阅读说明：本技术 一种亲水性可调酞菁蓝颜料的制备方法 (Preparation method of hydrophilic adjustable phthalocyanine blue pigment ) 是由 汪国建 安国清 陶文大 何守琴 马书民 张鹏 黄婷婷 于 2021-01-03 设计创作，主要内容包括：本发明涉及一种亲水性可调的酞菁蓝颜料的制备方法,具体而言,其是先以酸胀后的酞菁蓝为原料,将其分散在去离子水中,使用机械搅拌的方式使其呈悬浊状态,然后向其中加入适量的疏水改性剂,再加入硅源及其水解剂,最后通过裂解剂的加入使得包覆的硅源中暴露出更多的硅羟基,从而提高其亲水性。通过疏水剂中疏水碳链和亲水的硅羟基基团之间的比例控制实现了酞菁蓝亲水性可调的效果。本发明方法制备的酞菁蓝可应用于水性颜料的制备,其在pH为6-9,水溶液温度为20-80℃的范围内均表现出较好的稳定性。(The invention relates to a preparation method of a phthalocyanine blue pigment with adjustable hydrophilicity, which specifically comprises the steps of firstly taking acid-swollen phthalocyanine blue as a raw material, dispersing the raw material in deionized water, enabling the raw material to be in a suspension state by using a mechanical stirring mode, then adding a proper amount of hydrophobic modifier, then adding a silicon source and a hydrolytic agent thereof, and finally adding a cracking agent to enable more silicon hydroxyl groups to be exposed in the coated silicon source, so that the hydrophilicity of the coated silicon source is improved. The adjustable effect of the hydrophilicity of the phthalocyanine blue is realized by controlling the proportion of the hydrophobic carbon chain and the hydrophilic silicon hydroxyl group in the hydrophobic agent. The phthalocyanine blue prepared by the method can be applied to the preparation of water-based pigments, and shows better stability in the ranges of pH 6-9 and aqueous solution temperature of 20-80 ℃.)

1. A preparation method of a hydrophilic tunable phthalocyanine blue pigment is characterized by comprising the following steps:

s1: taking acid swelled phthalocyanine blue as a raw material, and dispersing the acid swelled phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension;

s2: adding a hydrophobic agent into the suspension in the S1, stirring, and then adding a silicon source and a silicon source hydrolytic agent;

s3: after the hydrolysis in the step S2 is completed, a proper amount of cracking agent is added to crack the surface-coated silicon dioxide layer and expose a large amount of silicon hydroxyl groups therein, thereby achieving the hydrophilic purpose of the phthalocyanine blue pigment.

2. The preparation method of the hydrophilic tunable phthalocyanine blue pigment according to claim 1, wherein the hydrophilicity of the phthalocyanine blue is adjusted by adjusting and controlling the addition amounts of the hydrophobic agent and the silicon source.

3. The method for preparing a hydrophilic tunable phthalocyanine blue pigment according to claim 1, wherein the hydrophobic agent in step S2 is hexadecyl trimethoxy silane, and after the hexadecyl trimethoxy silane is added, the temperature of the mixed solution is raised to 50-70 ℃ and maintained for 2-3h, and a small amount of toluene is added.

4. The method for preparing a hydrophilic tunable phthalocyanine blue pigment according to claim 1, wherein the silicon source in step S2 is an organic silicon source, and more preferably, the organic silicon source is tetraethoxysilane.

5. The method for preparing hydrophilic tunable phthalocyanine blue pigment according to claim 1, wherein the silicon source hydrolytic reagent in step S2 is an acidic ethanol solution.

6. The method for preparing a hydrophilic tunable phthalocyanine blue pigment according to claim 1, wherein the cracking agent in step S3 is a strong alkali solution, such as NaOH solution or a mixed solution of NaOH and ethanol.

7. The phthalocyanine blue pigment prepared by the preparation method of the hydrophilic tunable phthalocyanine blue pigment according to any one of claims 1 to 6.

8. The phthalocyanine blue pigment of claim 7 is used in aqueous pigment preparation.

Technical Field

The invention relates to the technical field of modification preparation of colored pigments, in particular to a preparation method of a hydrophilic adjustable phthalocyanine blue pigment.

Background

The conventional colorants mainly include dye-type colorants and pigment-type colorants, wherein the dye-type colorants generate a large amount of waste water and waste water which are difficult to treat due to serious environmental pollution, so that the wide application thereof is greatly limited. The pigment type colorant has good universality, and generally speaking, the pigment type colorant is physically compounded with a matrix to be dyed, so that the advantages of bright color, bright hue and rich color spectrum can be well maintained in the actual use process. However, pigment-type colorants represented by phthalocyanine blue also have problems such as poor dispersibility in water, poor stability, and tendency to agglomerate or flocculate, which are disadvantageous for practical use.

In order to solve the problems, many researchers and industrial enterprises do a lot of work, for example, if the surfactant is used for modifying the product, the method is simple and efficient, but has the disadvantages of non-uniform product and easy sedimentation; the use of a hyperdispersant or microencapsulation modification means can improve the dispersibility and stability of phthalocyanine blue, but the methods have complex processes and higher cost, and are not beneficial to large-scale popularization and application. Specifically, as in the article "Encapsulation of organic phthalic acid pigment into polystyrene latex polymerization" published by Lelu S et al, a microemulsion polymerization method is used to coat the phthalocyanine blue pigment in the polystyrene latex particles to improve the dispersibility in the aqueous dispersion system. The properties of organic pigments can also be improved by grafting organic pigments onto the surface of inorganic nanoparticles, due to their good chemical inertness and heat resistance, by means of inorganic nanoparticles, such as silica, titania and the like, for example, the Naphthol red is grafted onto the surface of silica in the Modification draft a Naphthol as red pigment published by Fei Xuening et al, thereby improving the heat resistance, tinting strength and dispersion stability of the organic pigment Naphthol red. An article "Organic pigment coated with titanium via Sol-Gel process" published by professor of Wuli people of great university adopts Sol-Gel process to coat multiple layers of polymer on the surface of Organic pigment, and then coats titanium oxide on the surface of polymer, thereby improving the ultraviolet resistance and heat resistance of Organic pigment. In addition, chinese patent CN110028809A discloses an easily dispersible blue pigment for aqueous ink of PVC color film and a preparation method thereof, and the coating material prepared by modifying phthalocyanine blue with polyacrylamide is used for coating, thereby regulating the size and dispersibility of pigment particles.

Although the technical scheme can improve the dispersibility of the organic pigment to a certain extent, for practical application, the preparation method capable of realizing the hydrophilic adjustable phthalocyanine blue pigment has important significance.

Disclosure of Invention

Based on the above, the present invention aims to provide a method for preparing a phthalocyanine blue pigment with adjustable hydrophilicity, specifically, the method comprises the steps of firstly dispersing acid-swollen phthalocyanine blue as a raw material in deionized water, using a mechanical stirring manner to enable the phthalocyanine blue to be in a suspension state, then adding a proper amount of hydrophobic modifier, then adding a silicon source and a hydrolytic agent thereof, and finally adding a cracking agent to enable more silicon hydroxyl groups to be exposed in the coated silicon source, so as to improve the hydrophilicity of the coated silicon source. The adjustable effect of the hydrophilicity of the phthalocyanine blue is realized by controlling the proportion of the hydrophobic carbon chain and the hydrophilic silicon hydroxyl group in the hydrophobic agent.

The technical contents of the present invention will now be described in detail below in order to make the technical solutions of the present invention clearly and completely understood by those skilled in the art.

A preparation method of a hydrophilic tunable phthalocyanine blue pigment comprises the following steps:

s1: taking acid swelled phthalocyanine blue as a raw material, and dispersing the acid swelled phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension;

s2: adding a hydrophobic agent into the suspension in the S1, stirring, and then adding a silicon source and a silicon source hydrolytic agent;

s3: after the hydrolysis in the step S2 is completed, a proper amount of cracking agent is added to crack the surface-coated silicon dioxide layer and expose a large amount of silicon hydroxyl groups therein, thereby achieving the hydrophilic purpose of the phthalocyanine blue pigment.

Furthermore, the control of the hydrophilicity of the phthalocyanine blue is realized by controlling the addition amounts of the hydrophobizing agent and the silicon source.

Further, in step S2, the hydrophobic agent is hexadecyl trimethoxy silane, after the substance is added, the temperature of the mixed solution is raised to 50-70 ℃ and kept for 2-3h, and a small amount of toluene is added.

Further, the addition of a small amount of toluene in step S2 hydrolyzes hexadecyltrimethoxysilane to the hydroxyl group.

Further, the silicon source in step S2 is an organic silicon source, not an inorganic silicon source, because the hydrolysis controllability of the inorganic silicon source is worse and the coating is not uniform compared to the organic silicon source. Further preferably, the organic silicon source is tetraethoxysilane.

Further, the silicon source hydrolyzing agent in step S2 is an acidic ethanol solution.

Further, the cracking agent in step S3 refers to a strong alkaline solution, such as a NaOH solution or a mixed solution of NaOH and ethanol.

The invention also provides the phthalocyanine blue pigment with adjustable hydrophilicity, which is prepared by the method, has good dispersibility and good stability in an aqueous dispersion system, can be directly prepared into an aqueous colorant when being used in the colorant field, and avoids using a large amount of toxic and harmful organic solvents.

Compared with the prior art, the invention has the following beneficial technical effects:

1) the inventor firstly uses the hydrophobic agent and the silicon source in a matching way, and realizes the hydrophilic regulation and control of the phthalocyanine blue pigment through the use of the hydrophobic carbon chain and the silicon hydroxyl.

2) Compared with the prior art which can not regulate the hydrophilicity controllably, the method can realize the controllable regulation of the hydrophilicity by a single method and only by changing the consumption of raw materials, and the surface coating material has weak influence on the color of the phthalocyanine blue pigment and hardly causes influence on the color of the phthalocyanine blue pigment under the action of the cracking agent.

3) The phthalocyanine blue pigment prepared by the method can be directly applied to the water-based pigment, avoids using a large amount of toxic and harmful organic solvents in the prior art, and can provide a green and environment-friendly water-based pigment.

Drawings

FIG. 1 shows the stability profile of hydrophilic tunable phthalocyanine blue pigments prepared by the present invention in solutions of different pH;

FIG. 2 shows the stability distribution diagram of the hydrophilic tunable phthalocyanine blue pigment prepared by the invention in aqueous dispersants at different temperatures.

Detailed Description

The following embodiments of the present invention are provided to enable those skilled in the art to clearly understand the technical solutions and advantages of the present invention through the descriptions of the embodiments, and it should be noted that these embodiments do not constitute limitations to the claimed content of the present invention.

A preparation method of a hydrophilic tunable phthalocyanine blue pigment comprises the following steps:

s1: taking acid swelled phthalocyanine blue as a raw material, and dispersing the acid swelled phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension;

s2: adding a hydrophobic agent into the suspension in the S1, stirring, and then adding a silicon source and a silicon source hydrolytic agent;

s3: after the hydrolysis in the step S2 is completed, a proper amount of cracking agent is added to crack the surface-coated silicon dioxide layer and expose a large amount of silicon hydroxyl groups therein, thereby achieving the hydrophilic purpose of the phthalocyanine blue pigment.

Furthermore, the control of the hydrophilicity of the phthalocyanine blue is realized by controlling the addition amounts of the hydrophobizing agent and the silicon source.

Further, in step S2, the hydrophobic agent is hexadecyl trimethoxy silane, after the substance is added, the temperature of the mixed solution is raised to 50-70 ℃ and kept for 2-3h, and a small amount of toluene is added.

Further, the addition of a small amount of toluene in step S2 hydrolyzes hexadecyltrimethoxysilane to the hydroxyl group.

Further, the silicon source in step S2 is an organic silicon source, not an inorganic silicon source, because the hydrolysis controllability of the inorganic silicon source is worse and the coating is not uniform compared to the organic silicon source. Further preferably, the organic silicon source is tetraethoxysilane.

Further, the silicon source hydrolyzing agent in step S2 is an acidic ethanol solution.

Further, the cracking agent in step S3 refers to a strong alkaline solution, such as a NaOH solution or a mixed solution of NaOH and ethanol.

Example 1

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 10mL of hexadecyl trimethoxy silane and toluene, heating to 60 ℃, keeping the temperature and stirring for 2 hours, adding 5mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 5mL of 1M NaOH solution was added thereto to perform pyrolysis, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

Example 2

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 5mL of hexadecyl trimethoxy silane and toluene, heating to 60 ℃, keeping the temperature and stirring for 2 hours, adding 5mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 5mL of 1M NaOH solution was added thereto to perform pyrolysis, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

Example 3

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 2mL of hexadecyl trimethoxy silane and toluene, heating to 60 ℃, keeping the temperature and stirring for 2 hours, adding 5mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 5mL of 1M NaOH solution was added thereto to perform pyrolysis, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

Example 4

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 5mL of hexadecyl trimethoxy silane and toluene, heating to 70 ℃, keeping the temperature and stirring for 2 hours, adding 8mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 5mL of 1M NaOH solution was added thereto to perform pyrolysis, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

Example 5

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 5mL of hexadecyl trimethoxy silane and toluene, heating to 50 ℃, keeping the temperature and stirring for 3 hours, adding 5mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 10mL of 1M NaOH solution was added thereto for cleavage, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

Example 6

Firstly, taking 100g of acid-swollen phthalocyanine blue, dispersing the acid-swollen phthalocyanine blue in deionized water by using a mechanical stirrer to form a suspension, then adding 5mL of hexadecyl trimethoxy silane and toluene, heating to 60 ℃, keeping the temperature and stirring for 2 hours, adding 3mL of TEOS and acidic ethanol solution at the temperature, and continuing stirring for 1 hour; then, 5mL of 1M NaOH solution was added thereto to perform pyrolysis, so that the surface-coated silica was broken to expose the silicon hydroxyl groups therein. And finally, centrifugally separating the substances from the reaction solution, and washing the substances clean by using deionized water for multiple times.

From examples 1 to 3, it can be seen that continuous adjustment of the hydrophilicity of the phthalocyanine blue product can be achieved by using different proportions of the hydrophobizing agent and the silicon source. As can be seen from FIG. 1, the hydrophilic tunable phthalocyanine blue pigment of the invention has good dispersion stability in aqueous solution with pH of 6-9; as can be seen from FIG. 2, the hydrophilic phthalocyanine blue pigment of the invention has good dispersion stability at the temperature of 20-80 ℃ of the aqueous solution.