A reactive modifier and a method for preparing flame-retardant dyed wool-polyester fabric

Abstract

The invention belongs to the field of flame retardant technology, and specifically relates to a preparation method of a reactive modifier and flame retardant dyed wool-polyester fabric. First, cyanuric chloride and hydroxybenzaldehyde are reacted to synthesize the reactive modifier, then the reactive modifier and phosphite are used to modify the wool-polyester fabric, and then disperse dyes and cyclic phosphate flame retardants are used to perform flame retardant dyeing integrated treatment on the modified wool-polyester fabric to obtain the flame retardant dyed wool-polyester fabric. The flame retardant dyed wool-polyester fabric of the invention has high friction fastness and water fastness and good flame retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardancy, and in particular relates to a reactive modifier and a method for preparing flame retardant dyed wool-polyester fabric. Background Art

[0002] Wool-polyester blended fabrics have won the favor of consumers for their excellent warmth retention, comfort and durability. However, in the pursuit of fabric beauty and functionality, its traditional dyeing method - disperse dye / acid dye two-bath method, faces the challenges of cumbersome process, long time, high cost and significant damage to wool fibers. Although the disperse dye one-bath method attempts to simplify the process and save energy and reduce emissions, due to the significant differences in fiber structure and performance between wool and polyester, this method has encountered many technical bottlenecks while achieving efficient and uniform dyeing.

[0003] To overcome these problems, researchers have made unremitting efforts. The literature (Disperse dyeing of wool-polyester blended fabrics [J]. Printing and Dyeing, 2007, 33(5):5-8.) effectively improved the dyeing rate of disperse dyes on wool fibers by synthesizing three wool modifiers, opening up a new path for optimizing the dyeing process. In addition, the literature (One-bath dyeing of polyester-cotton and wool-polyester blended fabrics with disperse dyes [J]. Printing and Dyeing Auxiliary Agents, 2002, 19(6):14-16, 23.) showed that by adding auxiliaries with aromatic conjugated structures and reactive functional groups, the dyeing performance of wool-polyester blended fabrics was further improved in the disperse dye bath.

[0004] However, despite the progress made in dyeing technology, the flame retardant performance of wool-polyester fabrics is still a major shortcoming. Its inherent "bracket effect" exacerbates the difficulty of flame retardant treatment, making the existing multi-step finishing process (such as the anti-static flame retardant, oil-proof and water-repellent finishing method disclosed in CN104757721A) not only complicated, but also causes considerable damage to the fabric itself.

[0005] Therefore, it is particularly urgent and challenging to develop a new process that can simultaneously improve the dyeing fastness of wool-polyester blended fabrics and achieve one-bath durable flame retardant treatment. Summary of the invention

[0006] The purpose of the invention is to solve the problems existing in the prior art and to provide a reactive modifier and a method for preparing a flame retardant dyed wool-polyester fabric.

[0007] To achieve the above object, the scheme adopted by the present invention is as follows:

[0008] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabrics comprises the following steps:

[0009] (1) Prepare a reactive modifier, the structural formula of which is as follows:

[0010] ;

[0011] (2) Modifying wool-polyester fabric by using reactive modifier and phosphite, controlling chemical reaction between reactive modifier, phosphite and wool fiber in wool-polyester fabric, and obtaining modified wool-polyester fabric;

[0012] (3) The modified wool-polyester fabric was finished with a finishing liquid containing both disperse dyes and cyclic phosphate flame retardant FRC-1 to obtain flame-retardant dyed wool-polyester fabric.

[0013] As the preferred technical solution:

[0014] In the one-bath dyeing flame retardant finishing method for wool-polyester fabric as described above, the process of step (1) is as follows: Figure 1 The synthetic route of the reactive modifier shown is specifically to dissolve cyanuric chloride and hydroxybenzaldehyde (a slightly excessive amount of hydroxybenzaldehyde is helpful to promote the reaction) in a solvent a at a molar ratio of 1:2~2.2, first react at 0~5°C for 2~3h to allow the first active chlorine of cyanuric chloride to undergo a nucleophilic substitution reaction with the hydroxyl group of the hydroxybenzaldehyde, then react at 35~55°C for 1~2h to allow the second active chlorine of cyanuric chloride to undergo a nucleophilic substitution reaction with the hydroxyl group of the hydroxybenzaldehyde, and then perform post-treatment (purification by reduced pressure distillation) to obtain the reactive modifier;

[0015] The hydrogen nuclear magnetic resonance spectrum of the prepared reactive modifier is as follows: Figure 2 As shown, the chemical shifts at 7.7 and 6.9 ppm in the H NMR spectrum are caused by the hydrogen elements in the benzene ring, and the chemical shift at 9.8 ppm is caused by the hydrogen elements in the aldehyde group. The results show that the reactive modifier is successfully synthesized.

[0016] The one-bath dyeing flame retardant finishing method for wool-polyester fabric as described above comprises hydroxybenzaldehyde which is one or more of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde and vanillin; solvent a is acetone, and the mass ratio of cyanuric chloride to solvent a is 1:30-40. Increasing the amount of solvent a helps to promote uniform reaction, but too high an amount is wasteful.

[0017] In the one-bath dyeing flame retardant finishing method for wool-polyester fabric as described above, the specific process of step (2) is as follows: first, the reactive modifier and the wool-polyester fabric are added to the solvent b, and reacted at 85-95° C. for 20-40 min, then, while keeping the temperature constant, sodium carbonate or sodium bicarbonate is added to adjust the pH of the solution to 10-11, and the reaction is continued for 20-30 min, and finally, while keeping the temperature constant, phosphite is added to continue the reaction for 20-30 min, and post-treatment is performed to obtain the modified wool-polyester fabric.

[0018] At higher temperatures, the wool scale layer opens, and the reactive modifier and phosphite easily diffuse into the wool fiber. Wool fibers are rich in active amino and hydroxyl groups, which can undergo nucleophilic substitution reactions with the active chlorine groups of the reactive modifier. Sodium carbonate or sodium bicarbonate can promote the reaction. First adsorption and then adding alkali to promote the reaction can help improve the reactive grafting with wool fibers and reduce the degree of hydrolysis of active chlorine groups. The aldehyde group of the reactive modifier can undergo Schiff base addition reaction with the amino group of the wool fiber, and then after adding diethyl phosphite, its active PH bond can undergo addition reaction with the generated Schiff base C=N structure, thereby grafting the reactive modifier and phosphite on the wool fiber through covalent bonds. The reactive modifier is rich in aromatic conjugated benzene ring structure and has a high affinity with polyester fibers. It is combined through the principle of similar phase dissolution, so the reactive modifier has a good combination with wool-polyester fabrics.

[0019] In the one-bath dyeing flame retardant finishing method for wool-polyester fabric as described above, the ratio of reactive modifier to solvent b is 20-40 g:1 L, the mass ratio of wool-polyester fabric to solvent b is 1:30-40, the molar ratio of reactive modifier to phosphite is 1:2-2.2; the phosphite is one or more of diethyl phosphite and dimethyl phosphite; the content of wool fiber in the wool-polyester fabric is 40-80 wt%.

[0020] The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric as described above, in step (3), the components and contents in the finishing liquid are: disperse dye 1~2% owf, dispersant (NNO) 0.3~0.5g / L, carrier (methyl salicylate) 1.0~2.0g / L, cyclic phosphate flame retardant FRC-1 30~50g / L, water; finishing is carried out by immersion method, the finishing temperature is 95~98°C, the finishing time is 50~80min, and the bath ratio is 1:30~40.

[0021] During the finishing process, the carrier can promote the expansion and plasticization of polyester fibers, lower the glass transition temperature, open the pores for dyes to enter the fibers, and realize low-temperature dyeing treatment; the reactive modifier is rich in aromatic benzene ring structure, which can increase the van der Waals force, hydrogen bond force and π-π bond between disperse dyes and wool fibers, and help improve the dyeing rate and color fastness of disperse dyes on wool fibers; the cyclic phosphate flame retardant FRC-1 molecule contains a six-membered ring structure, which can be combined with polyester fibers through the principle of similar dissolution, and the cyclic phosphate flame retardant FRC-1 can act as an acid regulator to keep the pH of the solution weakly acidic, which is conducive to the dyeing of disperse dyes.

[0022] According to the one-bath dyeing flame retardant finishing method for wool-polyester fabric, the flame retardant dyed wool-polyester fabric has a dry friction fastness of above grade 4, a wet friction fastness of above grade 3-4, a color change fastness of above grade 4, a staining fastness of above grade 3-4, and a high color yield and color fastness of disperse dye dyeing. This is because the reactive modifier is rich in aromatic benzene ring structure, which can increase the van der Waals force, hydrogen bond force and π-π bond between the disperse dye and the wool fiber, and is helpful to improve the dyeing rate and color fastness of the disperse dye on the wool fiber. The limiting oxygen index The number is ≥28.5%, the damaged length is ≤9.5cm, and it has excellent flame retardant properties, because the phosphate structure of phosphite and cyclic phosphate in the flame retardant dyed wool-polyester fabric acts as an acid source, the triazine ring acts as a gas source and a carbon source, and the aromatic structure containing hydroxybenzaldehyde acts as a carbon source, organically constructing an intumescent flame retardant system. After 30 times of washing, the damaged length is still ≤14.1cm, which meets the B1 grade standard, and has excellent water wash resistance, because the flame retardant modifier not only produces a covalent bond with the wool fiber, but also has a strong bonding ability with the polyester fiber.

[0023] Beneficial effects:

[0024] The reactive modifier designed and synthesized by the present invention can generate covalent bond crosslinking with wool fibers, is rich in active chlorine groups and active aldehyde groups, and is combined with wool fibers through multiple crosslinking methods, while grafting phosphite flame retardants onto the wool fibers; the cyclic phosphate flame retardant FRC-1 molecule contains a six-membered ring structure, and can be combined with polyester fibers through the principle of similar dissolution, thereby improving the flame retardant properties and water washability of flame-retardant dyed wool-polyester fabrics; and the cyclic phosphate flame retardant FRC-1 can act as an acid regulator, keep the pH of the solution at a weak acid, and facilitate dyeing with disperse dyes.

[0025] The reactive modifier designed and synthesized by the present invention is rich in aromatic benzene ring structure, which can increase the van der Waals force, hydrogen bond force and π-π bond effect between the disperse dye and the wool fiber, thereby improving the color fastness of the disperse dye on the wool fiber, as well as the flame retardant property and water washability of the flame retardant dyed wool-polyester fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Schematic diagram of the synthesis route of the reactive modifier of the present invention;

[0027] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum of the reactive modifier of the present invention. DETAILED DESCRIPTION

[0028] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0029] The structural formula of the reactive modifier prepared in the embodiment is: .

[0030] The following are the methods for testing the relevant performance indicators in the embodiments and comparative examples:

[0031] Dry rubbing fastness and wet rubbing fastness: Tested in accordance with GB / T 3920-2008 Textiles - Tests for colour fastness - Colour fastness to rubbing;

[0032] Color fastness and staining fastness: Tested in accordance with GB / T 3921-2008 Textiles - Tests for color fastness - Color fastness to washing with soap;

[0033] Limiting oxygen index: Tested in accordance with GB / T 5454-1997 "Oxygen Index Method for Textile Combustion Performance Test".

[0034] Damage length: measured in accordance with GB / T 5455-2014 "Determination of smoldering and afterflaming time of damage length in vertical direction of burning performance of textiles".

[0035] Damaged length after 30 washes: First wash the fabric 30 times with water according to AATCC 61-2013 "Accelerated test for color fastness to household and commercial washing" standard, and then test the damaged length of the fabric with reference to GB / T 5455-2014 "Determination of damage length in vertical direction, smoldering and afterflaming time of textile combustion performance" standard.

[0036] Example 1

[0037] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric, the specific steps are as follows:

[0038] (1) Raw material preparation:

[0039] Wool-polyester fabric: The wool fiber content is 40wt%;

[0040] Cyanuric chloride;

[0041] Containing hydroxybenzaldehyde: p-hydroxybenzaldehyde;

[0042] Solvent a: acetone;

[0043] Phosphite: diethyl phosphite;

[0044] Solvent b: ethanol aqueous solution, ethanol accounts for 20% of the total volume;

[0045] pH adjuster: sodium carbonate;

[0046] Finishing liquid: The components and contents are as follows: disperse dye (disperse blue 2BLN) 1% owf, dispersant (NNO) 0.3 g / L, carrier (methyl salicylate) 1 g / L, cyclic phosphate flame retardant FRC-1 30 g / L, water;

[0047] (2) Preparation of reactive modifier:

[0048] Dissolve cyanuric chloride and hydroxybenzaldehyde in a solvent a at a molar ratio of 1:2 (the mass ratio of cyanuric chloride to solvent a is 1:30), react at 0°C for 3 hours, then at 35°C for 2 hours, and then purify by reduced pressure distillation to obtain a reactive modifier;

[0049] (3) Modification of wool-polyester fabrics:

[0050] First, the reactive modifier prepared in step (2) and the wool-polyester fabric are added to solvent b, and reacted at 85° C. for 40 minutes, then the temperature is kept constant, a pH regulator is added to adjust the pH of the solution to 10, and the reaction is continued for 30 minutes, and finally the temperature is kept constant, a phosphite is added, and the reaction is continued for 30 minutes, and post-treatment is performed to obtain a modified wool-polyester fabric;

[0051] The ratio of the reactive modifier to the solvent b is 20 g:1 L, the mass ratio of the wool-polyester fabric to the solvent b is 1:40, and the molar ratio of the reactive modifier to the phosphite is 1:2;

[0052] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0053] The modified wool-polyester fabric was finished with a finishing liquid (impregnation method) to obtain a flame-retardant dyed wool-polyester fabric; wherein the finishing temperature was 95°C, the finishing time was 80 min, and the bath ratio was 1:30.

[0054] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of 4-5, a wet rubbing fastness of 4, a color fastness of 4-5, a staining fastness of 4, a limiting oxygen index of 28.5%, a damaged length of 9.5 cm, and a damaged length of 14.1 cm after 30 washes.

[0055] Comparative Example 1

[0056] A method for dyeing wool-polyester fabrics, comprising: using a finishing liquid (basically the same as in Example 1, except that the cyclic phosphate flame retardant FRC-1 is replaced by water of equal mass) to finish the wool-polyester fabrics (the method and process parameters are the same as in Example 1) to obtain dyed wool-polyester fabrics.

[0057] The final dyed wool-polyester fabric has a dry rubbing fastness of 2-3, a wet rubbing fastness of 2, a color fastness of 2-3, a staining fastness of 2-3, a limiting oxygen index of 20.6%, a damaged length of 30 cm, and a damaged length of 30 cm after 30 washes.

[0058] Comparative Example 2

[0059] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric is basically the same as in Example 1, and the specific steps are as follows:

[0060] (1) Raw material preparation:

[0061] Same as step (1) in Example 1;

[0062] (2) Preparation of modifier:

[0063] The molar ratio of cyanuric chloride to hydroxybenzaldehyde is 1:3.3, and the other conditions are the same as step (2) of Example 1;

[0064] (3) Modification of wool-polyester fabrics:

[0065] Same as step (3) in Example 1;

[0066] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0067] Same as step (4) of Example 1.

[0068] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of 3-4, a wet rubbing fastness of 3, a color fastness of 3-4, a staining fastness of 3, a limiting oxygen index of 28.0%, a damaged length of 9.8 cm, and a damaged length of 20.9 cm after 30 washes.

[0069] It can be seen from Comparative Example 2 and Example 1 that the flame retardant dyed wool-polyester fabric prepared in Comparative Example 2 has decreased in rubbing fastness, washing fastness and flame retardant and water-washing resistance; the root cause of this phenomenon is that the modifier used in Comparative Example 2 contains three aldehyde groups. When the wool-polyester fabric is modified by this modifier, the three aldehyde groups all react with the amino groups of the wool fiber, but it is difficult to reach and effectively react with the hydroxyl groups of the wool fiber. This reaction selectivity leads to a significant reduction in the amount of modifier grafted onto the wool fiber. In other words, the modification degree of the wool-polyester fabric fails to reach the ideal level; ultimately, this insufficient modification directly leads to a significant decrease in the rubbing fastness, washing fastness and flame retardant and water-washing resistance of the prepared flame retardant dyed wool-polyester fabric.

[0070] Comparative Example 3

[0071] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric is basically the same as in Example 1, and the specific steps are as follows:

[0072] (1) Raw material preparation:

[0073] Methanol was added to the raw materials of Example 1;

[0074] (2) Preparation of modifier:

[0075] Dissolve cyanuric chloride and hydroxybenzaldehyde in solvent a, react at 0°C for 3h, then at 35°C for 2h, add methanol, raise the temperature to 70°C, react for 2h, and then purify by reduced pressure distillation to obtain a modifier;

[0076] The molar ratio of cyanuric chloride, hydroxybenzaldehyde and methanol is 1:2:1, and the mass ratio of cyanuric chloride and solvent a is 1:30.

[0077] (3) Modification of wool-polyester fabrics:

[0078] Same as step (3) in Example 1;

[0079] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0080] Same as step (4) of Example 1.

[0081] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of level 4, a wet rubbing fastness of level 3-4, a color fastness of level 4, a staining fastness of level 3-4, a limiting oxygen index of 28.2%, a damaged length of 9.7 cm, and a damaged length of 16.8 cm after 30 washes.

[0082] It can be seen from Comparative Example 3 and Example 1 that the flame retardant dyed wool-polyester fabric prepared in Comparative Example 3 has decreased in rubbing fastness, washing fastness and flame retardant and water washing resistance; this is because the modifier prepared in Comparative Example 3 contains two aldehyde groups. When this modifier containing two aldehyde groups participates in the reaction, it only reacts with the amino group of the wool fiber, but cannot react with the hydroxyl group. The selectivity of this reaction leads to a significant reduction in the amount of modifier grafted onto the wool fiber, and the grafting efficiency fails to reach the ideal level, resulting in an inadequate modification process. This inadequate modification is directly reflected in the performance of the prepared flame retardant dyed wool-polyester fabric, that is, its rubbing fastness, washing fastness and flame retardant and water washing resistance are significantly reduced.

[0083] Comparative Example 4

[0084] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric is basically the same as in Example 1, and the specific steps are as follows:

[0085] (1) Raw material preparation:

[0086] Same as step (1) in Example 1;

[0087] (2) Preparation of reactive modifier:

[0088] The molar ratio of cyanuric chloride to hydroxybenzaldehyde is 1:1, and the other conditions are the same as step (2) of Example 1;

[0089] (3) Modification of wool-polyester fabrics:

[0090] Same as step (3) in Example 1;

[0091] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0092] Same as step (4) of Example 1.

[0093] The flame retardant dyed wool-polyester fabric finally obtained has a dry rubbing fastness of 3-4, a wet rubbing fastness of 3, a color fastness of 3-4, a staining fastness of 3-4, a limiting oxygen index of 27.2%, a damaged length of 10.6 cm, and a damaged length of 30 cm after 30 washes.

[0094] It can be seen from Comparative Example 4 and Example 1 that the flame retardant dyed wool-polyester fabric prepared in Comparative Example 4 has reduced rubbing fastness, washing fastness and flame retardant and water-washing resistance. The root cause of this phenomenon is that the modifier prepared in Comparative Example 4 contains one aldehyde group and two active chlorines. Since the modifier contains only one aldehyde group, the amount of phosphite flame retardant grafted on the wool fiber is relatively reduced. In addition, the reaction temperature of dichlorotriazine in the modifier is low (room temperature), but the temperature of the grafting process is high, which makes the second active chlorine easily hydrolyzed and loses its activity. Therefore, the modification degree of the wool fiber is significantly affected, which is manifested as insufficient modification. This insufficient modification directly and significantly affects the performance of the prepared flame retardant dyed wool-polyester fabric, which is specifically manifested in a significant decrease in its rubbing fastness, washing fastness and flame retardant and water-washing resistance.

[0095] Example 2

[0096] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric, the specific steps are as follows:

[0097] (1) Raw material preparation:

[0098] Wool-polyester fabric: The wool fiber content is 45wt%;

[0099] Cyanuric chloride;

[0100] Containing hydroxybenzaldehyde: m-hydroxybenzaldehyde;

[0101] Solvent a: acetone;

[0102] Phosphite: dimethyl phosphite;

[0103] Solvent b: ethanol aqueous solution, ethanol accounts for 23% of the total volume;

[0104] pH adjuster: sodium bicarbonate;

[0105] Finishing liquid: components and contents are as follows: disperse dye (disperse blue 2BLN) 1.4% owf, dispersant (NNO) 0.35 g / L, carrier (methyl salicylate) 1.4 g / L, cyclic phosphate flame retardant FRC-1 40 g / L, water;

[0106] (2) Preparation of reactive modifier:

[0107] Dissolve cyanuric chloride and hydroxybenzaldehyde in a molar ratio of 1:2.1 in solvent a (the mass ratio of cyanuric chloride to solvent a is 1:40), react at 2°C for 2.6 hours, then react at 40°C for 1.8 hours, and then purify by reduced pressure distillation to obtain a reactive modifier;

[0108] (3) Modification of wool-polyester fabrics:

[0109] First, the reactive modifier prepared in step (2) and the wool-polyester fabric are added to solvent b, and reacted at 90° C. for 30 minutes, then the temperature is kept constant, a pH regulator is added to adjust the pH of the solution to 10.5, and the reaction is continued for 27 minutes, and finally the temperature is kept constant, a phosphite is added, and the reaction is continued for 27 minutes, and post-treatment is performed to obtain a modified wool-polyester fabric;

[0110] Among them, the ratio of the reactive modifier to the solvent b is 25g:1L, the mass ratio of the wool-polyester fabric to the solvent b is 1:35, and the molar ratio of the reactive modifier to the phosphite is 1:2.1;

[0111] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0112] The modified wool-polyester fabric was finished with a finishing liquid (impregnation method) to obtain a flame-retardant dyed wool-polyester fabric; wherein the finishing temperature was 96°C, the finishing time was 70 min, and the bath ratio was 1:35.

[0113] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of 4-5, a wet rubbing fastness of 4, a color fastness of 4-5, a staining fastness of 4, a limiting oxygen index of 30.1%, a damaged length of 8.6 cm, and a damaged length of 13.4 cm after 30 washes.

[0114] Comparative Example 5

[0115] A method for dyeing wool-polyester fabrics, comprising: using a finishing liquid (basically the same as in Example 2, except that the cyclic phosphate flame retardant FRC-1 is replaced by water of equal mass) to finish the wool-polyester fabrics (the method and process parameters are the same as in Example 2) to obtain dyed wool-polyester fabrics.

[0116] The final dyed wool-polyester fabric has a dry rubbing fastness of 2-3, a wet rubbing fastness of 2, a color fastness of 2-3, a staining fastness of 2-3, a limiting oxygen index of 20.8%, a damaged length of 30 cm, and a damaged length of 30 cm after 30 washes.

[0117] Comparative Example 6

[0118] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric is basically the same as in Example 2, and the specific steps are as follows:

[0119] (1) Raw material preparation:

[0120] The hydroxybenzaldehyde in step (1) of Example 2 was replaced by glyceraldehyde, and the other raw materials remained unchanged;

[0121] (2) Preparation of reactive modifier:

[0122] Dissolve cyanuric chloride and glyceraldehyde in a molar ratio of 1:2.1 in solvent a (the mass ratio of cyanuric chloride to solvent a is 1:40), react at 2°C for 2.6 hours, then react at 40°C for 1.8 hours, and then purify by reduced pressure distillation to obtain a reactive modifier;

[0123] (3) Modification of wool-polyester fabrics:

[0124] Same as step (3) in Example 2;

[0125] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0126] Same as step (4) of Example 2.

[0127] The flame retardant dyed wool-polyester fabric finally obtained has a dry rubbing fastness of 3, a wet rubbing fastness of 3, a color fastness of 3, a staining fastness of 3, a limiting oxygen index of 27.0%, a damaged length of 10.9 cm, and a damaged length of 30 cm after 30 washes.

[0128] It can be seen from Comparative Example 6 and Example 2 that the flame retardant dyed wool-polyester fabric prepared in Comparative Example 6 has decreased rubbing fastness, washing fastness, and flame retardant and water-washing resistance. The root cause of this phenomenon is that the modifier prepared in Comparative Example 6 lacks an aromatic structure. This structural feature makes it difficult for the modifier to effectively improve the adsorption capacity of disperse dyes and cyclic phosphate flame retardants on wool fibers, which leads to a decrease in the color fastness of the fabric, as well as a decrease in flame retardant properties and water-washing resistance.

[0129] Example 3

[0130] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric, the specific steps are as follows:

[0131] (1) Raw material preparation:

[0132] Wool-polyester fabric: The wool fiber content is 60wt%;

[0133] Cyanuric chloride;

[0134] Contains hydroxybenzaldehyde: vanillin;

[0135] Solvent a: acetone;

[0136] Phosphite: diethyl phosphite;

[0137] Solvent b: ethanol aqueous solution, ethanol accounts for 26% of the total volume;

[0138] pH adjuster: sodium carbonate;

[0139] Finishing liquid: components and contents are as follows: disperse dye (disperse blue 2BLN) 1.7% owf, dispersant (NNO) 0.4 g / L, carrier (methyl salicylate) 1.7 g / L, cyclic phosphate flame retardant FRC-1 45 g / L, water;

[0140] (2) Preparation of reactive modifier:

[0141] Dissolve cyanuric chloride and hydroxybenzaldehyde in a solvent a (the mass ratio of cyanuric chloride to solvent a is 1:35) in a molar ratio of 1:2, react at 3°C ​​for 2.3 hours, then react at 45°C for 1.5 hours, and then purify by reduced pressure distillation to obtain a reactive modifier;

[0142] (3) Modification of wool-polyester fabrics:

[0143] First, the reactive modifier prepared in step (2) and the wool-polyester fabric are added to solvent b, reacted at 93° C. for 25 minutes, then the temperature is kept constant, a pH regulator is added to adjust the pH of the solution to 11, and the reaction is continued for 24 minutes, and finally the temperature is kept constant, a phosphite is added, and the reaction is continued for 24 minutes, and post-treatment is performed to obtain a modified wool-polyester fabric;

[0144] Among them, the ratio of the reactive modifier to the solvent b is 30g:1L, the mass ratio of the wool-polyester fabric to the solvent b is 1:33, and the molar ratio of the reactive modifier to the phosphite is 1:2.2;

[0145] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0146] The modified wool-polyester fabric was finished with a finishing liquid (impregnation method) to obtain a flame-retardant dyed wool-polyester fabric; wherein the finishing temperature was 97°C, the finishing time was 60 min, and the bath ratio was 1:40.

[0147] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of 4-5, a wet rubbing fastness of 3-4, a color fastness of 4, a staining fastness of 3-4, a limiting oxygen index of 31.2%, a damaged length of 7.9 cm, and a damaged length of 12.9 cm after 30 washes.

[0148] Comparative Example 7

[0149] A method for dyeing wool-polyester fabrics, comprising: using a finishing liquid (basically the same as in Example 3, except that the cyclic phosphate flame retardant FRC-1 is replaced by water of equal mass) to finish the wool-polyester fabrics (the method and process parameters are the same as in Example 3) to obtain dyed wool-polyester fabrics.

[0150] The final dyed wool-polyester fabric has a dry rubbing fastness of 2-3, a wet rubbing fastness of 2, a color fastness of 2-3, a staining fastness of 2-3, a limiting oxygen index of 20.9%, a damaged length of 30 cm, and a damaged length of 30 cm after 30 washes.

[0151] Example 4

[0152] A method for one-bath dyeing and flame retardant finishing of wool-polyester fabric, the specific steps are as follows:

[0153] (1) Raw material preparation:

[0154] Wool-polyester fabric: The wool fiber content is 80wt%;

[0155] Cyanuric chloride;

[0156] Hydroxybenzaldehyde-containing: a mixture of p-hydroxybenzaldehyde and m-hydroxybenzaldehyde in a mass ratio of 1:1;

[0157] Solvent a: acetone;

[0158] Phosphite: dimethyl phosphite;

[0159] Solvent b: ethanol aqueous solution, ethanol accounts for 30% of the total volume;

[0160] pH adjuster: sodium bicarbonate;

[0161] Finishing liquid: The components and contents are as follows: disperse dye (disperse blue 2BLN) 2% owf, dispersant (NNO) 0.5 g / L, carrier (methyl salicylate) 2 g / L, cyclic phosphate flame retardant FRC-1 50 g / L, water;

[0162] (2) Preparation of reactive modifier:

[0163] Dissolve cyanuric chloride and hydroxybenzaldehyde in a solvent a (the mass ratio of cyanuric chloride to solvent a is 1:40) at a molar ratio of 1:2.2, react at 5°C for 2 hours, then react at 55°C for 1 hour, and then purify by reduced pressure distillation to obtain a reactive modifier;

[0164] (3) Modification of wool-polyester fabrics:

[0165] First, the reactive modifier prepared in step (2) and the wool-polyester fabric are added to solvent b, reacted at 95° C. for 20 minutes, then the temperature is kept constant, a pH regulator is added to adjust the pH of the solution to 10.5, and the reaction is continued for 20 minutes, and finally the temperature is kept constant, a phosphite is added, and the reaction is continued for 20 minutes, and post-treatment is performed to obtain a modified wool-polyester fabric;

[0166] Among them, the ratio of the reactive modifier to the solvent b is 40g:1L, the mass ratio of the wool-polyester fabric to the solvent b is 1:30, and the molar ratio of the reactive modifier to the phosphite is 1:2.2;

[0167] (4) Preparation of flame-retardant dyed wool-polyester fabrics:

[0168] The modified wool-polyester fabric was finished with a finishing liquid (impregnation method) to obtain a flame-retardant dyed wool-polyester fabric; wherein the finishing temperature was 98°C, the finishing time was 50 min, and the bath ratio was 1:40.

[0169] The final flame-retardant dyed wool-polyester fabric has a dry rubbing fastness of level 4, a wet rubbing fastness of level 3-4, a color fastness of level 4, a staining fastness of level 3-4, a limiting oxygen index of 32.1%, a damaged length of 7.6 cm, and a damaged length of 12.5 cm after 30 washes.

[0170] Comparative Example 8

[0171] A method for dyeing wool-polyester fabric, using a finishing liquid (basically the same as in Example 4, except that the cyclic phosphate flame retardant FRC-1 is replaced by water of equal mass) to finish the wool-polyester fabric (the method and process parameters are the same as in Example 4) to obtain a dyed wool-polyester fabric.

[0172] The final dyed wool-polyester fabric has a dry rubbing fastness of 2-3, a wet rubbing fastness of 2, a color fastness of 2-3, a staining fastness of 2-3, a limiting oxygen index of 21%, a damaged length of 30 cm, and a damaged length of 30 cm after 30 washes.

Claims

1. A method for one-bath dyeing and flame retardant finishing of wool-polyester fabrics, characterized in that: The following steps are involved: (1) Prepare a reactive modifier, the structural formula of which is as follows: ； (2) Modifying wool-polyester fabric by using reactive modifier and phosphite, controlling chemical reaction between reactive modifier, phosphite and wool fiber in wool-polyester fabric, and obtaining modified wool-polyester fabric; (3) The modified wool-polyester fabric was finished with a finishing liquid containing both disperse dyes and cyclic phosphate flame retardant FRC-1 to obtain flame-retardant dyed wool-polyester fabric.

2. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 1, characterized in that: The process of step (1) is: dissolving cyanuric chloride and hydroxybenzaldehyde in a molar ratio of 1:2-2.2 in solvent a, first reacting at 0-5°C for 2-3h, then reacting at 35-55°C for 1-2h and then post-treating to obtain a reactive modifier, wherein solvent a is acetone.

3. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 2, characterized in that: The hydroxybenzaldehyde is p-hydroxybenzaldehyde.

4. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 1, characterized in that: The specific process of step (2) is as follows: first, the reactive modifier and wool-polyester fabric are added to solvent b, reacted at 85-95° C. for 20-40 minutes, then, while keeping the temperature constant, sodium carbonate or sodium bicarbonate is added to adjust the pH of the solution to 10-11, and the reaction is continued for 20-30 minutes, and finally, while keeping the temperature constant, phosphite is added to continue the reaction for 20-30 minutes, and post-processed to obtain the modified wool-polyester fabric, wherein solvent b is an ethanol aqueous solution, and ethanol accounts for 20%, 23%, 26% or 30% of the total volume.

5. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 4, characterized in that: The ratio of the reactive modifier to the solvent b is 20-40 g:1 L, the mass ratio of the wool-polyester fabric to the solvent b is 1:30-40, the molar ratio of the reactive modifier to the phosphite is 1:2-2.2; the phosphite is one or more of diethyl phosphite and dimethyl phosphite; the content of wool fiber in the wool-polyester fabric is 40-80 wt%.

6. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 1, characterized in that: In step (3), the components and contents in the finishing liquid are as follows: disperse dye 1-2% owf, dispersant 0.3-0.5 g / L, carrier 1.0-2.0 g / L, cyclic phosphate flame retardant FRC-1 30-50 g / L, water; the carrier is methyl salicylate; the finishing is carried out by immersion method, the finishing temperature is 95-98°C, the finishing time is 50-80 min, and the bath ratio is 1:30-40.

7. The method for one-bath dyeing and flame retardant finishing of wool-polyester fabric according to claim 1, characterized in that: The dry rubbing fastness of flame retardant dyed wool-polyester fabric is above level 4, the wet rubbing fastness is above level 3-4, the color change fastness is above level 4, the staining fastness is above level 3-4, the limiting oxygen index is ≥28.5%, the damaged length is ≤9.5cm, and the damaged length is still ≤14.1cm after 30 washes.

Images