Environment-friendly wool protection resin as well as preparation method and application thereof

Abstract

The invention belongs to the field of textile auxiliaries, and discloses environment-friendly wool protection resin as well as a preparation method and application thereof. After wool is treated by the environment-friendly wool protection resin, the breaking strength retention rate of the wool is relatively high, no negative influence is caused on color fastness and hand feeling in the finishing process, and the environment-friendly wool protection resin has obvious advantages compared with commercially available competitive products.

Description

Technical Field

[0001] The invention belongs to the field of textile auxiliaries, and particularly relates to an environmentally friendly wool protection resin and a preparation method and application thereof. Background Art

[0002] Among the dyeing processes of many textile fibers, wool is one of the fibers that is extremely vulnerable to damage. Peptides, cystine and disulfide bonds in its molecular structure will undergo varying degrees of chemical degradation under acid, alkaline and even neutral conditions, causing damage to the fibers. And the degree of this damage shows a certain degree of linear relationship with the changes in dyeing time, temperature and pH value. Generally speaking, the longer the time, the higher the temperature, the stronger the pH, the more severe the chemical degradation, the greater the fiber damage, and the greater the decrease in strength. The greater the negative impact on the tensile / tear strength, abrasion resistance and spinnability of dyed fabric products. The entire processing process of wool, including bleaching, dyeing, stripping, steaming, anti-felting and antibacterial and mildew removal dyeing and finishing processes, all have the risk of causing wool strength loss. Therefore, it is very important to protect wool fibers and reduce their damage during dyeing.

[0003] Currently, there are many types of resins on the market that use anti-setting mechanisms to protect wool, but most of them are resin pre-condensates used for fabric finishing (such as dimethylolethylene urea). Although they can protect wool fibers, they often leave a large amount of free formaldehyde on the fabric, which does not meet environmental protection requirements.

[0004] In order to achieve the goal of green environmental protection, researchers have invested a lot of energy in recent years to further study the mechanism of wool dyeing damage and anti-setting protection, and have also developed some formaldehyde-free wool protective agents. Zhang Mingwen et al. (Journal of Textile Research, 2007, 28, 88) used substituted alkyl urea instead of dihydroxymethylethylene urea to prepare anti-setting protective agent A, which significantly improved the mechanical properties of cashmere after dyeing, and no harmful aldehyde substances were released. However, the synthesis of this type of urea compound needs to be completed in a high-pressure reactor, and the reaction time is more than 30 hours. The preparation process is relatively harsh, and the cost of industrialization is too high. Patent CN101545221A discloses a process for dyeing and protecting wool fibers under high temperature conditions. The wool protective agent used in the process is a compound of a two-headed cation containing a quaternary ammonium salt base or a two-headed anion containing sodium sulfonate and maleic anhydride. This combination of components can provide double protection for wool fibers during the dyeing process. Compared with the case without adding a protective agent, the degree of decrease in dry and wet breaking strength is reduced to less than 40%, and the color fastness of about level 4 can be maintained, which reduces fiber damage and improves dyeing quality. However, the process requires more other dyeing auxiliaries and strict temperature and pH control to achieve the above effect, and its target fabric is a wool / polyester interwoven or blended fabric, which is mainly polyester and has a low proportion of wool.

[0005] Moreover, existing common wool dyeing protective agents have adverse effects on the breaking strength and dyeing effect of wool, such as poor fastness after dyeing.

[0006] Therefore, there is an urgent need to provide a new wool protection agent, which does not release formaldehyde, has good environmental protection, and has a good protective effect on wool dyeing. Summary of the invention

[0007] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides an environmentally friendly wool protective resin and a preparation method and application thereof. After the wool is treated with the environmentally friendly wool protective resin of the present invention, the breaking strength retention rate of the wool is high, and there is no negative impact on the color fastness and hand feel during the finishing process, which has obvious advantages over commercially available competitive products.

[0008] A first aspect of the present invention provides an environmentally friendly wool protective resin.

[0009] Specifically, the environmentally friendly wool protection resin has the following structural formula:

[0010]

[0011] wherein R represents hydrogen, alkyl or carboxyl-substituted alkyl;

[0012] x, y, m, and n are positive integers greater than 1.

[0013] Preferably, the value of x is a positive integer of 2-25, and more preferably a positive integer of 4-20.

[0014] Preferably, the value of y is 10-30.

[0015] Preferably, the value of m is 10-30.

[0016] Preferably, the value of n is 10-30.

[0017] Preferably, the carbon number of the alkyl group is 1-10, more preferably 1-6.

[0018] Preferably, R represents any one of H, -CH3, -C6H6, -CH2COOH, and -CH(COOH)-CH2COOH.

[0019] The second aspect of the present invention provides a method for preparing an environmentally friendly wool protection resin.

[0020] Specifically, the preparation method of the environmentally friendly wool protection resin comprises the following steps:

[0021] In a protective gas atmosphere, polyethylene glycol and maleic anhydride are mixed for a first reaction to obtain a pre-shrinkage product, and then an unsaturated organic acid is added for a second reaction to obtain the environmentally friendly wool protective resin.

[0022] Preferably, the polyethylene glycol includes at least one selected from PEG200, PEG400, PEG600 and PEG800.

[0023] Preferably, the maleic anhydride substance is selected from at least one of maleic anhydride and maleic acid.

[0024] Preferably, the unsaturated organic acid is at least one selected from itaconic acid, ethylidene succinic acid, acrylic acid, methacrylic acid, cis-aconitic acid, and cinnamic acid.

[0025] Preferably, the molar ratio of the polyethylene glycol to the maleic anhydride substance is 1:(1.8-2.5), and more preferably 1:(2.0-2.2).

[0026] Preferably, when polyethylene glycol is mixed with maleic anhydride, a polymerization inhibitor is also added.

[0027] Preferably, the polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, bisphenol A, ferric chloride, cupric chloride and sodium sulfate.

[0028] Preferably, the mass of the polymerization inhibitor is 0.01-2.0% of the total mass of the polyethylene glycol and the maleic anhydride substances, and more preferably 0.1-1.0%.

[0029] Preferably, the molar ratio of the unsaturated organic acid to the maleic anhydride substance is 0.9-1.5:1, more preferably 1.0-1.1:1.

[0030] Preferably, an initiator is also added when the unsaturated organic acid is added.

[0031] Preferably, the initiator is selected from at least one of ammonium persulfate, sodium persulfate and potassium persulfate.

[0032] Preferably, the mass of the initiator is 0.01-2.0% of the total mass of the polyethylene glycol, the maleic anhydride substance and the unsaturated organic acid, and more preferably 0.1-1.0%.

[0033] Preferably, after the second reaction is completed, a solvent is added, wherein the solvent is at least one selected from diethylene glycol, dipropylene glycol, diethylene glycol and dipropylene glycol.

[0034] Preferably, the protective gas is selected from nitrogen or a rare gas, such as argon or helium.

[0035] Preferably, the temperature of the first reaction is 40-60°C, more preferably 55-60°C.

[0036] Preferably, the first reaction time is 0.5-2.5 hours, more preferably 1.5-2.5 hours.

[0037] Preferably, the temperature of the second reaction is 78-82°C, more preferably 80-82°C.

[0038] Preferably, the second reaction time is 1-3 hours, more preferably 2-3 hours.

[0039] The preparation method of the present invention is to firstly subject low molecular weight polyethylene glycol and maleic acid substances to ring-opening esterification to obtain a pre-shrinkage product, then subject it to free radical copolymerization with an unsaturated organic acid at high temperature to prepare a high molecular weight polycarboxylic acid polymer (i.e., an environmentally friendly wool protection resin), and finally add a solvent and mix them evenly to obtain the product.

[0040] The third aspect of the present invention provides the use of an environmentally friendly wool protection resin.

[0041] Application of the above-mentioned environmentally friendly wool protection resin in the preparation of wool textiles.

[0042] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0043] (1) The environmentally friendly wool protective resin of the present invention has a high carboxyl content in its molecular structure, and can quickly combine with the thiol groups on the wool fibers, which can effectively inhibit the exchange reaction between the thiol groups and the disulfide bonds, greatly reducing the possible damage to the wool, and having a significant protective effect. In addition, the environmentally friendly wool protective resin has a large molecular weight and has an obvious coating and film-forming function, which can effectively prevent the mutual movement and friction between the wool fibers and play a certain role in preventing felting. The application results show that after being treated with the environmentally friendly wool protective resin of the present invention, the breaking strength retention rate of the wool is relatively high, and there is no negative impact on the color fastness and feel during the finishing process, which has obvious advantages over commercially available competitive products.

[0044] (2) The environmentally friendly wool protection resin of the present invention has good water solubility, can be miscible with cold water in any proportion, and the solution is uniform and stable without precipitation or phase separation. No other acid needs to be added to adjust the pH of the dye bath during dyeing and finishing. At the same time, the environmentally friendly wool protection resin has strong application compatibility and can be mixed with other dyeing auxiliaries of different ion types such as anionic, non-ionic, weakly cationic, etc. in the same bath, and has a wide range of applications.

[0045] (3) The environmentally friendly wool protection resin of the present invention is green and environmentally friendly, does not contain formaldehyde itself, and does not generate any formaldehyde or other harmful substances such as aldehydes during use.

[0046] (4) The preparation process of the environmentally friendly wool protection resin of the present invention is simple, the conditions are mild, and the reaction rate is high. No by-products are generated in the reaction, the finished product conversion rate is above 98%, the manufacturing cost is low, and the requirements of industrial production are met. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is the infrared spectrum of the environmentally friendly wool protection resin of Example 1. DETAILED DESCRIPTION

[0048] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0049] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0050] Example 1

[0051] Environmentally friendly wool protection resin, its structural formula is:

[0052]

[0053] -CH2COOH, the values ​​of x, y, m, and n are 5, 20, 20, and 20 respectively.

[0054] Figure 1 This is the infrared spectrum of the environmentally friendly wool protection resin of Example 1. Figure 1 It can be seen that 3434cm -1 The broad peak at 2875 cm-1 is attributed to the stretching vibration of OH in the carboxyl group. -1 The stretching vibration peaks of C=O in carboxyl group appear at 1720 and 1635 cm -1 , while the characteristic peaks of CH bending vibration of methyl and methylene are at 1451-1410cm -1 1209-1035cm -1 The composite peak at 976, 940, 887, 818 cm-1 is derived from the out-of-plane swing vibration of CH in the -CH2CH2O- chain and the stretching vibration of CO in the ether bond. -1 Both are characteristic peaks of the in-plane rocking vibration of the methylene CH in the structure.

[0055] The preparation method of the environmentally friendly wool protection resin comprises the following steps:

[0056] (1) Pre-shrinkage: In a 1000 mL four-necked flask equipped with a mechanical stirrer and a condenser, add 176 g of ground maleic anhydride, turn on the nitrogen protection and maintain the gas flow rate at 50 mL / min, then add 60 g of polyethylene glycol 200 and 0.10 g of hydroquinone, and start stirring at the same time, and maintain the speed at 200 rpm. Then, heat the reaction mixture to 55° C. and keep stirring for 30 min. Then, continue to add the remaining 120 g of polyethylene glycol 200 dropwise using a constant pressure dropping funnel, and complete the addition within 45 min. Finally, continue the reaction for 40 min to obtain a light yellow transparent solution.

[0057] (2) Copolymerization: The light yellow transparent solution of step (1) was heated to 80°C and the stirring speed was set to 300 rpm. 0.40 g of ammonium persulfate was added as an initiator while the temperature was kept at 80±2°C. Then, a total of 236 g of itaconic acid was added to the reaction bottle in 4 times. The feeding time for each time was 5 min. After the addition was completed, the reaction was stirred for 40 min. The reaction was continued for a total of 3 h. After the reaction was completed, a light yellow transparent viscous substance was obtained, which was an environmentally friendly wool protection resin, which can be referred to as wool protection resin.

[0058] Preparation of finished product: After cooling the light yellow transparent viscous substance in step (2) to 50°C, 80 mL of dipropylene glycol was added and stirred for 15 min to obtain 708 g of finished product. The pH (5% aqueous solution) of the finished product was 3.06, and the kinematic viscosity (20°C, S3, 30 rpm, S3 means rotor No. 3) was 2868 mPa·s.

[0059] Example 2

[0060] Environmentally friendly wool protection resin, its structural formula is:

[0061]

[0062] -CH3, the values ​​of x, y, m, and n are 10, 15, 15, and 15 respectively.

[0063] The preparation method of the environmentally friendly wool protection resin comprises the following steps:

[0064] (1) Pre-shrinkage: 140 g of maleic acid crystals were added to a 1000 mL four-necked flask equipped with a mechanical stirrer and a condenser. The nitrogen protection was turned on and the gas flow rate was maintained at 40 mL / min. 78 g of polyethylene glycol 400 and 100 g of deionized water were added. At the same time, 0.15 g of anhydrous ferric chloride was added. The stirring was turned on and the speed was set to 200 rpm. The reaction mixture was then heated to 60° C. and stirred for 30 min. The remaining 156 g of polyethylene glycol 400 was added within 45 min. The reaction was continued for 1 h to obtain a light yellow transparent solution.

[0065] (2) Copolymerization: The mixed system was heated to 80°C and the rotation speed was adjusted to 300 rpm. 0.60 g of ammonium persulfate was added while the temperature was kept at 80±2°C. Then, a total of 110 g of methacrylic acid was added in 4 portions using a constant pressure funnel. The feeding time for each portion was 5 min. After the addition was completed, the mixture was stirred for 40 min. The total reaction time was 3 h. After the reaction was completed, a yellow transparent viscous substance was obtained, which was the environmentally friendly wool protection resin.

[0066] Preparation of finished product: When the yellow transparent viscous substance in step (2) is cooled to 50°C, dipropylene glycol is added and stirred to obtain 636 g of finished product. The pH (5% aqueous solution) of the finished product is 3.25, and the kinematic viscosity (20°C, S3, 30rpm) is 2598 mpa·s.

[0067] Comparative Example 1

[0068] A method for preparing a resin comprises the following steps: replacing polyethylene glycol 200 in Example 1 with 360 g polyethylene glycol 3000 (weight average Mw≈3000), and the amounts of maleic anhydride and itaconic acid used in Comparative Example 1 are 24 g and 33 g respectively, and the remaining raw materials and experimental process are the same as those in Example 1. The reaction process is divided into two times, and 50 g of deionized water is added each time to reduce the viscosity of the system, and finally 525 g of yellow finished resin is obtained. The pH (5% aqueous solution) of the finished product is 3.30, and the kinematic viscosity (20°C, S3, 30 rpm) is 3339 mpa·s.

[0069] Comparative Example 2

[0070] A method for preparing a resin comprises the following steps: 120 g of polyvinyl alcohol 1788 (Mw≈6000) is used to replace polyethylene glycol 200 in Example 1, maleic anhydride and itaconic acid are used in amounts of 202 g and 33 g respectively, and the remaining raw materials and experimental process are the same as those in Example 1. During the reaction, due to the serious viscosity increase of the mixed solution, deionized water is added 4 times, 35 g each time, to dilute, and finally 507 g of a dark yellow finished resin is obtained. The pH (5% aqueous solution) of the finished product is 3.83, and the kinematic viscosity (20°C, S3, 30 rpm) is 4016 mpa·s.

[0071] Product effect testing

[0072] Dyeing and finishing of pure wool fabric (process a): first, soak the wool cloth in 2g / L non-ionic cleaning liquid TF-115K for 15min, then rinse it with clean water for 15min, dehydrate it and dry it at 60℃, take 200g of dried wool cloth and put it into infrared dyeing machine, then add 5g of leveling agent TF-217K and 8g of resin prepared in the above embodiment or comparative example in sequence, the bath ratio is 1:20, and the pH in the dye bath is 5.2. After running for 30min, heat it to 40℃ and add 2g of acid dye (acid red B-3G01: 0.52%, acid yellow 3GN: 0.48%, acid blue C-G01: 0.72%). After continuing to operate for 30 minutes, the temperature began to rise, maintaining a heating rate of 1°C / min and heating to 98°C and keeping warm for 60 minutes. After completion, drain the water, wash with 3g / L ammonia-containing soap solution for 10 minutes at 75°C, then rinse with 60°C warm water for 10 minutes, take out of the cylinder and dehydrate and dry.

[0073] Dyeing and finishing of wool / polyester blended (70 / 30) fabric (i.e. wool blended fabric) (process b): first, the wool blended fabric is immersed in 2g / L non-ionic cleaning solution for 15min, then taken out and rinsed with clean water for 15min, dried at 60℃ after dehydration, 200g of wool blended fabric is put into infrared dyeing machine, then 35g of sodium sulfate, 5g of acid leveling agent TF-217K, 5g of anti-staining agent TF-288A and the resin prepared in the above embodiment or comparative example are added in sequence, and the bath ratio is 1:20. After running for 30min, 1.4g of acid dye (acid red B-3G01: 0.52%, acid yellow 3GN: 0.48%, acid blue C-G01: 0.70%) and 0.6g of disperse dye (disperse green C-6B: 0.72%, disperse red SE-FL: 0.28%) are added after heating to 40℃. After 30 minutes, heat up and maintain the heating rate of 1.5℃ / min to 120℃ and keep warm for 60 minutes. After draining, wash with 5g / L ammonia soap solution for 10 minutes, rinse with 60℃ warm water for 10 minutes, then take out of the tank and dehydrate and dry.

[0074] The breaking strength, free formaldehyde content on the surface, color fastness and other performance indicators of pure wool and wool blended fabrics finished by the above process a and process b were measured according to the standard methods of "GB / T 3923.2-2013 Textile fabric tensile properties Part 2: Determination of breaking strength (grab method)", "GB / T 2912.1-2009 Textile formaldehyde determination Part 1: Free and hydrolyzed formaldehyde (water extraction method)" and "GB / T3921-2008 Textile color fastness test: color fastness to soap and soap" respectively. The feel of the finished fabric was evaluated by the touch of 8 application technicians, mainly in terms of softness and fluffiness, and was divided into 5 levels, with 5 being the best and 1 being the worst.

[0075] In addition, a blank group was set up. The only difference between the blank group and process a or process b was that the resin prepared in the examples or comparative examples was not used.

[0076] Unfinished raw fabric refers to the original pure wool fabric and wool blended fabric that have not been treated by process a and process b.

[0077] The test results are shown in Table 1 and Table 2.

[0078] Table 1: Comparison of properties of pure wool fabrics after finishing with process a

[0079]

[0080] Table 2: Comparison of properties of wool / polyester blended (70 / 30) fabrics after finishing with process b

[0081]

[0082] Note: Commercially available wool protectants H, W, P: H is a formaldehyde precursor type, W is a hydrolyzed protein type, and P is an anti-setting type.

[0083] From the results in Table 1 and Table 2 above, it can be seen that the environmentally friendly wool protection resin prepared in the embodiment of the present invention has a high strength retention rate for the wool after finishing, and has no negative impact on color fastness and hand feel, and has obvious advantages over commercially available competitive products. In addition, when high molecular weight polyethylene glycol or polyvinyl alcohol with a high hydroxyl content is used instead of low molecular weight polyethylene glycol in the comparative example, the protection ability of the obtained copolymer resin is not significantly improved compared with the embodiment, but the fabric after finishing tends to be hardened and the hand feel is deteriorated.

Claims

1. Environmentally friendly wool protection resin, characterized in that: Its structural formula is as follows: wherein R represents hydrogen, alkyl or carboxyl-substituted alkyl; x, y, m, and n are positive integers greater than 1.

2. The environmentally friendly wool protection resin according to claim 1, characterized in that: x is a positive integer of 2-25; and / or y is a positive integer of 10-30; and / or m is a positive integer of 10-30; and / or n is a positive integer of 10-30.

3. The environmentally friendly wool protection resin according to claim 1, characterized in that: The carbon number of the alkyl group is 1-10.

4. The environmentally friendly wool protection resin according to claim 1, characterized in that: The R represents any one of H, -CH3, -C6H6, -CH2COOH, and -CH(COOH)-CH2COOH.

5. The method for preparing the environmentally friendly wool protective resin according to any one of claims 1 to 4, characterized in that: The following steps are involved: In a protective gas atmosphere, polyethylene glycol and maleic anhydride are mixed for a first reaction to obtain a pre-shrinkage product, and then an unsaturated organic acid is added for a second reaction to obtain the environmentally friendly wool protective resin.

6. The preparation method according to claim 5, characterized in that: The polyethylene glycol includes at least one selected from PEG200, PEG400, PEG600 and PEG800; and / or the maleic anhydride substance is selected from at least one of maleic anhydride or maleic acid; and / or the unsaturated organic acid is selected from at least one of itaconic acid, ethylene succinic acid, acrylic acid, methacrylic acid, cis-aconitic acid and cinnamic acid.

7. The preparation method according to claim 5, characterized in that: The molar ratio of the polyethylene glycol to the maleic anhydride substance is 1:(1.8-2.5); and / or the molar ratio of the unsaturated organic acid to the maleic anhydride substance is 0.9-1.5:

1.

8. The preparation method according to claim 5, characterized in that: When polyethylene glycol is mixed with maleic anhydride, a polymerization inhibitor is also added, wherein the polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, bisphenol A, ferric chloride, cupric chloride, and sodium sulfate; and / or, an initiator is added after adding an unsaturated organic acid, wherein the initiator is selected from at least one of ammonium persulfate, sodium persulfate, and potassium persulfate.

9. The preparation method according to claim 5, characterized in that: The temperature of the first reaction is 40-60° C.; and / or, the time of the first reaction is 0.5-2.5 hours; and / or, the temperature of the second reaction is 78-82° C.; and / or, the time of the second reaction is 1-3 hours.

10. Use of the environmentally friendly wool protection resin according to any one of claims 1 to 4 in the preparation of wool textiles.

Images