阅读说明：本技术 针对聚丙烯纤维织物的染色方法 (Dyeing method for polypropylene fiber fabric ) 是由 江华 郭广落 陈维国 崔志华 于 2020-11-24 设计创作，主要内容包括：本发明公开了一种针对聚丙烯纤维织物的染色方法,包括如下步骤：将0.01～10g染料溶于100ml溶剂中,配制成染液；将聚丙烯纤维织物浸入染液中浸染；取出浸泡后的聚丙烯纤维织物干燥；再置于两片不锈钢薄板中,整体放入加热装置中加热；最终将聚丙烯纤维织物从加热装置中取出,自然冷却。本发明的染色方法操作简单,染色织物具有优异的耐皂洗、耐摩擦、耐升华等色牢度,应用前景潜力巨大。(The invention discloses a dyeing method for polypropylene fiber fabric, which comprises the following steps: dissolving 0.01-10 g of dye in 100ml of solvent to prepare a dye solution; immersing the polypropylene fiber fabric into a dye solution for dip dyeing; taking out the soaked polypropylene fiber fabric and drying; then placing the stainless steel sheets into two stainless steel sheets, and integrally placing the stainless steel sheets into a heating device for heating; finally, taking the polypropylene fiber fabric out of the heating device and naturally cooling. The dyeing method disclosed by the invention is simple to operate, and the dyed fabric has excellent color fastness such as soaping resistance, friction resistance, sublimation resistance and the like, and has a huge application prospect potential.)

1. The dyeing method for the polypropylene fiber fabric is characterized by comprising the following steps:

(1) dissolving 0.01-10 g of dye in 100ml of solvent to prepare a dye solution;

(2) immersing a polypropylene fiber fabric into the dye liquor obtained in the step (1); the dyeing liquid temperature is 60-80 ℃, the dip dyeing time is 0.5-5 h, and the mass ratio of the polypropylene fiber fabric to the dyeing liquid is 1: 5-1: 100;

(3) taking out the soaked polypropylene fiber fabric obtained in the step (2), and drying at 30-100 ℃;

(4) placing the polypropylene fiber fabric obtained in the step (3) into two stainless steel sheets, and integrally placing the two stainless steel sheets into a heating device for heating; the heating temperature is 100-160 ℃, the heating time is 0.5-10 h,

(5) and (4) taking the polypropylene fiber fabric obtained in the step (4) out of the heating device, and naturally cooling.

2. The dyeing method for polypropylene fiber fabric according to claim 1, wherein the dye is:

3. the dyeing method for polypropylene fiber fabric according to claim 2, characterized in that:

the solvent in the step (1) is as follows: methanol, ethanol, acetone, diethyl ether, dichloromethane, ethyl acetate, N-dimethylformamide and dimethyl sulfoxide.

4. The dyeing method for polypropylene fiber fabric according to claim 3, wherein:

in the step (2), the dip dyeing time is 0.5-2 h.

5. The dyeing method for polypropylene fiber fabric according to claim 4, wherein:

in the step (4), the heating temperature is 120-160 ℃; the heating time is 0.5-4 h.

6. The method for dyeing a polypropylene fiber fabric according to any one of claims 1 to 5, wherein: further comprises the following step (6): repeating the steps (1) to (5) for 1 to 4 times.

7. The method for dyeing a polypropylene fiber fabric according to any one of claims 1 to 5, wherein: the thickness of the stainless steel sheet is 0.2-0.5 mm.

Technical Field

The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a dyeing method for polypropylene fiber fabrics.

Background

Polypropylene fibers (commonly known as polypropylene) were successfully developed in 1955 and were commercially produced in 1957 in italy. The polypropylene fibers are of various varieties, including filaments, short fibers, split fibers, bristles, flat filaments and the like. Polypropylene is particularly light in weight and has a density of only 0.91g/cm³The fiber is the lightest fiber of all synthetic fibers at present. The polypropylene fiber has higher strength and better chemical corrosion resistance, is an ideal material for manufacturing ropes, fishing nets and cables, is widely used for industrial textiles, and can be used as a substitute material of cigarette filters. The common polypropylene fiber is used as the clothing fiber, has good warmth retention property and moisture conductivity, is not cold when being used as underwear, and is mostly used as underwear and disposable sanitary articles. (reference: in Weidong, Main edition, textile materials science, Beijing: Chinese textile Press, 2006 version 1)

The polypropylene fiber is obtained by polymerizing propylene as a monomer and has a molecular structure ofBecause the structure only contains carbon-carbon bonds and carbon-hydrogen bonds and the fiber structure is compact, the polypropylene fiber is difficult to dye by adopting a conventional dyeing method, and the polypropylene fiber is also known as a difficult-to-dye fiber (refer to: Zhu-Li-printing and dyeing, 2006, (22), 57). One commonly used method at present adopts a stock solution coloring method before spinning, but has the problems of incomplete color spectrum, high cost and the like (refer to Yang Meng Yang, et al. textile guide, 2019, (06), 87-90).

Therefore, there is an urgent need to develop an effective dyeing solution.

Korean scholars reported a reactive dye A for polypropylene fibers as shown in the following formula for dyeing polypropylene fibers in a fast red-orange color in the last eighties of the seventies of the last century (refer to Liuyi, et al. dyes and dyeings 2004, 41(3), 125-432; Journal of the Korea Chemical Society,1979,23(6), 412-416; Journal of the Korea Chemical Society,1984,28(6), 425-432).

The general formula of the dye is as follows:

wherein D is a dye chromophore.

The main problems of this dye are: (1) the dye is obtained by processing a dye precursor by adopting n-butyllithium, and the dye contains a nitrogen-lithium bond, is sensitive to water and is not easy to store; the used n-butyllithium is easy to spontaneously combust when meeting water and the like, the danger is high, and the dye synthesis is not beneficial to large-scale industrial application; (2) the carbon-nitrogen double bond contained in the dye structure can form a conjugated system with an azo color body, so that the double bond can influence the color of the dye; however, according to the dyeing mechanism reported in the literature, the carbon-nitrogen double bond is replaced by a carbon-carbon single bond between the dye and the fiber after dyeing, that is, the conjugated system formed by the carbon-nitrogen double bond and the azo color former is destroyed after dyeing, so that the color of the dyed fiber and the color of the dye per se are changed; (3) according to literature reports, the color depth value of polypropylene fibers dyed by the dye is generally lower; (4) the dye can generate byproducts such as p-toluenesulfonate and lithium salt after dyeing, and the like, which need to be treated, and is unfavorable for energy conservation and environmental protection.

These problems have severely limited the development of the above-mentioned dyes.

The bis-aziridine compounds are a new class of substances and are widely studied in the fields of materials, chemistry, biology and the like. It is reported (see: Lepage et al, Science 2019,366,875-878) that the bis-aziridine structure forms an active carbene intermediate under high temperature (>100 ℃) or ultraviolet irradiation (wavelength around 350 nm) and thus has the ability to insert oxygen-hydrogen bonds, nitrogen-hydrogen bonds and even carbon-hydrogen bonds. The general structural formula of the bis-aziridines is as follows:

reactive dyes with a diazirine structure as a reactive group and a corresponding dyeing method with polypropylene as a dyeing object are not available.

Disclosure of Invention

The problem to be solved by the invention is to provide a method for dyeing polypropylene fiber fabrics by using dyes containing diazirine reactive groups as coloring substances.

In order to solve the technical problems, the invention provides a dyeing method for polypropylene fiber fabric, which comprises the following steps:

(1) dissolving 0.01-10 g of dye in 100ml of solvent to prepare a dye solution;

(2) immersing a polypropylene fiber fabric (polypropylene fabric) into the dye liquor obtained in the step (1); the dyeing liquid temperature is 60-80 ℃, the dip dyeing time is 0.5-5 h, and the mass ratio of the polypropylene fiber fabric to the dyeing liquid is 1: 5-1: 100;

(3) taking out the soaked polypropylene fiber fabric obtained in the step (2), and drying at 30-100 ℃ to constant weight;

(4) placing the polypropylene fiber fabric obtained in the step (3) into two stainless steel sheets, and integrally placing the two stainless steel sheets into a heating device (oven) for heating; the heating temperature is 100-160 ℃, the heating time is 0.5-10 h,

(5) and (4) taking the polypropylene fiber fabric obtained in the step (4) out of the heating device, and naturally cooling (cooling to room temperature).

As an improvement of the dyeing method of the invention, which aims at the polypropylene fiber fabric, the dye is as follows:

as a further improvement of the dyeing method of the invention for polypropylene fiber fabrics, the solvents in step (1) are: methanol, ethanol, acetone, diethyl ether, dichloromethane, ethyl acetate, N-dimethylformamide and dimethyl sulfoxide.

Methanol, ethanol, acetone, N-dimethylformamide are preferred, and methanol is more preferred.

As a further improvement of the dyeing process of the present invention for polypropylene fiber fabrics: in the step (2), the dip dyeing time is 0.5-2 h (preferably 1 h).

As a further improvement of the dyeing process of the present invention for polypropylene fiber fabrics: in the step (4), the heating temperature is 120-160 ℃ (more preferably 140 ℃); the heating time is 0.5-4 h (more preferably 2 h).

As a further improvement of the dyeing process of the present invention for polypropylene fiber fabrics: further comprises the following step (6): repeating the steps (1) to (5) for 1 to 4 times.

As a further improvement of the dyeing process of the present invention for polypropylene fiber fabrics: the thickness of the stainless steel sheet is 0.2-0.5 mm.

The dye containing the bisaziridine reactive group is used as a coloring matter, and after the dye is uniformly attached to the polypropylene fabric, the dye and the fiber are combined by a covalent bond and cannot fall off by a high-temperature color fixing method. In the repeated dyeing process, the original dye on the fabric is covalently combined with the fiber, so that the dye in the dye liquor can be used for dyeing the fiber continuously, and the aim of deep dyeing is fulfilled.

Compared with the prior art, the invention has the following technical advantages:

the dye used in the invention is a dye containing a bisaziridine reactive group, a bisaziridine structure generates a carbene active intermediate under the action of high temperature, the carbene active intermediate has the capacity of being inserted into a methine carbon-hydrogen bond in polypropylene to generate chemical reaction, and after high-temperature color fixation, a covalent bond is formed between the dye and a fiber, so that the dye has excellent color fastness grade; the dye is convenient to synthesize, the color of the dye is not influenced by the structure of the bis-aziridine, only nitrogen molecules are released during color fixation, and no additional by-product is generated; the invention provides a repeated dyeing method, which can obtain the deep dyeing effect of the polypropylene fiber textile; the dyeing method is simple to operate, and the dyed fabric has excellent color fastness such as soaping resistance, friction resistance, sublimation resistance and the like, and has a huge application prospect potential.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 is a reaction mechanism of a bisaziridine dye with polypropylene fibers; the color body is 1-aminoanthraquinone;

FIG. 2 is a schematic view of the dyeing step of the present invention.

Detailed Description

The present invention will be described in detail and specifically by the following examples to better understand the present invention, but the following examples do not limit the scope of the present invention.

The raw material 1 can be obtained commercially or synthesized according to the methods provided by the literature (Angew. chem. int. Ed.2018,57, 16688-16692); starting material 2 (1-aminoanthraquinone) was obtained commercially.

Dye example 1: synthesis of dyes

Adding a stirrer, raw material 1(5mmol, 1.395g), raw material 2(5mmol, 1.116g), potassium carbonate (10mmol, 1.382g) and N, N-dimethylformamide (60ml) into a dry 250ml three-neck flask under the protection of nitrogen, placing the three-neck flask in an oil bath, stirring, heating to 80 ℃ and keeping for 4 hours; the reaction was stopped when the starting material was consumed, as monitored by thin layer chromatography.

Adding 100ml of water and 50ml of ethyl acetate, extracting for three times (50 ml of ethyl acetate multiplied by 3), combining organic phases, evaporating the solvent by using a rotary evaporator, separating the rest substance by using column chromatography (200-300 meshes of silica gel), and obtaining the dye by using petroleum ether/ethyl acetate (10/1) and V/V as eluent, wherein the yield is 84.5 percent, and the red solid is 1.78 g.

¹H NMR(CDCl₃,400MHz)δ8.65(s,1H),8.33-8.31(m,1H),7.90-7.84(m,2H),7.81-7.79(m,2H),7.47(dd,J¹＝J²＝7.2Hz,1H),7.32-7.26(m,4H),7.23(dd,J¹＝7.6Hz,J²＝2.0Hz,1H),4.32(s,2H).¹³C NMR(CDCl₃,100MHz)δ186.21,182.58,145.86,139.62,134.95,133.95,133.82,133.46,133.37,129.31,129.28,128.58,126.66,126.62,125.39,122.61(q,J＝268Hz),122.15,119.22,118.98,80.67,47.28.ESI-MS:m/z＝422.1[M+H].

Comparative example 1:

synthesis of comparative dye II

The synthesis of comparative dye II is described with reference to dye example 1, except that starting material 3(5mmol, 1.335g) is used instead of starting material 1(5mmol, 1.395 g).

The obtained comparative dye II, red solid, 1.65g, yield 80.6%;¹H NMR(CDCl₃,400MHz)δ8.33-8.31(m,1H),8.02(d,J＝7.6Hz,2H),7.87-7.84(m,2H),7.81-7.79(m,2H),7.43(dd,J¹＝J²＝7.6Hz,1H),7.39(d,J＝7.6Hz,2H),7.14(d J＝7.2Hz,1H),4.32(s,2H).¹³C NMR(CDCl₃,100MHz)δ186.21,182.58,177.84(q,J＝32Hz),145.86,140.22,134.95,133.95,133.82,133.46,133.37,130.60,130.00,128.58,128.25,126.66,126.62,122.15,119.22,118.98,116.77(q,J＝267Hz),47.28.ESI-MS:m/z＝410.1[M+H].

example 1, a dyeing method for polypropylene fiber fabric (polypropylene fabric), which comprises the following steps in sequence:

1) 0.5g of the dye (obtained in dye example 1) was dissolved in a flask (with reflux tube) containing 100ml of methanol, stirred well, placed in an oil bath and heated to 60 ℃;

2) 2g of polypropylene fabric is immersed in the solution, the temperature is kept at 60 ℃, and the dip-dyeing time is 1 h;

3) taking out the soaked polypropylene fabric, and drying the polypropylene fabric in a 60 ℃ oven to constant weight;

the constant weight state means that the weighing error of each gram of the fabric is not more than 0.002g before and after airing for 30 minutes (the common sense is that);

4) and placing the dried polypropylene fiber fabric into two stainless steel sheets, clamping, placing into an oven at 140 ℃, heating for 2h, taking out, cooling to room temperature to obtain red dyed polypropylene fiber fabric, and testing that the K/S value of the fabric is 4.2.

The thickness of the stainless steel sheet is 0.2-0.5 mm.

Comparative example 1:

the dye of example 1 was changed to comparative dye II (obtained in comparative example 1), and the remainder was identical to that of example 1; a red dyed polypropylene fabric was obtained, the dyed fabric having a K/S value of 4.0.

Comparative example 2:

the dye of example 1 was changed to the following comparative dye III, the remainder being identical to example 1; a red dyed polypropylene fabric was obtained, the dyed fabric having a K/S value of 2.3.

The structure of comparative dye III is as follows:

comparative example 3:

the dye in example 1 was changed to the commercial dye c.i. disperse red 9, and the remainder was identical to example 1; a red dyed polypropylene fabric was obtained, the dyed fabric having a K/S value of 3.8.

C.i. disperse red 9 has the formula:

comparative examples 4,

The dye in the example 1 is changed into the dye A described in the background technology, and the rest is equal to the dye A in the example 1; an orange dyed polypropylene fabric was obtained, the dyed fabric having a K/S value of 1.8.

Dye A has the following structure:

experiment 1:

the fabric dyed in example 1 and the fabric dyed in comparative examples 1 to 4 were placed in a single-neck flask containing N, N-dimethylformamide (100ml), heated to 100 ℃, held for 30min, taken out of the flask, cooled, washed with clear water, and air-dried, and the K/S value and color of the fabric were measured as shown in table 1 below:

TABLE 1

	K/S value	Colour(s)
			Example 1 dyed Fabric	4.1	Red colour
Comparative example 1 dyed Fabric	0.05	White colour
			Comparative example 2 dyed Fabric	1.2	Light red
Comparative example 3 dyed Fabric	0.04	White colour
			Comparative example 4 dyed Fabric	0.6	Near white color

As can be seen from the results of Table 1 above, the color of the dyed fabric of example 1 can be hardly extracted by N, N-dimethylformamide, which indirectly proves that the dye (I) provided by the present invention forms a firm covalent bond with the polypropylene fabric; whereas the dye used in comparative example 1 contained only the bisaziridine structure, and the color on the resulting dyed fabric was completely extracted by N, N-dimethylformamide; the dye color body in comparative example 2 has one more primary amino group, so that the color yield of the dyed fabric is reduced, and part of the color is extracted by N, N-dimethylformamide, presumably because the carbene intermediate generated by the bis-aziridine reacts preferentially with the primary amino group, the dye cannot be combined with the fiber due to self-crosslinking; comparative example 3 used a conventional commercial disperse dye, and the color of the dyed fabric could be extracted completely; the dyed fabric of comparative example 4 also had a lower color yield and the color was easily extracted by the solvent, presumably because the nitrogen-lithium bond in the structure was dissociated by methanol, which resulted in partial deactivation of the dye in methanol and a large amount of the deactivated dye could not be bound to the fiber.

Experiment 2: GB/T3921-2008 soaping color fastness resistance of textile color fastness test, GB/T3920-2008 friction color fastness resistance of textile color fastness test, GB/T6152-1997 hot pressing color fastness resistance of textile color fastness test are adopted to test the soaping color fastness, friction color fastness and sublimation color fastness of the dyed fabrics in example 1 and comparative examples 1-4, and the results are shown in the following table 2:

TABLE 2

The results in the table show that the polypropylene fiber fabric dyed by the dyeing method provided by the invention has good fastness to soaping, friction and sublimation.

Example 2: repeated dyeing

Replacing the original polypropylene fabric with the red dyed polypropylene fabric obtained in the example 1, continuously dyeing for 1-3 times according to the method described in the example 1, and then detecting according to the method described in the experiment 1, wherein the obtained results are shown in the following table 3;

TABLE 3

Example 3 repeated dyeing

0.5g of the dye (obtained in dye example 1) was dissolved in a flask (with reflux tube) containing 20ml of methanol, stirred well, placed in an oil bath and heated to 75 ℃; 1g of polypropylene fabric is immersed into the solution for 1h at the temperature of 75 ℃; taking out the polypropylene fabric, and drying the polypropylene fabric in a 60 ℃ oven to constant weight; and placing the polypropylene fabric into two stainless steel sheets, clamping, placing into an oven at 140 ℃, heating for 2 hours, taking out, and cooling to room temperature to obtain the red dyed polypropylene fabric after the first dyeing.

And (3) replacing the original polypropylene fabric with the red dyed polypropylene fabric dyed for the first time, and continuously dyeing for 1-3 times according to the method in the embodiment 3.

Then, the test was carried out according to the method described in experiment 1, and the results are shown in the following table 4;

TABLE 4

The results of the embodiments 2 and 3 show that the dyeing method provided by the invention can greatly improve the color depth value of the dyed polypropylene fiber fabric through repeated dyeing, and obtain satisfactory high color yield; the dye and the polypropylene fiber are combined by covalent bonds after being fixed, and can further adsorb more dye after being immersed in the dye liquor again, so that the color is deepened.

Comparative example 5: repeat dyeing of comparative dye II

Replacing the original polypropylene fabric with the dyed polypropylene fabric obtained in the comparative example 1, continuously dyeing for 1-3 times according to the method of the comparative example 1, and then detecting according to the method of the experiment 1, wherein the obtained results are shown in the following table 5;

TABLE 5

The results show that the polypropylene fabric cannot be deeply dyed by a repeated dyeing method when the dye has no bisaziridine structure.

Comparative example 6: repeat dyeing of comparison dye III

Replacing the original polypropylene fabric with the dyed polypropylene fabric obtained in the comparative example 2, continuously dyeing for 1-3 times according to the method of the comparative example 2, and then detecting according to the method of the experiment 1, wherein the obtained results are shown in the following table 6;

TABLE 6

The results show that, although the comparative dye III has a certain effect of improving the color yield in the repeated dyeing method, it is apparently not as effective as the present invention.

Comparative example 7: repeat dyeing of commercial dye C.I. disperse Red 9

Replacing the original polypropylene fabric with the dyed polypropylene fabric obtained in the comparative example 3, continuously dyeing for 1-3 times according to the method of the comparative example 3, and then detecting according to the method of the experiment 1, wherein the obtained results are shown in the following table 7;

TABLE 7

Comparative example 8: repeated dyeing of dye A

Replacing the original polypropylene fabric with the dyed polypropylene fabric obtained in the comparative example 4, continuously dyeing for 1-3 times according to the method described in the comparative example 4, and then detecting according to the method described in the experiment 1, wherein the obtained results are shown in the following table 8;

TABLE 8

Example 4, the methanol in example 1 was changed to the solvent described in table 9 below, and the rest was identical to example 1. The K/S values of the resulting fabrics compared to example 1 are set forth in Table 9 below.

TABLE 9

Example 5, the amount of the dye used in example 1 was changed to the amount described in table 10 below, and the remainder was the same as in example 1. The resulting fabric K/S values are as described in Table 10 below for the comparative example 1.

Watch 10

Example 6, the oven temperature and time in step 4) of example 1 were changed as described in table 11 below, and the rest was identical to example 1. The resulting fabric K/S values are as described in Table 11 below for the comparative example 1.

TABLE 11

From the above table in combination with the results of example 1, it can be seen that when the heating temperature is less than 140 ℃ or the heating time is less than 2 hours in step (4), it is difficult to completely react the dye with the fiber, resulting in part of the dye being extracted by the solvent.

Comparative example 9, "the polypropylene fiber fabric obtained in step 3) of example 1 was dried in an oven at 60 ℃ until the weight of the polypropylene fiber fabric was constant," modified "to" the polypropylene fiber fabric was dried at room temperature until the mass content of methanol on the fabric was 5% (i.e., a small amount of methanol was also contained) ", and the rest was the same as in example 1.

The fabric was tested to have a K/S value of 3.9. The dyed polypropylene fiber fabric is treated by the method of experiment 1, and the K/S value of the dyed fabric after the treatment is tested to be 3.1.

Namely, when the fixation is carried out under the condition of incomplete airing, the residual methanol can carry out competitive reaction with the dye at high temperature to inactivate the dye, and compared with the example 1, the K/S value after the fixation is slightly reduced.

Comparative example 10, the use of stainless steel sheet in step 4 of example 1 was eliminated, i.e. the polypropylene fabric was directly hung in an oven at 140 ℃ and heated for 2 h; the rest is equivalent to embodiment 1.

The fabric was tested to have a K/S value of 3.3.

The lower K/S value for the dyed fabric obtained in comparative example 10 compared to example 1 may be due to the fact that the dried polypropylene fabric was not placed in two stainless steel sheets, resulting in a small amount of dye sublimating away from the surface of the fabric before it was unreacted.

Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.