 to obtain a phosphate ester dispersant

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects: the phosphate ester dispersing agent prepared by the invention is suitable for water-soluble paint and ink printing, has the best effect especially when used in the water-soluble paint, can effectively disperse solid particles, and avoids the occurrence of adverse phenomena such as precipitation, extinction, spots, thickening and the like; the preparation method is simple, the used raw materials are common reagents, the reaction is carried out at a lower temperature in the production process, the reaction time is prolonged, the reaction can be more sufficient, the yield of the phosphate ester dispersing agent in unit weight is improved, and the generation of side reactions and byproducts is reduced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A preparation method of a phosphate ester dispersing agent for matte powder comprises the following preparation steps: preparation before preparation: heating the reaction kettle, and fully drying the reaction kettle; continuously filling inert gas into the reaction kettle, discharging air in the reaction kettle, removing air and various impurities in the reaction kettle, and enabling the reaction kettle to be in an oxygen-free environment; adding a solvent into a reaction kettle, then adding an initiator, and stirring to obtain an initiator solution, wherein the initiator solvent is an organic solvent, and the organic solvent is one or more of dimethylbenzene, chlorobenzene, n-butyl alcohol, sec-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethanol and methanol.

Example 1

Filling nitrogen into an organic solvent in a reaction kettle, then sequentially and slowly adding 30g of methacrylic acid, 25g of succinic anhydride and 30g of straight-chain alkenyl ether, fully stirring and uniformly mixing, reacting at 100 ℃ for 2 hours, heating to 120 ℃, continuing to react for 3 hours, and continuously introducing nitrogen into the reaction kettle to cool to room temperature; adding 20g of ethylenediamine; in a nitrogen environment, adding 0.5g of potassium hexachloroplatinate into a reaction kettle, slowly adding 26g of low-hydrogen silicone oil, reacting for 12 hours at 60 ℃, and distilling under reduced pressure at low temperature to remove an organic solvent to obtain a light yellow viscous polydimethylsiloxane modified organic polymer; 15g of phosphorus pentoxide was added to the polydimethylsiloxane-modified organic polymer, stirred at 60 ℃ for 8 hours, and the pH was adjusted to 7 with diethanolamine to give a phosphate ester dispersant.

Example 2

Filling nitrogen into an organic solvent in a reaction kettle, then sequentially and slowly adding 30g of methacrylic acid, 25g of succinic anhydride and 30g of straight-chain alkenyl ether, fully stirring and uniformly mixing, reacting at 100 ℃ for 2 hours, heating to 120 ℃, continuing to react for 3 hours, and continuously introducing nitrogen until the temperature in a four-mouth bottle is reduced to room temperature; adding 23g of diphenylamine; adding 0.1g of potassium hexachloroplatinate into a four-mouth bottle in a nitrogen environment, slowly adding 26g of low-hydrogen silicone oil, reacting for 12 hours at 60 ℃, and distilling under reduced pressure at low temperature to remove an organic solvent to obtain a light yellow viscous polydimethylsiloxane modified organic polymer; 16g of polyphosphoric acid was added to the polydimethylsiloxane-modified organic polymer, and stirred at 60 ℃ for 8 hours to obtain a phosphate ester dispersant.

Example 3

Filling nitrogen into an organic solvent in a reaction kettle, then sequentially and slowly adding 30g of methacrylic acid, 20g of maleic anhydride and 30g of straight-chain alkenyl ether, fully stirring and uniformly mixing, reacting at 105 ℃ for 2 hours, heating to 120 ℃, continuing to react for 3 hours, and continuously introducing nitrogen into the reaction kettle to cool to room temperature; adding 23g of triethanolamine; slowly adding 26g of low-hydrogen silicone oil and 0.1g of potassium hexachloroplatinate into a reaction kettle in a nitrogen environment, reacting for 12 hours at 60 ℃, and distilling under reduced pressure at low temperature to remove an organic solvent and water to obtain a light yellow viscous polydimethylsiloxane modified organic polymer; 16g of polyphosphoric acid was added to the polydimethylsiloxane-modified organic polymer, and stirred at 60 ℃ for 8 hours to obtain a phosphate ester dispersant.

Example 4

Filling nitrogen into an organic solvent in a reaction kettle, then sequentially and slowly adding 30g of methacrylic acid, 18g of acrylic anhydride and 30g of straight-chain alkenyl ether, fully stirring and uniformly mixing, reacting at 105 ℃ for 2 hours, heating to 120 ℃, continuing to react for 3 hours, and continuously introducing nitrogen into the reaction kettle to cool to room temperature; adding 23g of triethanolamine; slowly adding 26g of low-hydrogen silicone oil and 0.1g of potassium hexachloroplatinate into a reaction kettle in a nitrogen environment, reacting for 12 hours at 60 ℃, and distilling under reduced pressure at low temperature to remove an organic solvent to obtain a faint yellow viscous polyether modified organic silicon polymer; adding 16g of polyphosphoric acid into the polyether modified organic silicon polymer, and stirring for 8 hours at 60 ℃ to obtain the phosphate ester dispersing agent.

To test the effectiveness of the present phosphate ester dispersant for matte, which was applied to a water-soluble coating system, the following water-borne coatings were prepared:

adding 1 part of defoaming agent and 25 parts of deionized water into 5 containers, adding no phosphate dispersing agent into one container, adding 10 parts of the phosphate dispersing agent in the other four containers respectively, stirring for 1 hour, then slowly adding 65 parts of titanium dioxide powder into the four containers while stirring, continuously stirring for 45min, then adding a small amount of organic bentonite, continuously stirring and mixing for 2 hours to obtain the water-based paint, and recording the viscosity of the water-based paint by using a viscometer. 30 parts of the aqueous coating, 60 parts of acrylic resin and 6 parts of a cross-linking agent are uniformly mixed and then tested, and the following results are obtained, (the viscosity unit in the table is Pa/s):

	blank space	Example 1	Example 2	Example 3	Example 4
						Viscosity of the solution	656.32	288.52	265.45	316.26	211.25
Gloss of	81.3	83.7	86.5	84.3	89.1
						Color developing power	Has spots	Good whiteness and dispersion	Good whiteness dispersion	Good whiteness and dispersion	Good whiteness and dispersion

The test result shows that the water-based paint without any dispersant has high viscosity, spots appear in the solution, the water-based paint is difficult to be uniformly coated when in use, and the construction effect is poor. After the phosphate ester dispersing agent is added, the fluidity of the water-based paint is obviously improved, so that the water-based paint is easier to smear and disperse, is more uniform, and has no precipitation, extinction and spot phenomena.

It should be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention. Although an embodiment of the present invention has been described, it is to be understood that the present invention should not be limited to this embodiment, and variations and modifications can be made by those skilled in the art within the spirit and scope of the present invention as defined in the appended claims.