阅读说明：本技术 一种再生甲壳素色浆的制备方法 (Preparation method of regenerated chitin color paste ) 是由 隋晓锋 丁雷 王碧佳 冯雪凌 毛志平 徐红 于 2020-05-15 设计创作，主要内容包括：本发明涉及一种再生甲壳素色浆的制备方法。该方法包括：将不同脱乙酰化程度的再生甲壳素悬浮液和活性染料混合,将得到的混合溶液进行染色,得到染液,加入固色碱剂进行固色,降温,将得到的染色的再生甲壳素悬浮液加水稀释,过滤,然后分散于水中。该方法使用活性染料对再生甲壳素进行彩色化修饰,通过调控染料的种类和再生甲壳素的脱乙酰化程度可以得到不同色彩和色深的再生甲壳素色浆；所得到的再生甲壳素色浆继承了再生甲壳素的特点。(The invention relates to a preparation method of regenerated chitin color paste. The method comprises the following steps: mixing the regenerated chitin suspension liquid with different deacetylation degrees with reactive dye, dyeing the obtained mixed solution to obtain dye solution, adding a color fixing alkaline agent for color fixing, cooling, diluting the obtained dyed regenerated chitin suspension liquid with water, filtering, and dispersing in water. The method uses reactive dye to carry out colorized modification on the regenerated chitin, and can obtain regenerated chitin color pastes with different colors and color depths by regulating and controlling the types of the dye and the deacetylation degree of the regenerated chitin; the obtained regenerated chitin color paste inherits the characteristics of the regenerated chitin.)

1. A preparation method of regenerated chitin color paste comprises the following steps:

(1) preparing regenerated chitin suspensions with different deacetylation degrees by using chitin;

(2) mixing the regenerated chitin suspension liquid with different deacetylation degrees in the step (1) with reactive dye, and dyeing the obtained mixed solution to obtain dye liquor, wherein the concentration of the regenerated chitin with different deacetylation degrees in the mixed solution is 0.1-50g/L, and the concentration of the reactive dye is 0.01-50 g/L;

(3) adding a color fixing alkaline agent into the dye liquor obtained in the step (2) for color fixing, and cooling to obtain a dyed regenerated chitin suspension, wherein the dosage of the color fixing alkaline agent is 1-50 g/L;

(4) and (4) adding water to dilute the dyed regenerated chitin suspension in the step (3), filtering, and dispersing in water to obtain the regenerated chitin color paste.

2. The method of claim 1, wherein the step (1) of preparing the regenerated chitin suspensions with different deacetylation degrees by using chitin is as follows: deacetylating chitin by using 30-40% sodium hydroxide solution to obtain chitin with different deacetylation degrees, and dissolving and regenerating the chitin with different deacetylation degrees by using a phosphoric acid method or a sodium hydroxide/urea method to obtain the regenerated chitin suspension with the deacetylation degree of 0.5-40%.

3. The method as claimed in claim 1, wherein the reactive dye in the step (2) is one of monochlorotriazine-type reactive dye, dichloros-triazine-type reactive dye, vinyl sulfone-type reactive dye and monochlorotriazine double-reactive-group-type reactive dye.

4. The method according to claim 1, wherein the dyeing temperature in the step (2) is 20-40 ℃ and the dyeing time is 5-60 min.

5. The method according to claim 1, wherein the fixation alkaline agent in step (3) is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and sodium dihydrogen phosphate.

6. The method according to claim 1, wherein the process parameters for fixing in the step (3) are as follows: firstly, raising the temperature of a dye solution to 45-100 ℃ at a heating rate of 1-3 ℃/min, then adding 1-50g/L of a fixation alkaline agent, and fixing color at a color fixing temperature of 45-100 ℃ for 30-150 min.

7. The method as claimed in claim 1, wherein the regenerated chitin suspension dyed in step (3) is diluted to 0.1-5g/L by adding water in step (4).

8. The regenerated chitin color paste prepared by the method of claim 1.

9. The application of the regenerated chitin color paste prepared by the method of claim 1.

Technical Field

The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a preparation method of regenerated chitin color paste.

Background

Chitin is the second largest natural polymer material with the second best in nature than cellulose, has good biocompatibility and biodegradability, is widely derived from shells of arthropods (such as shrimps, crabs and the like), and has been increasingly emphasized in recent years. Chitin contains a large amount of acetamido and hydroxyl functional groups, wherein the acetamido can obtain amino with good reaction activity after deacetylation, and the existence of the amino and the hydroxyl endows the chitin with good chemical reactivity, thereby creating conditions for high added value utilization of the chitin. The chitin can be prepared into regenerated chitin through a dissolving and regenerating process, and the obtained regenerated chitin has a larger amorphous area, which is beneficial to more functional substances to modify and modify the chitin.

The reactive dye is a water-soluble dye, has the characteristics of bright color, wide color spectrum, strong applicability, simple dyeing process, high dyeing fastness and the like, is widely applied to dyeing of fibers or fabrics such as cotton, hemp, viscose, wool and the like, and is firmly fixed on the surfaces of the fibers or the fabrics through covalent bonds in the dyeing process. At present, most of researches on dyeing of fibers or fabrics by using reactive dyes are focused on dyeing of regenerated cellulose suspension, but the research on preparing regenerated chitin color paste by using reactive dyes to dye regenerated chitin is rarely reported in China. The regenerated chitin prepared through deacetylation and dissolution regeneration processes has amino and hydroxyl functional groups, and the suspension of the regenerated chitin shows positive charges in water. According to the dyeing theory of reactive dyes, the reactive dyes show negative charges in water, and the regenerated chitin showing positive charges more easily adsorbs the reactive dyes having negative charges than the regenerated cellulose suspension showing negative charges. Therefore, the regenerated chitin color paste prepared by using the reactive dye and the regenerated chitin suspension has good development prospect.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of regenerated chitin color paste to fill the blank of the prior art.

The invention provides a preparation method of regenerated chitin color paste, which comprises the following steps:

(1) preparing regenerated chitin suspensions with different deacetylation degrees by using chitin;

(2) mixing the regenerated chitin suspension liquid with different deacetylation degrees in the step (1) with reactive dye, and dyeing the obtained mixed solution to obtain dye liquor, wherein the concentration of the regenerated chitin with different deacetylation degrees in the mixed solution is 0.1-50g/L, and the concentration of the reactive dye is 0.01-50 g/L;

(3) adding a color fixing alkaline agent into the dye liquor obtained in the step (2) for color fixing, and cooling to obtain a dyed regenerated chitin suspension, wherein the dosage of the color fixing alkaline agent is 1-50 g/L;

(4) and (4) adding water to dilute the dyed regenerated chitin suspension in the step (3), filtering, and dispersing in water to obtain the regenerated chitin color paste.

The preparation of the regenerated chitin suspensions with different deacetylation degrees by using chitin in the step (1) comprises the following steps: deacetylating chitin by using 30-40% sodium hydroxide solution to obtain chitin with different deacetylation degrees, and dissolving and regenerating the chitin with different deacetylation degrees by using a phosphoric acid method or a sodium hydroxide/urea method to obtain the regenerated chitin suspension with the deacetylation degree of 0.5-40%.

The reactive dye in the step (2) is one of monochlorotriazine type reactive dye, dichloros-triazine type reactive dye, vinyl sulfone or monochlorotriazine double-reactive group type reactive dye.

And (3) in the step (2), the dyeing temperature is 20-40 ℃, and the dyeing time is 5-60 min.

And (3) the color fixing alkaline agent is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and sodium dihydrogen phosphate.

The color fixing process parameters in the step (3) are as follows: firstly, raising the temperature of a dye solution to 45-100 ℃ at a heating rate of 1-3 ℃/min, then adding 1-50g/L of a fixation alkaline agent, and fixing color at a color fixing temperature of 45-100 ℃ for 30-150 min.

In the step (4), the regenerated chitin suspension dyed in the step (3) is diluted to 0.1-5g/L by adding water.

And (4) filtering in the step (4) by using a Buchner funnel. The washing was repeated with a buchner funnel until the filtrate was colorless. The filtration is to wash off the unfixed reactive dye on the dyed regenerated chitin.

The step (4) of dispersing in water is as follows: redisperse the colored regenerated chitin in the buchner funnel in water.

The redispersion of the colored regenerated chitin in the buchner funnel in water is as follows: adding the color regenerated chitin in a Buchner funnel into water, and uniformly dispersing the color regenerated chitin in the water by using a homogenizer at a rotating speed of 500-15000 r/min to obtain the regenerated chitin color paste.

The invention also provides the regenerated chitin color paste prepared by the method.

The invention also provides application of the regenerated chitin color paste prepared by the method.

Advantageous effects

The invention uses the reactive dye to carry out colorized modification on the regenerated chitin, and can obtain the regenerated chitin color paste with different colors and color depths by regulating and controlling the types of the dye and the deacetylation degree of the regenerated chitin.

The method has simple process and easy production, and the obtained regenerated chitin color paste inherits the characteristics of the regenerated chitin, such as good viscoelasticity, excellent emulsifying capacity, biodegradability, environmental protection and the like, so that the regenerated chitin color paste serving as a colorful biomass material can be used as a rheological regulator, an emulsifier, an environment-friendly reinforcing material and the like, can also be used for preparing ink, a colored coating, a colored textile or a colored composite material, and realizes the high added value utilization of natural macromolecules of the chitin.

Drawings

FIG. 1 is a schematic view of the preparation process of the regenerated chitin color paste of the invention.

FIG. 2 is a schematic diagram of the deacetylation process of chitin according to the present invention.

FIG. 3 is a schematic diagram of the dyeing reaction of the reactive dye of the present invention to regenerated chitin.

Fig. 4 is a rheological curve diagram of the polyurethane/red regenerated chitin composite emulsion prepared by the invention.

Fig. 5 is a photomicrograph of a yellow regenerated chitin stabilized sunflower oil emulsion prepared in accordance with the present invention.

Fig. 6 is an optical photograph of the blue polyacrylate/regenerated chitin composite film prepared by the present invention.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.