Bio-based chinlon hydrophilic softening finishing agent as well as preparation method and application thereof

Abstract

The invention discloses a bio-based chinlon hydrophilic softening finishing agent and a preparation method thereof. The bio-based chinlon hydrophilic softening finishing agent is synthesized, silicone oil is endowed with excellent hydrophilic performance by means of a side-chain polyether group and a high-hydrophilic sulfonic acid group, a hydrophilic flexible cross-linked network is formed by a bio-based modified polyether amine intermediate and end-side polyether epoxy silicone oil, and further cross-linking is performed in the subsequent heat setting process; a three-dimensional net-shaped film is formed on the surface of the fiber, and a dyeing agent and a softening agent are anchored on the chinlon fabric, so that the soft and glutinous hand feeling and the water-soaking-resistant fastness of the softening finishing agent are improved. The softening finishing agent prepared by the preparation method has the advantages that the high hydrophilicity of the traditional side chain polyether silicone oil is reserved, the softening property and the color fastness are improved, the application effect is good, the market demand is met, and the obvious social benefit and the wide market prospect are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical materials, in particular to a bio-based nylon hydrophilic soft finishing agent and a preparation method and application thereof. BACKGROUND

[0002] Nylon fiber, also known as polyamide fiber or nylon, has a macromolecular main chain connected by amide bonds, is the first synthetic fiber to achieve industrial production in the world, and is one of the main fibers of textile fabrics at present. Nylon fiber has many outstanding characteristics in textile applications, such as high breaking strength, excellent wear resistance, good low temperature resistance and resilience, so nylon fiber has significant advantages in outdoor, sports and casual clothing fields, and becomes the first choice for making fabrics such as down jackets, outdoor jackets, women's underwear, yoga clothes and sportswear.

[0003] With the improvement of living standards, consumers' demand for comfort and functionality of textile fabrics has further increased, and the problems of nylon fabrics in wearing have gradually emerged. The commonly used nylon fiber finishing agent is a silicone oil system, and the hydrophilicity of the treated nylon fiber is not strong, the wearing comfort is poor, and people feel hot and uncomfortable. In addition, in order to prevent the phenomenon of color loss of consumers when washing nylon fabrics, the amount of color fixing agent is generally increased during finishing, and the interaction between the color fixing agent and the dye is strengthened through a large number of active groups in the color fixing agent. The above method can improve the color fastness of nylon fabric, but also affects the hand feeling of the fabric, which cannot meet the requirements of consumers for the comfort of clothes. Therefore, how to solve the problems of nylon fabrics and provide a finishing agent that can provide both hydrophilic and color fixing functions has become a research hotspot in the textile industry. SUMMARY

[0004] In view of the problem that the finishing agent in the prior art cannot simultaneously satisfy the functions of hydrophilicity and color fixing, the present application provides a bio-based nylon hydrophilic soft finishing agent and a preparation method and application thereof. The bio-based nylon hydrophilic soft finishing agent is synthesized, the side chain polyether group and the high hydrophilicity sulfonic acid group are used to give the silicone oil excellent hydrophilic performance, and the bio-based modified polyether amine intermediate is further crosslinked with the end side polyether epoxy silicone oil to form a hydrophilic flexible crosslinked network, and further crosslinking is carried out in the subsequent heat setting process to form a three-dimensional network film on the fiber surface, so that the dyeing agent and the softening agent are anchored on the nylon fabric, thereby improving the soft and sticky hand feeling and water resistance of the soft finishing agent.

[0005] Specifically, the present application adopts the following technical scheme: a bio-based nylon hydrophilic soft finishing agent and a preparation method thereof, comprising the following steps: 1. Preparation of end side polyether modified epoxy silicone oil Dimethylcyclosiloxane mixture (DMC), tetramethyldihydrodisiloxane (hydrogen-containing double-seal HMM), side-chain polyether silicone oil are added to the reaction bottle, stirring is started, after uniform stirring, concentrated sulfuric acid is added, the reaction is carried out in an oil bath at 40-50℃, and the reaction is carried out for 5-7 hours; after the reaction is completed, a small amount of sodium bicarbonate is added for neutralization, and finally water washing, liquid separation and purification are carried out to obtain the end-side hydrogen-containing silicone oil. Under the nitrogen atmosphere, the end-side hydrogen-containing silicone oil, isopropyl alcohol, allyl polyether, and allyl epoxy polyether are added to the reaction bottle with stirring and condensing device, stirring is started, the temperature is raised to 65-80℃, and then chloroplatinic acid catalyst is added, and the reaction is carried out at 80℃ for 3-5 hours to obtain the end-side polyether modified epoxy silicone oil.

[0006] 2. Preparation of bio-based modified polyether amine intermediate Bio-based polyethylene glycol is added to the reaction bottle with stirring and condensing device, and slowly heated to 50-55℃, and stirred until fully dissolved, then epoxy chloropropane and catalyst tetrabutylammonium bromide are added, and stirred for 20 minutes; then sodium hydroxide / ethanol solution is added in 3 batches, and continues to be stirred for 10 hours, after the reaction is completed, hot filtration is carried out to remove the generated sodium chloride solid, then unreacted epoxy chloropropane and anhydrous ethanol are removed by distillation under reduced pressure, and finally water is removed by rotary evaporation to obtain the product bio-based polyethylene glycol diglycidyl ether. The bio-based polyethylene glycol diglycidyl ether and polyether amine (or organic amine), and solvent isopropyl alcohol are added to the reaction bottle with stirring and condensing device, and the reaction temperature is controlled at 50-80℃, and the reaction is carried out for 2-10 hours to obtain the bio-based modified polyether amine intermediate.

[0007] 3. Preparation of bio-based nylon hydrophilic soft finishing agent The end-side polyether modified epoxy silicone oil, bio-based modified polyether amine intermediate, and solvent isopropyl alcohol are added to the reaction bottle with stirring and condensing device, and the reaction temperature is controlled at 50-80℃, and the reaction is carried out for 2-20 hours, then 2-aminoethanesulfonic acid is added, and the reaction is continued for 2-20 hours, then the solvent is removed under vacuum to obtain the bio-based nylon hydrophilic soft finishing agent.

[0008] Further, in step 1), the hydrogen content of the side-chain polyether silicone oil is 1.58%, the molecular weight is about 3162g / mol, the mass ratio of the side-chain hydrogen-containing silicone oil to DMC is between 1:6 and 1:15, the mass ratio of the hydrogen-containing double-seal HMM to DMC is between 1:25 and 1:40, the mass of the concentrated sulfuric acid accounts for about 2% of the total mass, and the molar ratio of sodium bicarbonate to concentrated sulfuric acid is between 1.3:1 and 1.6:1.

[0009] Further, in step 1), the purity of the end-side hydrogen-containing silicone oil is ≥96.0%, and the theoretical hydrogen content is between 0.1% and 0.2%.

[0010] Further, in the step 1), the molecular weight of the allyl polyether and allyl epoxy polyether is 500, 800 or 1000 g / mol, the molar ratio of the allyl polyether, the allyl epoxy polyether and the end-hydrogen-containing silicone oil is between 1:1 and 1.1:2, the molar ratio of the allyl polyether and the allyl epoxy polyether is between 1:0.5 and 1:2, the chloroplatinic acid catalyst is an isopropyl alcohol solution of chloroplatinic acid, and the amount of chloroplatinic acid used in the reaction is between 20-40 ppm.

[0011] Further, in the step 2), the molecular weight of the bio-based polyethylene glycol is 600, 800 or 1000 g / mol, the molar ratio of the bio-based polyethylene glycol and the epichlorohydrin is between 1:2 and 1:4, the molar ratio of the bio-based polyethylene glycol and the catalyst tetrabutylammonium bromide is between 1:0.05 and 1:0.2, and the molar ratio of the bio-based polyethylene glycol and the sodium hydroxide is between 1:1 and 1:4.

[0012] Further, in the step 2), the polyether amine is one or a mixture of several of ED-2003, ED-900, ED-600, ED-410, ED-210, D400 and D230, the organic amine is one or a mixture of several of ethylenediamine, propylenediamine, N,N-dimethyl-1,3-propanediamine, tetramethylhexanediamine, diethylenetriamine and triethylenetetramine, and the molar ratio of the bio-based polyethylene glycol diglycidyl ether and the polyether amine (or organic amine) is between 1:1 and 1:2.

[0013] Further, in the step 3), when the end-polyether-modified epoxy silicone oil and the bio-based modified polyether amine intermediate react, the molar ratio of the epoxy group and the amine group is between 1:1 and 1:1.5, and the molar ratio of the bio-based modified polyether amine intermediate and 2-aminoethanesulfonic acid is between 2:1 and 4:1.

[0014] Preferably, in the step 1), the reaction temperature for preparing the end-hydrogen-containing silicone oil is 40°C.

[0015] Preferably, in the step 1), the temperature for adding the chloroplatinic acid catalyst is between 68-72°C, the reaction solution warms up quickly after the chloroplatinic acid catalyst is added, and if the subsequent temperature is too high, the end-polyether-modified epoxy silicone oil generated has a brownish appearance, so the chloroplatinic acid catalyst needs to be added at about 70°C.

[0016] Preferably, in the synthesis of the end-side polyether-modified epoxy silicone oil in step 1), the molar ratio of allyl polyether to allyl epoxy polyether is between 1:0.5 and 1:1. If the proportion of allyl epoxy polyether is high, the content of epoxy groups in the generated end-side polyether-modified epoxy silicone oil is high, and it is easy to over-crosslink when reacting with the bio-based modified polyether amine intermediate subsequently. If the proportion of allyl epoxy polyether is low, it is difficult to form a crosslinked network when reacting with the bio-based modified polyether amine intermediate subsequently. Therefore, the content of epoxy groups in each mole of end-side polyether-modified epoxy silicone oil is between 3-4 moles, which is the best.

[0017] Preferably, in step 2), the molecular weight of the bio-based polyethylene glycol is 1000 g / mol, the polyether amine is one or a mixture of several of ED-900, ED-600, and ED-410; and the organic amine is one or a mixture of several of ethylenediamine, tetramethylhexanediamine, and N,N-dimethyl-1,3-propanediamine. The molecular weight of the synthesized bio-based modified polyether amine intermediate should be between 1500-2500 g / mol. If the molecular weight is too low, the bio-based modified polyether amine intermediate is prone to react with the end-side polyether-modified epoxy silicone oil, and over-crosslinking is easy to occur. Therefore, the high molecular weight of the bio-based modified polyether amine intermediate can prevent over-crosslinking to some extent.

[0018] Preferably, in step 2), the molar ratio of bio-based polyethylene glycol to epichlorohydrin is between 1:3 and 1:4. Bio-based polyethylene glycol (1000 molecular weight) reacts with epichlorohydrin, and the theoretical molar ratio is 1:2. However, the molecular weight of bio-based polyethylene glycol (1000 molecular weight) is large, and the activity is low, so the reaction is not easy to occur. If the theoretical molar ratio is used for feeding, the yield is not high. Therefore, an excess of epichlorohydrin will be beneficial to improve the yield of the product.

[0019] Preferably, in step 2), the molar ratio of bio-based polyethylene glycol to sodium hydroxide is between 1:2 and 1:3. Sodium hydroxide is a key reagent for removing hydrogen chloride and forming a bio-based polyethylene glycol diglycidyl ether. If the amount of sodium hydroxide is small, the ring closure reaction is not complete. If the amount of sodium hydroxide is too large, epichlorohydrin will undergo ring-opening polymerization under the action of strong base, which will reduce the epoxy value of the product. Therefore, an appropriate amount of sodium hydroxide will be beneficial to improve the yield of the product.

[0020] Preferably, in step 2), the molar ratio of bio-based polyethylene glycol diglycidyl ether to polyether amine (or organic amine) is between 1:1.3 and 1:1.8, the reaction temperature is controlled at 50-60°C, and the reaction time is 2-6 hours. During the reaction, the amino group is slightly excessive, and the reaction time cannot be too long, so as to form ABA and AB block molecules, and at the same time, a certain unreacted epoxy group is retained to provide a reaction site for the subsequent reaction with 2-aminoethanesulfonic acid.

[0021] Preferably, in the step 3), the reaction temperature of the end side polyether modified epoxy silicone oil and the bio-based modified polyether amine intermediate is 50-60℃, the reaction time is 4-6 hours, and the reaction continues for 2-4 hours after adding 2-aminoethanesulfonic acid. If the reaction temperature is too high and the reaction time is too long, it will be over crosslinked. Therefore, low temperature and short time reaction can prevent over crosslinking to a certain extent.

[0022] The bio-based nylon hydrophilic soft finishing agent of the application forms a hydrophilic flexible crosslinked network through the remaining epoxy groups in the end side polyether epoxy silicone oil molecules as crosslinking points, and can further covalently crosslink in the subsequent heat setting process, forming a three-dimensional network film on the fiber surface, thereby anchoring the dyeing agent and softening agent in the nylon fabric, having a certain color fixing effect. In addition, the bio-based nylon hydrophilic soft finishing agent of the application is synthesized on the basis of traditional side chain polyether silicone oil, and long chain polyether amine modified by bio-based polyethylene glycol and high hydrophilicity sulfonic acid groups are introduced, further improving the hydrophilicity, making the finished nylon fabric have excellent hydrophilicity, softness and wearing comfort, and more meeting the market demand. DETAILED DESCRIPTION

[0023] The following examples are used to further illustrate the application, and the purpose is to illustrate the application, and should not be interpreted as limiting the scope of the application. The following uses weight parts and weight percentage unless otherwise specified.

[0024] The raw materials used in the application are conventional commercially available products unless otherwise specified; the methods used in the application are conventional methods in the art unless otherwise specified.

[0025] In the dimethylcyclosiloxane mixture (DMC) used in the application, the mass ratio of D4 (octamethylcyclotetrasiloxane) is greater than 95%, and the ratio of D5 (decamethylcyclopentasiloxane) and D6 (dodecamethylcyclohexasiloxane) is less than 5%.

[0026] The HYPERLINK concentrated sulfuric acid described in the application is a sulfuric acid aqueous solution with a mass fraction of not less than 70%.

[0027] In the application, the hand style evaluation method: select 5 professional personnel with experience in evaluating the hand feeling of nylon fabric, blind touch the soft finished fabric sample, and score according to the soft and sticky hand feeling of the fabric, 1-5 score represents the hand feeling evaluation result, 5 points represent the best, and 1 point represents the worst.

[0028] Hydrophilic property evaluation method: the fabric is fixed on the beaker mouth with rubber band, and a drop of deionized water is dropped on the surface of the nylon fabric from a distance of 1 cm from the fabric surface. The time required for the water droplet to disappear from the mirror surface is recorded with a stopwatch, which is the wetting time. At least 5 points of each fabric are detected. The shorter the wetting time, the better the hydrophilic property of the fabric.

[0029] Soak water fastness test: the soft finished nylon fabric (red) is soaked in warm water with detergent, the detergent content is 5g / L, the water temperature is 50-60℃, the bath ratio is 1:50, after oscillation in 60℃ water bath for 20min (50ppm), 5 people with relevant experience are selected to evaluate the color loss in water, and the rating is 5 for the best and 1 for the worst.

[0030] The embodiments of the application are further described in the following examples.

[0031] It should be clear that the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0032] The terms used in the embodiments of the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0033] Example 1: Preparation of end-side polyether modified epoxy silicone oil A 430g DMC, 15g hydrogen-containing double-seal HMM, 35g side-chain polyether silicone oil (hydrogen content 1.58%, molecular weight 3162g / mol) were added to the reaction bottle, stirring was started, 9.6g concentrated sulfuric acid was added after uniform stirring, the reaction was carried out in an oil bath at 40℃, and the reaction was carried out for 6 hours; after the reaction was completed, a small amount of 12g sodium bicarbonate was added for neutralization, and finally 5 times of water washing, liquid separation and purification were carried out to obtain end-side hydrogen-containing silicone oil A.

[0034] Under a nitrogen atmosphere, 200g of the above-mentioned end-side hydrogen-containing silicone oil A, 570g of isopropyl alcohol, 150g of allyl polyether (molecular weight 1000g / mol), and 195g of allyl epoxy polyether (molecular weight 1000g / mol) were added to a reaction bottle with stirring and condensing device, stirring was started, and 4g of chloroplatinic acid isopropyl alcohol solution (1%) was added after heating to 70℃. The reaction was carried out at 80℃ for 4 hours to obtain end-side polyether modified epoxy silicone oil A.

[0035] Preparation of bio-based modified polyether amine intermediate A Put 200g of bio-based polyethylene glycol with a molecular weight of 1000 into a reaction bottle with stirring condensing device, slowly warm up to 50-55℃, stir until fully dissolved, then add 74g of epoxy chloropropane, 11.6g of catalyst tetrabutylammonium bromide, and keep stirring for 20 minutes; then add sodium hydroxide / ethanol solution (20g of sodium hydroxide + 500mL of ethanol) in 3 batches, continue to keep stirring for 10 hours, after the reaction is completed, filter while hot to remove the generated sodium chloride solid, then remove the unreacted epoxy chloropropane and anhydrous ethanol under reduced pressure, and finally remove the water by rotary evaporation to obtain the product bio-based polyethylene glycol diglycidyl ether.

[0036] Take 200g of the above bio-based polyethylene glycol diglycidyl ether, 100g of polyether amine ED-900, 115g of polyether amine ED-600, and 400g of isopropyl alcohol, and put them into a reaction bottle with stirring condensing device, warm up to 80℃, and react for 10 hours to obtain the bio-based modified polyether amine intermediate A.

[0037] Preparation of bio-based nylon hydrophilic soft finishing agent A Put 200g of end-side polyether modified epoxy silicone oil A and 136g of bio-based modified polyether amine intermediate A into a reaction bottle with stirring condensing device, control the reaction temperature to be 80℃, react for 4 hours, then add 2.0g of 2-aminoethanesulfonic acid, continue to react for 2 hours, and then remove the solvent isopropyl alcohol under vacuum to obtain the bio-based nylon hydrophilic soft finishing agent A.

[0038] Example 2: Preparation of end-side polyether modified epoxy silicone oil B Put 430g of DMC, 15g of hydrogen-containing double-seal HMM, and 48g of side-chain polyether silicone oil (hydrogen content of 1.58%, molecular weight of 3162g / mol) into a reaction bottle, start stirring, add 9.9g of concentrated sulfuric acid after uniform stirring, warm up to 40℃ in an oil bath for reaction, and react for 7 hours; after the reaction is completed, add 12.5g of sodium bicarbonate in small amounts and multiple times for neutralization, and finally obtain the end-side hydrogen-containing silicone oil B after water washing 5 times for separation and purification.

[0039] Under a nitrogen atmosphere, put the above 200g of end-side hydrogen-containing silicone oil A and 580g of isopropyl alcohol, 220g of allyl polyether (molecular weight of 1000g / mol), and 160g of allyl epoxy polyether (molecular weight of 800g / mol) into a reaction bottle with stirring condensing device, start stirring, warm up to 65℃, then add 4g of chloroplatinic acid isopropyl alcohol solution (1%), and react at 80℃ for 3 hours to obtain the end-side polyether modified epoxy silicone oil B.

[0040] Preparation of bio-based modified polyether amine intermediate B 200g of bio-based polyethylene glycol with a molecular weight of 600 was added to a reaction flask equipped with a stirring and condenser. The temperature was slowly raised to 50-55℃ and stirred until fully dissolved. Then, 74g of epichlorohydrin and 11.6g of tetrabutylammonium bromide catalyst were added, and the mixture was kept warm and stirred for 20 minutes. Then, sodium hydroxide / ethanol solution (20g sodium hydroxide + 500mL ethanol) was added in three batches, and the mixture was kept warm and stirred for 10 hours. After the reaction was completed, the mixture was filtered while hot to remove the generated sodium chloride solid. Unreacted epichlorohydrin and anhydrous ethanol were then removed by vacuum distillation. Finally, water was removed by rotary evaporation to obtain the product, bio-based polyethylene glycol diglycidyl ether.

[0041] Weigh 200g of the above-mentioned bio-based polyethylene glycol diglycidyl ether, 174g of polyetheramine ED-900, 40g of polyetheramine ED-410, and 400g of isopropanol, add them to a reaction flask equipped with a stirring and condensing device, heat to 50°C, and react for 4 hours to obtain bio-based modified polyetheramine intermediate B.

[0042] Preparation of Bio-based Nylon Hydrophilic Softening Agent B 200g of end-side polyether modified epoxy silicone oil B and 136g of bio-based modified polyether amine intermediate B were added to a reaction flask equipped with a stirring and condensing device. The reaction temperature was controlled at 50℃ and the reaction was carried out for 20 hours. Then, 1.8g of 2-aminoethanesulfonic acid was added and the reaction was continued for another 20 hours. After that, the solvent isopropanol was removed under vacuum to obtain bio-based nylon hydrophilic softening agent B.

[0043] Example 3: Preparation of end-side polyether modified epoxy silicone oil C 430g of DMC, 12g of hydrogen-containing double-ended HMM, and 30g of side-chain polyether silicone oil (hydrogen content of 1.58% and molecular weight of 3162g / mol) were added to a reaction flask. Stirring was started, and after stirring evenly, 9.5g of concentrated sulfuric acid was added. The mixture was heated to 50°C in an oil bath and reacted for 5 hours. After the reaction was completed, 12g of sodium bicarbonate was added in small amounts several times for neutralization. Finally, after washing with water 5 times, separation and purification were performed to obtain end-chain hydrogen-containing silicone oil C.

[0044] Under a nitrogen atmosphere, 200g of end-side hydrogen-containing silicone oil C, 465g of isopropanol, 165g of allyl polyether (molecular weight 1000g / mol), and 100g of allyl epoxy polyether (molecular weight 800g / mol) were added to a reaction flask equipped with a stirring and condensing device. The stirring was turned on, and the temperature was raised to 80°C. Then, 3g of isopropanol solution of chloroplatinic acid (1%) was added, and the reaction was carried out at 80°C for 5 hours to obtain end-side polyether modified epoxy silicone oil C.

[0045] Preparation of bio-based modified polyetheramine intermediate C Repeat the steps of Example 1 to obtain the product bio-based polyethylene glycol diglycidyl ether.

[0046] Take 200g of the above-mentioned bio-based polyethylene glycol diglycidyl ether, 122g of polyether amine ED-600, 17g of tetramethylhexanediamine, 17g of glacial acetic acid, 360g of isopropyl alcohol, and add them to a reaction flask with stirring and condensing device, and heat to 60°C, and react for 2 hours to obtain bio-based modified polyether amine intermediate C.

[0047] Preparation of bio-based nylon hydrophilic soft finishing agent C Take 200g of the above-mentioned bio-based polyethylene glycol diglycidyl ether, 122g of polyether amine ED-600, 17g of tetramethylhexanediamine, 17g of glacial acetic acid, 360g of isopropyl alcohol, and add them to a reaction flask with stirring and condensing device, and heat to 60°C, and react for 2 hours to obtain bio-based modified polyether amine intermediate C.

[0048] Example 4: Preparation of bio-based polyethylene glycol diglycidyl ether Repeat the steps of Example 1 to obtain the product end-side hydrogen-containing silicone oil A.

[0049] Under a nitrogen atmosphere, take 200g of the above-mentioned end-side hydrogen-containing silicone oil A and 460g of isopropyl alcohol, 180g of allyl polyether (molecular weight 1000g / mol), 80g of allyl epoxy polyether (molecular weight 500g / mol), and add them to a reaction flask with stirring and condensing device, and start stirring, heat to 70°C, then add 3.5g of chloroplatinic acid in isopropyl alcohol solution (1%), and react at 80°C for 4 hours to obtain end-side polyether modified epoxy silicone oil D.

[0050] Preparation of bio-based modified polyether amine intermediate D Repeat the steps of Example 1 to obtain the product bio-based polyethylene glycol diglycidyl ether.

[0051] Take 200g of the above-mentioned bio-based polyethylene glycol diglycidyl ether, 120g of polyether amine ED-900, 100g of polyether amine ED-600, 400g of isopropyl alcohol, and add them to a reaction flask with stirring and condensing device, and heat to 60°C, and react for 7 hours to obtain bio-based modified polyether amine intermediate D.

[0052] Preparation of bio-based nylon hydrophilic soft finishing agent D Take 200g of the above-mentioned bio-based polyethylene glycol diglycidyl ether, 122g of polyether amine ED-600, 17g of tetramethylhexanediamine, 17g of glacial acetic acid, 360g of isopropyl alcohol, and add them to a reaction flask with stirring and condensing device, and heat to 60°C, and react for 2 hours to obtain bio-based modified polyether amine intermediate C.

[0053] Comparative Example 1: The procedure of Example 1 was repeated to obtain the product hydrogen-terminated silicone oil A.

[0054] 2) Under a nitrogen atmosphere, 200 g of hydrogen-terminated silicone oil A, 550 g of isopropyl alcohol, and 350 g of allyl polyether (molecular weight 1000 g / mol) were added to a reaction flask with a stirring condenser, stirring was started, and the temperature was raised to 70°C, then 4 g of chloroplatinic acid isopropyl alcohol solution (1%) was added, and the reaction was carried out at 80°C for 4 hours to obtain the end-polyether silicone oil.

[0055] Comparative Example 2: 200 g of double-end epoxy silicone oil with a molecular weight of 4000 (solid content 99.8%) was weighed into a reaction flask with a stirring condenser, 66 g of polyether amine ED-900 and 250 g of isopropyl alcohol were added, the reaction temperature was controlled at 78-82°C, and the reaction was carried out for 10 hours, and finally the isopropyl alcohol was removed by vacuum to obtain the polyether block silicone oil.

[0056] In the bio-based nylon hydrophilic soft finishing agent prepared in Examples 1-4 above, the end-polyether silicone oil prepared in Comparative Example 1, and the polyether block silicone oil prepared in Comparative Example 2, a suitable amount of ethylene glycol monobutyl ether was added until the solid content was 70%, 20% of the emulsifier AEO9 was added, and the mixture was mixed uniformly using a dispersion disc, and then deionized water was gradually added for emulsification to obtain a nylon hydrophilic soft finishing agent with a solid content of 20%.

[0057] Comparative tests were carried out on nylon knitted fabrics, the working solution of the soft finishing agent had a content of 30 g / L, and a dip-nip treatment method was used, and the temperature was set at 180°C for 90 s of drying.

[0058] Table 1 Application performance comparison test

[0059] As can be seen from the above table, the nylon knitted fabric treated with the bio-based nylon hydrophilic soft finishing agent of the present application has very good hydrophilic properties, water resistance, and soft and sticky hand feeling. As can be seen from the data of Example 1 and Comparative Example 1 in the above table, the preparation method described in the present application can form a three-dimensional hydrophilic flexible crosslinked network during the preparation of the bio-based nylon hydrophilic soft finishing agent, which can improve the soft hand feeling and water resistance of the soft finishing agent while maintaining excellent hydrophilicity; as can be seen from the data of Example 2 and Comparative Example 2 in the above table, compared with the traditional polyether block silicone oil, the bio-based nylon hydrophilic soft finishing agent prepared in the present application has improved hydrophilicity and water resistance.

[0060] The above embodiments illustrate the structure, features and effects of the present application, and the above description is only the preferred embodiments of the present application. Any changes made in accordance with the concept of the present application, or equivalent embodiments with equivalent changes, shall be within the scope of the present application.

Claims

1. A method for preparing a bio-based hydrophilic softening agent for nylon, characterized in that, It includes the following steps: (1) Preparation of end-side polyether modified epoxy silicone oil; (2) Preparation of bio-based modified polyetheramine intermediate, wherein the bio-based modified polyetheramine intermediate is obtained by reacting bio-based polyethylene glycol diglycidyl ether with polyetheramine or organic amine in an organic solvent at 50-80°C for 2-10 hours; (3) To prepare a bio-based hydrophilic softening agent for nylon, the end-side polyether modified epoxy silicone oil and the bio-based modified polyether amine intermediate were reacted in an organic solvent at 50-80°C for 2-20 hours. Then, 2-aminoethanesulfonic acid was added and the reaction was continued for another 2-20 hours. After that, the solvent was removed under vacuum to obtain the bio-based hydrophilic softening agent for nylon. When the end-side polyether modified epoxy silicone oil and the bio-based modified polyether amine intermediate reacted, the molar ratio of epoxy groups to amine groups was 1:1 to 1:1.5, and the molar ratio of bio-based modified polyether amine intermediate to 2-aminoethanesulfonic acid was 2:1 to 4:

1.

2. The method according to claim 1, characterized in that, The method for preparing end-side polyether modified epoxy silicone oil in step (1) is as follows: after stirring the dimethylcyclosiloxane mixture, tetramethyldihydrodisiloxane, and side-chain polyether silicone oil evenly, concentrated sulfuric acid is added, and the temperature is raised to 40-50℃ for reaction for 5-7 hours; after the reaction is completed, sodium bicarbonate is added for neutralization, and finally, after washing with water, separation and purification, end-side hydrogen-containing silicone oil is obtained; under a nitrogen atmosphere, end-side hydrogen-containing silicone oil, isopropanol, allyl polyether, and allyl epoxy polyether are added to a reaction flask equipped with a stirring and condensing device, stirring is turned on, the temperature is raised to 65-80℃, chloroplatinic acid catalyst is added, and the reaction is carried out at 80℃ for 3-5 hours to obtain end-side polyether modified epoxy silicone oil.

3. The method according to claim 2, characterized in that, The side-chain polyether silicone oil has a hydrogen content of 1.58% and a molecular weight of 3162 g / mol. The mass ratio of the side-chain hydrogen-containing silicone oil to the dimethylcyclosiloxane mixture is 1:6 to 1:15, and the mass ratio of the tetramethyldihydrodisiloxane to the dimethylcyclosiloxane mixture is 1:25 to 1:

40. The concentrated sulfuric acid accounts for 2% of the total mass, and the molar ratio of sodium bicarbonate to concentrated sulfuric acid is between 1.3:1 and 1.6:

1. The allyl polyether and allyl epoxy polyether have a molecular weight range of 500-1000 g / mol. When the allyl polyether, allyl epoxy polyether, and end-chain hydrogen-containing silicone oil react, the molar ratio of allyl to silanol groups is between 1:1 and 1.1:2, and the molar ratio of allyl polyether to allyl epoxy polyether is between 1:0.5 and 1:

2. The chloroplatinic acid catalyst is an isopropanol solution of chloroplatinic acid.

4. The method according to claim 1, characterized in that, The method for preparing the bio-based modified polyetheramine intermediate in step (2) is as follows: heat the bio-based polyethylene glycol to 50-55℃, stir until fully dissolved, add epichlorohydrin and the catalyst tetrabutylammonium bromide, and keep warm and stir for 20 minutes; then add sodium hydroxide / ethanol solution in 3 portions, continue to keep warm and stir for 10 hours, filter while hot after the reaction to remove the generated sodium chloride solid, then remove the unreacted epichlorohydrin and anhydrous ethanol by vacuum distillation, and finally remove water to obtain the product bio-based polyethylene glycol diglycidyl ether; add the above bio-based polyethylene glycol diglycidyl ether, polyetheramine or organic amine, and solvent isopropanol to a reaction flask equipped with a stirring and condensing device, control the reaction temperature at 50-80℃, and react for 2-10 hours to obtain the bio-based modified polyetheramine intermediate.

5. The method according to claim 4, characterized in that, The bio-based polyethylene glycol has a molecular weight range of 600-1000 g / mol, the molar ratio of the bio-based polyethylene glycol to epichlorohydrin is between 1:2 and 1:4, the molar ratio of the bio-based polyethylene glycol to the catalyst tetrabutylammonium bromide is between 1:0.05 and 1:0.2, the molar ratio of the bio-based polyethylene glycol to sodium hydroxide is between 1:1 and 1:4, and the molar ratio of the bio-based polyethylene glycol diglycidyl ether to polyetheramine or organic amine is between 1:1 and 1:

2.

6. The method according to claim 4, characterized in that, The polyetheramine is one or a mixture of several of ED-2003, ED-900, ED-600, ED-410, ED-210, D400, and D230, and the organic amine is one or a mixture of several of ethylenediamine, propylenediamine, N,N-dimethyl-1,3-propanediamine, tetramethylhexanediamine, diethylenetriamine, and triethylenetetramine.

7. A bio-based nylon hydrophilic softening agent prepared by the preparation method described in claim 1.

8. The application of a bio-based nylon hydrophilic softening agent as described in claim 7.

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