Polysulfonamide dyeing auxiliary agent and preparation method thereof

Abstract

The invention discloses a polysulfonamide dyeing assistant and a preparation method thereof, and aims to provide the polysulfonamide dyeing assistant which is environment-friendly, non-toxic, odorless, good in level dyeing effect and high in color yield K / S value, and various fastnesses meet requirements. The polysulfonamide dyeing auxiliary agent has the following structural formula: # imgabs0 #, wherein in the formula (I), n is equal to 1-100; belongs to the technical field of applied chemistry.

Description

Technical Field

[0001] The invention relates to an aromatic sulfone dyeing auxiliary, in particular to an auxiliary for dyeing aromatic sulfone with a cationic dye carrier. The invention also discloses a preparation method of the auxiliary, belonging to the technical field of applied chemistry. Technical Background

[0002] Polyphenylsulfone terephthalamide fiber, whose scientific name is polyphenylsulfone terephthalamide fiber, is a special fiber. Due to its excellent high temperature resistance and flame retardant properties, it is widely used in special protective equipment, aerospace, optical cables and other high-tech fields.

[0003] Aromatic sulfone contains rigid benzene rings and strong polar groups amide and sulfone in its structure, with strong intermolecular forces and high crystallinity. Therefore, it is difficult for dyes to enter its structure, making dyeing difficult.

[0004] At present, cationic dye carrier dyeing is usually used for the dyeing of sulfone fibers. However, this method also has the following defects: 1) Improper carrier selection leads to poor dyeing levelness or unstable dye solution during dyeing, resulting in fabric defects; 2) Most current carriers are not environmentally friendly, toxic and harmful, have a strong odor, and are harmful to the human body and the environment; 3) Carrier dyeing still has difficulties in dark dyeing, the color K / S value is low, and various fastnesses are poor; therefore, it is particularly important to develop an environmentally friendly, non-toxic and odorless sulfone fiber dyeing auxiliary. Summary of the invention

[0005] The purpose of the present invention is to provide an aromatic sulfone dyeing auxiliary agent which is environmentally friendly, non-toxic and tasteless, has good leveling effect, high color yield K / S value and meets the requirements of various fastnesses.

[0006] The second object of the present invention is to provide a method for preparing the above-mentioned aromatic sulfone dyeing auxiliary agent.

[0007] To this end, the first technical solution provided by the present invention is as follows:

[0008] A dyeing auxiliary agent for aromatic sulfone fiber, having the structural formula (I) as follows:

[0009]

[0010] Wherein, in formula (I), n=1-100.

[0011] The second technical solution provided by the present invention is as follows:

[0012] The preparation method of the aromatic sulfone dyeing auxiliary agent described in the first technical solution comprises the following steps in sequence:

[0013] 3) Add 200 ml of pretreated N-methylpyrrolidone into a four-necked flask, then add 10 g of pretreated calcium chloride, and turn on the nitrogen protection device to purge the equipment;

[0014] 4) Add 28.5-32.3 g of 4,4-diaminodiphenyl sulfone, stir to dissolve, and then cool the solution to 0° C. in an ice-water bath; then add 20.3 g of p-toluenesulfonyl chloride and stir for 20-40 minutes;

[0015] 3) Then the temperature is raised to 25° C., 6.2 g to 7.8 g of the compound represented by formula (II) is added to the reactor in step 2), and the reaction is continued for 1 to 2 hours to obtain a yellow viscous liquid, which is the aromatic sulfone dyeing auxiliary agent;

[0016]

[0017] R=C1-C18 saturated or unsaturated fatty chain.

[0018] Furthermore, in the preparation method of the above-mentioned aromatic sulfone dyeing auxiliary agent, the N-methylpyrrolidone pretreatment method is: adding molecular sieves and calcium hydride to N-methylpyrrolidone to remove water.

[0019] Furthermore, in the preparation method of the above-mentioned aromatic sulfone dyeing auxiliary agent, the calcium chloride pretreatment method is: heating the calcium chloride at 400° C. for 4 hours to remove crystal water.

[0020] Furthermore, in the above-mentioned preparation method of the aromatic sulfone dyeing auxiliary agent, the four-necked flask is equipped with a nitrogen protection device, a condenser, a stirrer and a thermometer.

[0021] Furthermore, in the above-mentioned method for preparing the aromatic sulfone dyeing auxiliary agent, the purging time is 10 minutes.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] 1. The dyeing auxiliary agent of aromatic sulfone provided by the present invention has a chemical structure very close to that of aromatic sulfone. According to the principle of like dissolves like, the auxiliary agent can well combine the fiber and the dye, achieve a very good leveling effect, have a high color yield K / S value, and meet the requirements for various fastnesses;

[0024] 2. The aromatic sulfone fiber additive provided by the present invention does not have an unpleasant odor similar to traditional carriers such as acetophenone, N-methyltoluidine, etc., and has relatively low toxicity and is friendly to humans and the environment;

[0025] 3. The aromatic sulfone dyeing auxiliary agent provided by the present invention is easy to prepare and has a simple process. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the FTIR spectrum of the aromatic sulfone dyeing auxiliary provided in Example 2. DETAILED DESCRIPTION

[0027] 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.

[0028] Example 1

[0029] The present invention provides an aromatic sulfone dyeing auxiliary agent, the structural formula of which is:

[0030]

[0031] Where R = -CH 3 , n=5.

[0032] The preparation of the aromatic sulfone dyeing auxiliary comprises the following steps in sequence:

[0033] 1) adding molecular sieves and calcium hydride to N-methylpyrrolidone (NMP) to remove water; heating calcium chloride at 400° C. for 4 hours to remove crystal water;

[0034] 2) Add 200 ml of the NMP pretreated in step 1) into a four-necked flask (equipped with a nitrogen protection device, a condenser, a stirrer, and a thermometer), then add 10 g of the calcium chloride pretreated in step 1), and open the nitrogen protection device to purge the equipment for 10 minutes;

[0035] 3) Add 32.3 g of 4,4-diaminodiphenyl sulfone, stir to dissolve, and then cool the solution to 0° C. in an ice-water bath; then add 20.3 g of p-toluenesulfonyl chloride and stir for 30 minutes;

[0036] 4) Raise the temperature to 25°C, add 6.2 g of the compound represented by formula (II) into the above reactor, and continue the reaction for 1 hour to obtain a yellow viscous liquid, which is the dyeing auxiliary agent for aromatic sulfone fiber.

[0037]

[0038] Where R = -CH 3。

[0039] Example 2

[0040] The present invention provides an aromatic sulfone dyeing auxiliary agent, the structural formula of which is:

[0041]

[0042] Where R = -C 12 H 25 , n=11.

[0043] The preparation of the aromatic sulfone dyeing auxiliary comprises the following steps in sequence:

[0044] 1) adding molecular sieves and calcium hydride to NMP to remove water; heating calcium chloride at 400° C. for 4 hours to remove crystal water;

[0045] 2) Add 200 ml of pretreated NMP into a four-necked flask (equipped with a nitrogen protection device, condenser, stirrer, and thermometer), then add 10 g of pretreated calcium chloride, and turn on the nitrogen protection device to purge the equipment for 10 minutes;

[0046] 3) Add 29.8 g of 4,4-diaminodiphenyl sulfone, stir to dissolve, and then cool the solution to 0° C. in an ice-water bath; add 20.3 g of p-toluenesulfonyl chloride and stir for 35 minutes;

[0047] 4) Raise the temperature to 25°C, add 7.6 g of the compound represented by formula (II) into the above reactor, and continue the reaction for 1.5 hours to obtain an orange-red viscous liquid, which is the dyeing auxiliary agent for aromatic sulfone fiber;

[0048]

[0049] Where R = -C 12 H 25。

[0050] Its FTIR spectrum can be found at Figure 1 , among which, 3200-3300cm -1 The NH vibration peak and OH vibration absorption peak of the amide bond, 2900, 2850cm -1 The absorption peaks of methyl and methylene are concentrated at 1600 cm -1 The vibration of C=O is around 1650-1700cm -1 The deformation, coupling, in-plane and out-of-plane bending vibrations of NH are around 1500cm -1 、1200cm -1 And fingerprint area 650cm -1 、720cm -1 The stretching vibration of sulfone group (-SO(=O)) is around 1300cm -1 、1100cm -1 And fingerprint area 700-900cm -1 about.

[0051] Example 3

[0052] The present invention provides an aromatic sulfone dyeing auxiliary agent, the structural formula of which is:

[0053]

[0054] Where R = -C 18 H 37 , n = 15

[0055] The preparation of the aromatic sulfone dyeing auxiliary comprises the following steps in sequence:

[0056] 1) Molecular sieves and calcium hydride were added to NMP to remove water, and calcium chloride was heated at 400° C. for 4 hours to remove crystal water;

[0057] 2) Add 200 ml of pretreated NMP into a four-necked flask (equipped with a nitrogen protection device, condenser, stirrer, and thermometer), then add 10 g of pretreated calcium chloride, and turn on the nitrogen protection device to purge the equipment for 10 minutes;

[0058] 3) Add 28.5 g of 4,4-diaminodiphenyl sulfone, stir to dissolve, and then cool the solution to 0° C. in an ice-water bath; then add 20.3 g of p-toluenesulfonyl chloride and stir for 40 minutes;

[0059] 4) Raise the temperature to 25°C, add 7.8 g of the compound represented by formula (II) into the above reactor, and continue the reaction for 2 hours to obtain a reddish brown viscous liquid, which is the aromatic sulfone dyeing auxiliary;

[0060]

[0061] Where R = -C 18 H 37 .

[0062] In order to better use the aromatic sulfone dyeing auxiliary provided in this application, the actual dyeing formula Table 1 is given below:

[0063] Table 1

[0064] Components Recipe dosage Cationic dye (red) (% owf) 3.5 Carrier / dyeing auxiliary prepared in Example 1 (g / l) 20 Sodium chloride / dye bath (g / l) 20 Dye bath pH 4 Bath ratio 1:20

[0065] When used, put the product to be dyed into the dyeing container, add the carrier according to the formula and dosage described in Table 1, heat it to 40°C, then add the dye, sodium chloride, and pH adjuster, stir for 20 minutes, then heat it to 130°C again and dye for 30 minutes, then cool it to room temperature 60°C and wash with soap.

[0066] In order to demonstrate the effect of the technical solution provided in the present application, the application and test data of the dyeing auxiliaries provided in Examples 1 to 3 when dyeing aromatic sulfone fibers with cationic dyes are given below:

[0067] 1. The apparent color value K / S value test of sulfone fiber after dyeing was tested by using SF600X Datacolor colorimetric spectrometer (D65 light source). The fabric surface was measured in parallel for 3 times at different positions and the average value was taken. The results are shown in Table 2:

[0068] Table 2

[0069]

[0070] 2. Color fastness to washing

[0071] The test method is based on GB / T3921.1-1997 Textiles - Tests for colour fastness to washing.

[0072] 3. Color fastness to rubbing

[0073] The test method is based on GB / T3920-1997 Textiles - Tests for colour fastness to rubbing.

[0074] Table 3

[0075]

[0076] It can be seen from Table 2 that when using cationic dyes to dye aromatic sulfone, compared with the blank (no dyeing auxiliary), the addition of the dyeing auxiliary in the embodiment can significantly improve the K / S value of aromatic sulfone, and compared with the traditional carrier, the K / S value is significantly improved, indicating that the dyeing auxiliary in the invention can significantly improve the dyeing power of cationic dyes on aromatic sulfone.

[0077] It can be seen from Table 3 that, compared with the blank (without dyeing auxiliary), adding the dyeing auxiliary in the example can significantly improve the soaping fastness and rubbing fastness of the cationic dye on the aromatic sulfone fiber, and is better than the traditional carrier.

Claims

1. A dyeing auxiliary agent for aromatic sulfone fiber, characterized in that: It has the following structural formula (I): Wherein (I) in the formula n = 1-100.

2. The method for preparing the aromatic sulfone dyeing auxiliary according to claim 1, characterized in that: The steps are as follows: 1) Add 200 ml of pretreated N-methylpyrrolidone into a four-necked flask, then add 10 g of pretreated calcium chloride, and turn on the nitrogen protection device to purge the equipment; 2) Add 28.5-32.3 g of 4,4-diaminodiphenyl sulfone, stir to dissolve, and then cool the solution to 0° C. in an ice-water bath; then add 20.3 g of p-toluenesulfonyl chloride and stir for 20-40 minutes; 3) Then the temperature is raised to 25° C., 6.2 g to 7.8 g of the compound represented by formula (II) is added to the reactor in step 2), and the reaction is continued for 1 to 2 hours to obtain a yellow viscous liquid, which is the aromatic sulfone dyeing auxiliary agent; R=C1-C18 saturated or unsaturated fatty chain.

3. The method for preparing the aromatic sulfone dyeing auxiliary according to claim 2, characterized in that: The method for pretreating N-methylpyrrolidone is: adding molecular sieve and calcium hydride to N-methylpyrrolidone to remove water.

4. The method for preparing the aromatic sulfone dyeing auxiliary according to claim 2, characterized in that: The calcium chloride pretreatment method is: heating the calcium chloride at 400° C. for 4 hours to remove crystal water.

5. The method for preparing the aromatic sulfone dyeing auxiliary according to claim 2, characterized in that: The four-necked flask is equipped with a nitrogen protection device, a condenser, a stirrer and a thermometer.

6. The method for preparing the aromatic sulfone dyeing auxiliary according to claim 2, characterized in that: The purge time is 10 minutes.

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