Nylon / spandex composite fiber dyeing auxiliary agent and preparation method thereof

Abstract

The invention discloses a chinlon / spandex composite fiber dyeing auxiliary agent and a preparation method thereof, and aims to provide a dyeing auxiliary agent capable of obviously improving the problems of'white exposure 'and staining of chinlon / spandex composite fibers. The structural formula is as follows: # imgabs0 #, wherein x is equal to 1-50; y is equal to 1 to 50; z is equal to 1-10; belongs to the technical field of applied chemistry.

Description

Technical Field

[0001] The invention relates to a nylon / spandex composite fiber dyeing auxiliary agent and also discloses a preparation method of the auxiliary agent; the invention belongs to the technical field of applied chemistry. Technical Background

[0002] Spandex, also known as polyurethane fiber, is often compounded with nylon because of its excellent breathability, elastic elongation and elastic recovery rate. It is widely used in yoga clothes, swimsuits, underwear and other fields.

[0003] The dyes that can be used to dye nylon include acid dyes, neutral dyes, reactive dyes, etc. However, no matter which dye is used, the dyeing effect on spandex is very limited. Therefore, there are two major problems in the dyeing of nylon-spandex composite fibers: the "whitening" problem of spandex and the problem of spandex staining. The "whitening" of spandex refers to the fact that the spandex is not dyed during dyeing, and the white undyed spandex appears when the fiber is stretched. This is particularly obvious on dark fabrics. This problem greatly lowers the grade of the fabric. The staining of spandex is mostly reflected in poor soap fastness.

[0004] In response to the above problems, current research mainly focuses on the following two aspects:

[0005] (1) Modify spandex from the fiber perspective to make it easier to dye

[0006] At present, scientific researchers mainly modify spandex by adjusting the polyol / isocyanate or chain extender part to improve its dyeability. Chinese patents CN103483478A, CN104141176A, CN101096779A, etc. all describe how to modify spandex to improve its dyeing performance. Generally speaking, the effect is general, and its mechanical properties will be affected while modifying the spandex. The price of dyeable spandex is also much higher than that of ordinary spandex, which increases the cost pressure of dyeing factories.

[0007] (2) From the dye perspective, develop dyes specifically for spandex

[0008] There are many studies and reports on modified disperse dyes, but almost no reports on acid dyes. In addition, the modification of dyes is relatively complicated and not widely applicable to fibers. Summary of the invention

[0009] To this end, the purpose of the present invention is to provide a dyeing auxiliary agent that can significantly improve the "whitening" and staining problems of nylon / spandex composite fibers and a method for preparing the auxiliary agent.

[0010] To this end, the first technical solution provided by the present invention is as follows:

[0011] A nylon / spandex composite fiber dyeing auxiliary agent, the structural formula is as follows:

[0012]

[0013] Among them: x=1~50; y=1~50; z=1~10.

[0014] The second technical solution provided by the present invention is a method for preparing the nylon / spandex composite fiber dyeing auxiliary agent described in the first technical solution, which comprises the following steps in sequence:

[0015] 1) 14.4-21.6 parts of sodium p-hydroxybenzenesulfonate, 6-9 parts of urea and 108.6-401 parts of intermediate (I) are sequentially added into a four-necked flask;

[0016] 2) Raise the temperature to 60°C, start dripping 28.4-30 parts of formaldehyde aqueous solution, and complete the dripping in 2-4 hours; continue the reaction at 60°C for 2-3 hours;

[0017] 3) Cooling to room temperature, a brown-red viscous liquid is obtained, which is the dyeing auxiliary agent for nylon / spandex composite fibers;

[0018] Wherein: The structural formula of intermediate (Ⅰ) is as follows:

[0019]

[0020] Where: R is -H or -CH 3 ; n = 1 ~ 100.

[0021] Furthermore, in the preparation method of the above-mentioned nylon / spandex composite fiber dyeing auxiliary agent, the intermediate (I) is prepared by the following steps:

[0022] 1) Add 75-150 parts of polyol, 75-150 parts of ethanol, 9.38 g-18.75 parts of methyl carbamate, and 0.005-0.01 parts of tetrabutyl titanate as catalyst into a three-necked flask;

[0023] 2) heating to boiling state and reacting for 3 hours, during which methanol as a byproduct is removed;

[0024] 3) vacuuming to remove the reaction solvent ethanol;

[0025] 4) Discharge the material to obtain a yellow viscous liquid intermediate (I).

[0026] Furthermore, in the method for preparing the nylon / spandex composite fiber dyeing auxiliary agent, the four-necked flask is equipped with a stirrer, a thermometer, and a nitrogen protection device.

[0027] Furthermore, in the method for preparing the nylon / spandex composite fiber dyeing auxiliary agent, the three-necked flask is equipped with a stirrer, a thermometer and a vacuum pumping device.

[0028] Furthermore, in the method for preparing the nylon / spandex composite fiber dyeing auxiliary agent, the mass concentration of the formaldehyde aqueous solution is 37%.

[0029] Furthermore, in the preparation method of the above-mentioned nylon / spandex composite fiber dyeing auxiliary agent, the polyol is one of PPG1500, PEG1000, and PEG3000.

[0030] Compared with the prior art, the present invention has the following advantages:

[0031] 1. The nylon / spandex composite fiber dyeing auxiliary provided by the present invention has abundant -OH, -NH groups and sulfonic acid groups, and can have good binding force with acid dyes, and can greatly improve various fastnesses of dyes on fibers;

[0032] 2. The nylon / spandex composite fiber dyeing auxiliary provided by the present invention has an NH-C(O) bond that is very close to that of spandex. According to the principle of like dissolves like, the dye can be more easily adsorbed on the spandex, effectively avoiding the problem of "whitening" and staining caused by the weak binding of the dye in the later stage.

[0033] 3. The nylon / spandex composite fiber dyeing auxiliary agent provided by the present invention has readily available raw materials and a simple process. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The compound provided in Example 3 of the present application 1 H NMR spectrum. DETAILED DESCRIPTION

[0035] The following is a clear and complete description of the technical solutions implemented in the present invention. Obviously, the described embodiments are only the main test processes of the present invention. For process parameters or conditions not specifically specified, conventional techniques can be used.

[0036] Example 1

[0037] The present invention provides a nylon / spandex composite fiber dyeing auxiliary agent, and its structural formula is as follows:

[0038]

[0039] Where: x=12, y=25, z=5.

[0040] The preparation method of the dyeing auxiliary agent comprises the following steps in sequence:

[0041] 1) 18 g of sodium p-hydroxybenzenesulfonate, 9 g of urea and 108.6 g of intermediate (I) were added sequentially into a 500 ml four-necked flask (equipped with a stirrer, a thermometer and a nitrogen protection device);

[0042] 2) Raise the temperature to 60°C, and when the temperature reaches 60°C, begin to dropwise add 28.4 g of 37% formaldehyde aqueous solution, and complete the addition within 3 hours;

[0043] 3) Keep the temperature at 60°C and continue the reaction for 2 hours;

[0044] 4) Cool to room temperature to obtain a brown-red viscous liquid, which is filtered through a 200-mesh sieve to remove possible impurities to obtain the dyeing auxiliary agent for nylon / spandex composite fibers.

[0045] Wherein, intermediate (I) is prepared by the following steps:

[0046] 1) 150g PPG1500, 150g ethanol, 18.75g methyl carbamate, and 0.01g catalyst tetrabutyl titanate were added sequentially into a 500ml three-necked flask (with a stirrer, a thermometer, and a vacuum pump);

[0047] 2) Turn on the heating device, raise the temperature to boiling state, and time the reaction for 3 hours, while the by-product methanol is removed;

[0048] 3) Turn on the vacuum pumping equipment and evacuate the reaction solvent ethanol (the vacuum degree is controlled below -0.8 MPa);

[0049] 4) Discharge the material and filter it through a 200-mesh sieve to obtain a yellow viscous liquid intermediate (I).

[0050]

[0051] Where: R = -CH 3 , n=25.

[0052] Example 2

[0053] The present invention provides a nylon / spandex composite fiber dyeing auxiliary agent, the structural formula of which is:

[0054]

[0055] Among them: x=9, y=20, z=2.

[0056] The preparation method of the dyeing auxiliary agent comprises the following steps in sequence:

[0057] 1) 14.4 g of sodium p-hydroxybenzenesulfonate, 7.2 g of urea and 401 g of intermediate (I) were added sequentially into a 500 ml four-necked flask (equipped with a stirrer, a thermometer and a nitrogen protection device);

[0058] 2) Raise the temperature to 60°C, and when the temperature reaches 60°C, begin to dropwise add 28.4 g of 37% formaldehyde aqueous solution, and complete the addition within 3 hours;

[0059] 3) Keep the temperature at 60°C and continue the reaction for 3 hours;

[0060] 4) Cool to room temperature to obtain a brown-red viscous liquid, which is filtered through a 200-mesh sieve to remove possible impurities to obtain the dyeing auxiliary agent for nylon / spandex composite fibers.

[0061] Wherein, intermediate (I) is prepared by the following steps:

[0062] 1) 150 g PEG3000, 150 g ethanol, 9.38 g methyl carbamate, and 0.005 g catalyst tetrabutyl titanate were sequentially added into a 500 ml three-necked flask (with a stirrer, a thermometer, and a vacuum pump);

[0063] 2) heating to boiling state and reacting for 3 hours, during which methanol as a byproduct is removed;

[0064] 3) Vacuuming (the vacuum degree is controlled below -0.8 MPa) to remove the reaction solvent ethanol;

[0065] 4) Discharge the material and filter it through a 200-mesh sieve to obtain a yellow viscous liquid intermediate (I).

[0066]

[0067] Wherein: R=-H, n=67.

[0068] Example 3

[0069] The present invention provides a nylon / spandex composite fiber dyeing auxiliary agent, the structural formula of which is:

[0070]

[0071] Where: x=15, y=15, z=3.

[0072] The preparation method of the dyeing auxiliary agent comprises the following steps in sequence:

[0073] 1) 21.6 g of sodium p-hydroxybenzenesulfonate, 6 g of urea and 238 g of the intermediate (I) were added sequentially into a 500 ml four-necked flask (equipped with a stirrer, a thermometer and a nitrogen protection device);

[0074] 2) Raise the temperature to 60°C, and when the temperature reaches 60°C, begin to dropwise add 30g of 37% formaldehyde aqueous solution, and complete the addition within 3 hours;

[0075] 3) Keep the temperature at 60°C and continue the reaction for 2 hours;

[0076] 4) Cool to room temperature to obtain a brown-red viscous liquid, which is filtered through a 200-mesh sieve to remove possible impurities to obtain the dyeing auxiliary agent for nylon / spandex composite fibers.

[0077] Wherein: intermediate (I) is prepared by the following steps:

[0078] 1) 50g PEG1000, 50g ethanol, 9.38g methyl carbamate, and 0.005g catalyst tetrabutyl titanate were added sequentially into a 250ml three-necked flask (with a stirrer, a thermometer, and a vacuum pump);

[0079] 2) heating to boiling state and reacting for 3 hours, during which methanol as a byproduct is removed;

[0080] 3) Vacuuming (the vacuum degree is controlled below -0.8 MPa) to remove the reaction solvent ethanol;

[0081] 4) Discharge the material and filter it through a 200-mesh sieve to obtain a yellow viscous liquid intermediate (I).

[0082]

[0083] Wherein: R=-H, n=22.

[0084] That 1 H NMR spectrum reference Figure 1 ,pass Figure 1 It can be seen that around 7.8 ppm is the peak of -OH on the benzene ring, 7.3-7.5 ppm is the peak of hydrogen on the benzene ring, the peak of 4.7-4.9 ppm corresponds to the peak of urea NH, and the peak of 2.3-3.3 ppm corresponds to the hydrogen on the methylene group.

[0085] In order to better use the nylon / spandex composite fiber dyeing auxiliary provided in this application, the actual dyeing formula Table 1 is given below:

[0086] Table 1

[0087]

[0088]

[0089] It should be noted that the percentage of the leveling agent and the dyeing auxiliary provided in Example 1 is the mass percentage of the product to be dyed.

[0090] Customers can choose leveling agent according to actual needs.

[0091] When used, put the product to be dyed into the dyeing container, add the components according to the dosage of formula 1 or formula 2, heat to 40°C, stir evenly, then heat to 98°C again and dye for 60 minutes, then cool to room temperature and wash with water.

[0092] In order to demonstrate the effect of the technical solution provided in the present application, the performance test process and data of the dyeing auxiliaries provided in Examples 1 to 3 are given below:

[0093] Test of performance after dyeing:

[0094] 1. The apparent color gain K / S value of nylon / spandex composite fabric (nylon / spandex 80 / 20) after dyeing was tested using SF600XDatacolor colorimetric spectrometer (D65 light source). The fabric surface was measured three times in parallel at different positions and the average value was taken. The results are shown in Table 2:

[0095] Table 2

[0096]

[0097] The blank described in Table 2 does not contain the nylon / spandex composite fiber dyeing auxiliary provided by the present application, and other formulas and conditions are the same as those of Examples 1-3.

[0098] 2. The color fastness to washing test was carried out according to the experimental scheme B(2) in GB / T3921-2008 Textiles - Color fastness to washing test to test the color fastness and staining fastness of the fabric. The adjacent fabrics were acetate, cotton, nylon, polyester, acrylic and wool. The results are shown in Table 3:

[0099] Table 3

[0100]

[0101] The blank described in Table 3 does not contain the nylon / spandex composite fiber dyeing auxiliary provided by the present application, and other formulas and conditions are the same as those of Examples 1-3.

[0102] It can be seen from Table 2 that when the spandex fabric is dyed in the same bath with an acid dye, the addition of the dyeing auxiliary in the embodiment can significantly improve the K / S value of the nylon / spandex blended fabric compared with the blank, and after soap washing, the K / S value of the fiber treated with the dyeing auxiliary in the embodiment is still much higher than that of the untreated blank, indicating that the dyeing auxiliary in the invention can well help the acid dye to dye onto the spandex and enter the fiber, and after soap washing, more dyes are still retained on the fiber, indicating that the acid dye and spandex are well combined.

[0103] It can be seen from Table 3 that, compared with the blank sample, the nylon / spandex blended fabric to which the dyeing auxiliary in the embodiment is added has excellent soap fastness, especially can improve the staining grade of the dye on nylon and wool, indicating that the dyeing auxiliary can help improve the binding force of acid dyes with nylon and spandex fabrics.

Claims

1. A nylon / spandex composite fiber dyeing auxiliary agent, characterized in that: The structural formula is as follows: Among them: x=1~50; y=1~50; z=1~10.

2. The method for preparing the nylon / spandex composite fiber dyeing auxiliary agent according to claim 1, characterized in that: The steps are as follows: 1) 14.4-21.6 parts of sodium p-hydroxybenzenesulfonate, 6-9 parts of urea and 108.6-401 parts of intermediate (I) are sequentially added into a four-necked flask; 2) Raise the temperature to 60°C, start dripping 28.4-30 parts of formaldehyde aqueous solution, and complete the dripping in 2-4 hours; continue the reaction at 60°C for 2-3 hours; 3) Cooling to room temperature, a brown-red viscous liquid is obtained, which is the dyeing auxiliary agent for nylon / spandex composite fibers; Wherein: The structural formula of intermediate (Ⅰ) is as follows: Wherein: R is -H or -CH3; n=1~100.

3. The method for preparing the nylon / spandex composite fiber dyeing auxiliary according to claim 2, characterized in that: Intermediate (I) is prepared by the following steps: 1) Add 75-150 parts of polyol, 75-150 parts of ethanol, 9.38 g-18.75 parts of methyl carbamate, and 0.005-0.01 parts of tetrabutyl titanate as catalyst into a three-necked flask; 2) heating to boiling state and reacting for 3 hours, during which methanol by-product is removed; 3) vacuuming to remove the reaction solvent ethanol; 4) Discharge the material to obtain a yellow viscous liquid intermediate (I).

4. The method for preparing the nylon / spandex composite fiber dyeing auxiliary according to claim 2, characterized in that: The four-necked flask is equipped with a stirrer, a thermometer and a nitrogen protection device.

5. The method for preparing the nylon / spandex composite fiber dyeing auxiliary agent according to claim 3, characterized in that: The three-necked flask is provided with a stirrer, a thermometer and a vacuum pumping device.

6. The method for preparing the nylon / spandex composite fiber dyeing auxiliary according to claim 3, characterized in that: The mass concentration of the formaldehyde aqueous solution is 37%.

7. The method for preparing the nylon / spandex composite fiber dyeing auxiliary agent according to claim 3, characterized in that: The polyol is one of PPG1500, PEG1000 and PEG3000.

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