Dyed fabric wet friction fastness improving agent and preparation method thereof

Abstract

The present invention relates to the technical field of textile printing and dyeing, and in particular to a dyed fabric wet rubbing fastness improver and a preparation method thereof. The preparation method comprises: first preparing a polyurethane prepolymer with polytetramethylene glycol and diisocyanate, then preparing a polyurethane intermediate with a small molecule diol 1,4-butanediol and a tertiary amine diol chain extender N-butyldiethanolamine as a chain extender, then preparing a polyurethane intermediate with diethyl iminodiacetate as a capping agent, and finally preparing a cationic polyurethane with bromobutyl as a quaternizing agent, polymerizing and cross-linking the cationic polyurethane with acrylamide under the action of an initiator to prepare the dyed fabric wet rubbing fastness improver, wherein an organosilicon segment is introduced into the polyurethane prepolymer molecular chain. The obtained dyed fabric wet rubbing fastness improver can effectively improve the wet rubbing fastness of the dyed fabric, and the dyed fabric treated with the dyed fabric wet rubbing fastness improver has good softness.

Description

Technical Field

[0001] The invention relates to the technical field of textile printing and dyeing, and in particular to a dyed fabric wet friction fastness improver and a preparation method thereof. Background Art

[0002] Reactive dyes have many characteristics such as bright colors, low price and easy use, and are widely used in the field of fabric dyeing. However, reactive dye molecules are highly water-soluble, and the wet rubbing fastness of fabrics dyed with reactive dyes is poor. There is a need to improve the wet rubbing fastness of dyed fabrics.

[0003] Chinese patent CN101492883B discloses a polymeric wet rubbing fastness enhancer, comprising a copolymer of 2-acrylamide-2-methylpropanesulfonic acid, acrylamide, dimethyldiallylammonium chloride, dimethyldiallylammonium, high molecular weight PVP, and an emulsifier, initiated by an initiator. The copolymer utilizes cationic groups, molecular attraction between fibers, reactive groups, and the film-forming properties of a colloidal protective agent, PE, to improve the color fastness and rubbing fastness of fabrics during the textile dyeing process. However, the cationic groups are provided solely by dimethyldiallylammonium chloride, resulting in a low content of cationic groups. Furthermore, the reaction raw material, 2-acrylamide-2-methylpropanesulfonic acid, contains anionic groups, which can weaken the cationic properties of the wet rubbing fastness enhancer and result in weak binding ability with water-soluble dyes containing anionic groups. Furthermore, film formation of the acrylic polymer can harden the fabric's feel, reducing its wearing comfort. Summary of the Invention

[0004] The present invention aims to improve the wet rubbing fastness of dyed fabrics and solve the problems in the prior art that the binding ability of the wet rubbing fastness improving agent with the fabric needs to be improved and the hand feel of the fabric is reduced.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a dyed fabric wet friction fastness improving agent comprises the following steps:

[0007] Step 1: mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding diisocyanate and dibutyltin dilaurate, reacting, cooling after the reaction, filtering, and obtaining a silicone-modified polyurethane prepolymer;

[0008] Step 2: adding N-butyldiethanolamine and 1,4-butanediol to the organosilicon-modified polyurethane prepolymer, reacting, and obtaining a polyurethane intermediate after the reaction is completed;

[0009] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, react, and after the reaction is completed, rotary evaporate, wash, filter, and dry to obtain polyurethane;

[0010] Step 4: adding polyurethane and bromobutyl to chloroform for reaction. After the reaction is completed, performing rotary evaporation, adding deionized water, and purifying and separating to obtain a cationic polyurethane solution;

[0011] Step 5: Add acrylamide to the cationic polyurethane solution, stir and mix, heat to a set temperature, dropwise add initiator solution, react, and after the reaction is completed, cool to obtain a dyed fabric wet friction fastness enhancer.

[0012] Preferably, in the step 1, the mass ratio of diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is (38-42):(10-15):(12-16):(0.1-0.3), and the reaction is carried out at a temperature of 85-95° C. for 2-3 hours.

[0013] Preferably, the diisocyanate comprises hexamethylene diisocyanate.

[0014] Preferably, the hydroxyl-terminated vinyl fluorosilicone oil in step 1 is prepared by the following steps:

[0015] The trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane and hexamethylcyclotrisiloxane are mixed, deionized water, an alkali catalyst and cyclodextrin are added, and the mixture is reacted. After the reaction is completed, the mixture is neutralized and purified to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

[0016] Preferably, the mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, base catalyst and cyclodextrin is 46.9:(8-12):(10-15):(3-6):(0.03-0.05):(0.005-0.01), and the reaction conditions are 40-60°C for 1-3h.

[0017] Preferably, the base catalyst comprises potassium hydroxide.

[0018] Preferably, in step 2, the mass ratio of the silicone-modified polyurethane prepolymer, N-butyldiethanolamine, and 1,4-butanediol is (130-150):(1-2):(0.5-1), and the reaction conditions are 45-55° C. for 1-3 hours.

[0019] Preferably, in step 3, the mass ratio of the polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is (65-82):(1200-1600):(3-5):(0.5-1), and the reaction is carried out at a temperature of 50-70° C. for 1-2 hours.

[0020] Preferably, in step 4, the mass ratio of polyurethane, bromobutyl and chloroform is 100:(15-20):(800-1200), the reaction conditions are reflux reaction at 60-80° C. for 2-4 hours, and the amount of deionized water added is 1-2 times the mass of chloroform.

[0021] Preferably, in step 5, the mass ratio of the cationic polyurethane solution, acrylamide, and initiator solution is 100:(2-4):(3-5), the initiator solution is added dropwise for 30-60 min, and the reaction is carried out at a set temperature for 1-3 h.

[0022] The set temperature is 60-80°C.

[0023] Preferably, the initiator solution comprises an aqueous solution of azobisisobutylamidine hydrochloride, and the aqueous solution of azobisisobutylamidine hydrochloride comprises a 0.5 wt % aqueous solution of azobisisobutylamidine hydrochloride.

[0024] The invention also discloses a dyed fabric wet rubbing fastness improving agent prepared by adopting the preparation method of the dyed fabric wet rubbing fastness improving agent.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The wet rubbing fastness improver of the present invention is a cationic waterborne polyurethane wet rubbing fastness improver. First, a polyurethane prepolymer is prepared using polytetramethylene ether glycol and diisocyanate. Then, a polyurethane intermediate is prepared using a small molecule diol 1,4-butanediol and a tertiary amine diol chain extender N-butyldiethanolamine as a chain extender. The polyurethane intermediate is reacted with a capping agent to prepare a polyurethane. Further, the polyurethane is reacted with a quaternizing agent to convert the tertiary amine group in the chain extender molecule into a quaternary ammonium salt to prepare a cationic polyurethane. The cationic group combines with a water-soluble dye containing an anionic group (carboxyl group, sulfonic acid group, etc.) to form a salt, thereby fixing the floating color on the fiber surface.

[0027] In the present invention, due to the presence of flexible molecular chains of polyether polyol in the polyurethane molecules, the polyurethane has good toughness and bendability, and has little effect on the feel of the fabric after film formation. In addition, when preparing the polyurethane prepolymer, hydroxyl-terminated vinyl fluorosilicone oil is also introduced. The introduction of the silicone molecular chain can give the fabric good softness and smoothness, improve the feel of the fabric, reduce the friction coefficient of the fabric surface, and make the dye less likely to fall off due to friction; the introduction of silicone can reduce the surface energy of the fabric, improve the hydrophobic effect, and thus improve the wet friction fastness of the dyed fabric; the introduction of vinyl enables the cationic polyurethane to crosslink and copolymerize with the crosslinking agent acrylamide under the action of an initiator, and the formed macromolecular network structure has the characteristics of horizontal film formation and vertical cationicity. The film formation can isolate the dye from the outside world and hinder the transfer of water-soluble staining; the introduction of organic fluoride can also improve the hydrophobicity of the fabric and further improve the wet friction fastness of the dyed fabric.

[0028] In the present invention, diethyl iminodiacetate is used as a capping agent for a polyurethane intermediate. The imino group reacts with an isocyanate group to protect the active isocyanate group while converting the imino group into a tertiary amine group. When the polyurethane reacts with a quaternizing agent, more quaternary ammonium salt structures can be formed, and the polyurethane has a stronger ability to bind to water-soluble dyes. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The present invention is a flow chart of the preparation process of the dyed fabric wet rubbing fastness improving agent. DETAILED DESCRIPTION

[0030] Example 1

[0031] This embodiment discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0032] Step 1, mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding hexamethylene diisocyanate and dibutyltin dilaurate, the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is 38:10:12:0.1, reacting at 85° C. for 3 hours, and after the reaction is completed, cooling to below 10° C. and filtering to obtain a silicone-modified polyurethane prepolymer;

[0033] The hydroxyl-terminated vinyl fluorosilicone oil is prepared by the following steps:

[0034] Mix trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethylcyclotrisiloxane, add deionized water, potassium hydroxide, and cyclodextrin, the mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide, and cyclodextrin is 46.9:8:10:3:0.03:0.005, react at 40°C for 3h, and after the reaction is completed, add 2mol / L hydrochloric acid to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture is 7, heat to 180°C, and evacuate to obtain hydroxyl-terminated vinyl fluorosilicone oil;

[0035] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the organosilicon-modified polyurethane prepolymer, wherein the mass ratio of the organosilicon-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 130:1:0.5, and react at 45° C. for 3 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0036] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 65:1200:3:0.5, and react at 50°C for 2h. After the reaction is completed, remove acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24h to obtain polyurethane;

[0037] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:15:800, and reflux at 60°C for 4 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water twice the mass of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0038] Step 5. Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 60° C., add dropwise 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution, the addition time of 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 30 min, the mass ratio of cationic polyurethane solution, acrylamide, and 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 100:2:3, react at 60° C. for 3 h, and after the reaction is completed, cool to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0039] Example 2

[0040] This embodiment discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0041] Step 1: Mix polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, add hexamethylene diisocyanate and dibutyltin dilaurate, and the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is 42:15:16:0.3, react at 95° C. for 2 hours, and after the reaction is completed, cool to below 10° C. and filter to obtain a silicone-modified polyurethane prepolymer;

[0042] The hydroxyl-terminated vinyl fluorosilicone oil is prepared by the following steps:

[0043] Mix trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethylcyclotrisiloxane, add deionized water, potassium hydroxide, and cyclodextrin, the mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide, and cyclodextrin being 46.9:12:15:6:0.05:0.01, and react at 60°C for 1h. After the reaction is completed, 2mol / L hydrochloric acid is added to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture is 7. The temperature is raised to 180°C, and vacuum is evacuated to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

[0044] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the silicone-modified polyurethane prepolymer, wherein the mass ratio of the silicone-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 150:2:1, and react at 55° C. for 1 hour. After the reaction is completed, a polyurethane intermediate is obtained;

[0045] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 82:1600:5:1, and react at 70°C for 1 hour. After the reaction is completed, remove the acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24 hours to obtain a polyurethane;

[0046] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:20:1200, and reflux at 80°C for 2h. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water (1 times the mass of bromobutyl) to the residue, stir at a stirring speed of 200r / min for 30min, let it stand for 2h, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0047] Step 5. Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 80° C., add dropwise 0.5wt% azobisisobutylamidine hydrochloride aqueous solution, the addition time of 0.5wt% azobisisobutylamidine hydrochloride aqueous solution is 60 min, the mass ratio of cationic polyurethane solution, acrylamide, and 0.5wt% azobisisobutylamidine hydrochloride aqueous solution is 100:4:5, react at 80° C. for 1 h, and after the reaction is completed, cool to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0048] Example 3

[0049] This embodiment discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0050] Step 1, mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding hexamethylene diisocyanate and dibutyltin dilaurate, the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is 39:11:13:0.15, reacting at 90° C. for 2.5 hours, and after the reaction is completed, cooling to below 10° C. and filtering to obtain a silicone-modified polyurethane prepolymer;

[0051] The hydroxyl-terminated vinyl fluorosilicone oil is prepared by the following steps:

[0052] Trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethylcyclotrisiloxane were mixed, and deionized water, potassium hydroxide, and cyclodextrin were added. The mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide, and cyclodextrin was 46.9:9:11:4:0.04:0.006. The mixture was reacted at 50° C. for 2 h. After the reaction was completed, 2 mol / L hydrochloric acid was added to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture was 7. The mixture was heated to 180° C. and vacuumed to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

[0053] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the silicone-modified polyurethane prepolymer, wherein the mass ratio of the silicone-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 135:1.2:0.6, and react at 50° C. for 2 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0054] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 69:1300:3.5:0.6, and react at 60°C for 1.5h. After the reaction is completed, remove the acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24h to obtain a polyurethane;

[0055] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:16:900, and reflux at 70°C for 3 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water with a mass of 1.5 times that of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0056] Step 5: Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 70°C, add dropwise a 0.5wt% aqueous solution of azobisisobutylamidine hydrochloride, and add the 0.5wt% aqueous solution of azobisisobutylamidine hydrochloride for 45 minutes. The mass ratio of the cationic polyurethane solution, acrylamide, and the 0.5wt% aqueous solution of azobisisobutylamidine hydrochloride is 100:2.5:3.5. The mixture is reacted at 70°C for 2 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0057] Example 4

[0058] This embodiment discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0059] Step 1, mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding hexamethylene diisocyanate and dibutyltin dilaurate, the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is 40:12.5:14:0.2, reacting at 90° C. for 2.5 hours, and after the reaction is completed, cooling to below 10° C. and filtering to obtain a silicone-modified polyurethane prepolymer;

[0060] The hydroxyl-terminated vinyl fluorosilicone oil is prepared by the following steps:

[0061] Trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethylcyclotrisiloxane were mixed, and deionized water, potassium hydroxide, and cyclodextrin were added. The mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide, and cyclodextrin was 46.9:10:12.5:4.5:0.04:0.007. The mixture was reacted at 50° C. for 2 h. After the reaction was completed, 2 mol / L hydrochloric acid was added to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture was 7. The mixture was heated to 180° C. and vacuumed to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

[0062] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the silicone-modified polyurethane prepolymer, wherein the mass ratio of the silicone-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 140:1.5:0.75, and react at 50° C. for 2 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0063] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 73:1400:4:0.75, react at 60°C for 1.5h, and after the reaction is completed, remove acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24h to obtain polyurethane;

[0064] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:17.5:1000, and reflux at 70°C for 3 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water with a mass of 1.5 times that of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0065] Step 5. Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 70° C., add dropwise 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution, the addition time of 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 45 min, the mass ratio of cationic polyurethane solution, acrylamide, and 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 100:3:4, react at 70° C. for 2 h, and after the reaction is completed, cool to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0066] Example 5

[0067] This embodiment discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0068] Step 1, mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding hexamethylene diisocyanate and dibutyltin dilaurate, the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is 40:12.5:14:0.2, reacting at 90° C. for 2.5 hours, and after the reaction is completed, cooling to below 10° C. and filtering to obtain a silicone-modified polyurethane prepolymer;

[0069] The hydroxyl-terminated vinyl fluorosilicone oil is prepared by the following steps:

[0070] Trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethylcyclotrisiloxane were mixed, and deionized water, potassium hydroxide, and cyclodextrin were added. The mass ratio of trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide, and cyclodextrin was 46.9:10:12.5:4.5:0.04:0.007. The mixture was reacted at 50° C. for 2 h. After the reaction was completed, 2 mol / L hydrochloric acid was added to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture was 7. The mixture was heated to 180° C. and vacuumed to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

[0071] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the silicone-modified polyurethane prepolymer, wherein the mass ratio of the silicone-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 140:1.5:0.75, and react at 50° C. for 2 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0072] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 73:1400:4:0.75, react at 60°C for 1.5h, and after the reaction is completed, remove acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24h to obtain polyurethane;

[0073] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:17.5:1000, and reflux at 70°C for 3 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water with a mass of 1.5 times that of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0074] Step 5. Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 70° C., add dropwise 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution, the addition time of 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 45 min, the mass ratio of cationic polyurethane solution, acrylamide, and 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 100:3:4, react at 70° C. for 2 h, and after the reaction is completed, cool to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0075] Comparative Example 1

[0076] This comparative example discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0077] Step 1: Mix polytetramethylene ether glycol and hydroxyl-terminated fluorosilicone oil, add hexamethylene diisocyanate and dibutyltin dilaurate, and the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated fluorosilicone oil, and dibutyltin dilaurate is 38:10:12:0.1, react at 85° C. for 3 hours, and after the reaction is completed, cool to below 10° C. and filter to obtain a silicone-modified polyurethane prepolymer;

[0078] The hydroxyl-terminated fluorosilicone oil is prepared by the following steps:

[0079] Mix trifluoropropylmethylcyclotrisiloxane and hexamethylcyclotrisiloxane, add deionized water, potassium hydroxide and cyclodextrin, the mass ratio of trifluoropropylmethylcyclotrisiloxane, hexamethylcyclotrisiloxane, deionized water, potassium hydroxide and cyclodextrin is 46.9:10:3:0.03:0.005, react at 40°C for 3h, and after the reaction is completed, add 2mol / L hydrochloric acid to the reaction mixture for neutralization. The pH value of the neutralized reaction mixture is 7. Heat to 180°C and evacuate to obtain hydroxyl-terminated vinyl fluorosilicone oil;

[0080] Step 2: Add N-butyl diethanolamine and 1,4-butanediol to the organosilicon-modified polyurethane prepolymer, wherein the mass ratio of the organosilicon-modified polyurethane prepolymer, N-butyl diethanolamine, and 1,4-butanediol is 130:1:0.5, and react at 45° C. for 3 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0081] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add acrylamide and triethylamine, the mass ratio of polyurethane intermediate, deionized water, acrylamide, and triethylamine is 65:1200:1.1:0.5, and react at 50°C for 2 hours. After the reaction is completed, remove the acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24 hours to obtain a polyurethane;

[0082] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:15:800, and reflux at 60°C for 4 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water twice the mass of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0083] Step 5, the cationic polyurethane solution was heated to 60 ° C, and 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution was added dropwise. The addition time of 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution was 30 min. The mass ratio of the cationic polyurethane solution and the 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution was 102:3. The reaction was carried out at 60 ° C for 3 h. After the reaction was completed, the temperature was cooled to room temperature to obtain a dyed fabric wet friction fastness improver.

[0084] Comparative Example 2

[0085] This comparative example discloses a method for preparing a dyed fabric wet friction fastness improving agent, comprising the following steps:

[0086] Step 1, adding hexamethylene diisocyanate and dibutyltin dilaurate to polytetramethylene ether glycol, the mass ratio of hexamethylene diisocyanate, polytetramethylene ether glycol, and dibutyltin dilaurate is 38:22:0.1, reacting at 85° C. for 3 hours, and after the reaction is completed, cooling to below 10° C. and filtering to obtain a polyurethane prepolymer;

[0087] Step 2: Add N-butyldiethanolamine and 1,4-butanediol to the polyurethane prepolymer, wherein the mass ratio of the polyurethane prepolymer, N-butyldiethanolamine, and 1,4-butanediol is 130:1:0.5, and react at 45° C. for 3 hours. After the reaction is completed, a polyurethane intermediate is obtained;

[0088] Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, the mass ratio of polyurethane intermediate, deionized water, diethyl iminodiacetate, and triethylamine is 65:1200:3:0.5, and react at 50°C for 2h. After the reaction is completed, remove acetonitrile by rotary evaporation at 40°C, wash the residue with cyclohexane, filter, and dry in a vacuum drying oven at 50°C for 24h to obtain polyurethane;

[0089] Step 4: Add polyurethane to chloroform, stir and dissolve, then add bromobutyl, the mass ratio of polyurethane, bromobutyl and chloroform is 100:15:800, and reflux at 60°C for 4 hours. After the reaction is completed, remove the chloroform by rotary evaporation at 40°C, add deionized water twice the mass of bromobutyl to the residue, stir at a stirring speed of 200 r / min for 30 minutes, let it stand for 2 hours, and remove the lower organic layer to obtain a cationic polyurethane solution;

[0090] Step 5. Add acrylamide to the cationic polyurethane solution, stir and mix, heat to 60° C., add dropwise 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution, the addition time of 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 30 min, the mass ratio of cationic polyurethane solution, acrylamide, and 0.5 wt% azobisisobutylamidine hydrochloride aqueous solution is 100:2:3, react at 60° C. for 3 h, and after the reaction is completed, cool to room temperature to obtain a dyed fabric wet rubbing fastness improver.

[0091] In the above embodiments and comparative examples: polytetramethylene ether glycol was purchased from Xuzhou Yihuiyang New Materials Co., Ltd., with the product number PTMG650 and a molecular weight of 650±25; hexamethylene diisocyanate was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd. with the CAS number 822-06-0; trifluoropropylmethylcyclotrisiloxane was purchased from Xinyuan Chemical (Shandong) Co., Ltd. with the CAS number 2374-14-3; tetramethyltetravinylcyclotetrasiloxane was purchased from Zhongshan Dixin Chemical Co., Ltd. with the CAS number 2554-06-5; hexamethylcyclotrisiloxane was purchased from Zhejiang Hengyecheng Organic Silicon Co., Ltd. with the CAS number 541-05-9; cyclodextrin was β-cyclodextrin purchased from Sinopharm Group Chemical Reagent Co., Ltd., CAS No.: 7585-39-9; N-butyldiethanolamine was purchased from Sinopharm Chemical Reagent Co., Ltd., N-butyldiethanolamine; 1,4-butanediol was purchased from Shanghai Kanglang Biotechnology Co., Ltd., CAS No.: 110-63-4; diethyl iminodiacetate was purchased from Zhongxin Chenshi (Wuhan) Technology Co., Ltd., CAS No.: 6290-05-7; bromobutane was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 109-65-9; acrylamide was purchased from Shanghai Qi'an Chemical Co., Ltd., CAS No.: 79-06-1; azobisisobutylamidine hydrochloride was purchased from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 2997-92-4.

[0092] Test Case

[0093] The performance tests were conducted on the dyed fabric wet rubbing fastness improving agents prepared in Examples 1-5 and Comparative Examples 1-2:

[0094] (1) Wet rubbing fastness test: The unfixed denim fabric dyed with Remazol ESP navy blue reactive dye was immersed and padded twice (the piling rate was 85%) with the dyed fabric wet rubbing fastness improver prepared in Examples 1-5 and Comparative Examples 1-2, dried at 100°C, and baked at 140°C for 5 minutes. The wet rubbing fastness of 7 groups of denim fabric samples treated with the dyed fabric wet rubbing fastness improver prepared in Examples 1-5 and Comparative Examples 1-2 and the untreated denim fabric sample were measured with reference to the standard GB / T3920-2008 "Textiles - Tests for Colour Fastness - Colour Fastness to Rubbing". The results are shown in Table 1:

[0095] Table 1

[0096]

[0097] As shown in Table 1, the wet rubbing fastness enhancer for dyed fabrics prepared by the present invention can effectively improve the wet rubbing fastness of dyed fabrics. The wet rubbing fastness enhancer is a cationic waterborne polyurethane wet rubbing fastness enhancer. The tertiary amine group in the tertiary amine diol chain extender and the tertiary amine group formed by the conversion of the imino-containing end-capping agent react with a quaternizing agent to form a large amount of quaternary ammonium salt structures, which have strong binding ability with water-soluble dyes containing anionic groups. When preparing the polyurethane prepolymer, hydroxyl-terminated vinyl fluorosilicone oil is introduced. The introduction of the organosilicon molecular chain and the organic fluoride can improve the hydrophobicity of the fabric and improve the wet rubbing fastness of the dyed fabric. The introduction of the vinyl group enables the cationic polyurethane to crosslink and copolymerize with the crosslinking agent acrylamide under the action of an initiator, isolating the dye from the outside world through film formation, and hindering water-soluble transfer staining. Compared with Example 1, in Comparative Example 1, hydroxyl-terminated vinyl fluorosilicone oil is replaced by hydroxyl-terminated fluorosilicone oil, and acrylamide is used instead of diethyl iminodiacetate as the end-capping agent. The cross-linking polymerization between the polyurethane molecules is achieved only through the acrylamide located at the end of the polyurethane, the degree of cross-linking polymerization is reduced, the film-forming performance is weakened, and the formed quaternary ammonium salt structure is reduced, and the wet rubbing fastness is significantly reduced; in Comparative Example 2, hydroxyl-terminated vinyl fluorosilicone oil is not added during the preparation of the polyurethane prepolymer, the polyurethane cannot participate in the cross-linking polymerization of the alkenyl group, the film-forming performance is significantly weakened, and the hydrophobic effect of the organosilicon molecular chain and the organic fluoride is lacking, and the wet rubbing fastness is greatly reduced.

[0098] (2) Softness Test: Denim fabrics dyed with unfixed Remazol ESP navy blue reactive dye were dipped and rolled twice (with a rolling rate of 85%), dried at 100°C, and baked at 140°C for 5 minutes. Five professionals formed a group to evaluate the touch of seven groups of denim fabric samples treated with the dyed fabric wet rubbing fastness improving agents prepared in Examples 1-5 and Comparative Examples 1-2, as well as the untreated denim fabric samples. The fabrics were ranked comprehensively based on their softness and smoothness. The hand feel was divided into five levels, with level 5 being the best and level 1 being the worst. The test results are shown in Table 2:

[0099] Table 2

[0100]

[0101] As shown in Table 2, the dyed fabric treated with the dyed fabric wet rubbing fastness enhancer prepared by the present invention exhibits excellent softness. The polyurethane exhibits good toughness and flexibility, with minimal impact on the fabric's feel. Furthermore, the addition of hydroxyl-terminated vinyl fluorosilicone oil during the preparation of the polyurethane prepolymer imparts excellent softness and smoothness to the fabric, enhancing its feel. Compared to Example 1, the polyurethane prepolymer prepared in Comparative Example 2, which omitted the addition of hydroxyl-terminated vinyl fluorosilicone oil, exhibited no improvement in the fabric's feel.

[0102] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a dyed fabric wet friction fastness improving agent, characterized in that: The following steps are involved: Step 1: mixing polytetramethylene ether glycol and hydroxyl-terminated vinyl fluorosilicone oil, adding diisocyanate and dibutyltin dilaurate, reacting, cooling after the reaction, filtering, and obtaining a silicone-modified polyurethane prepolymer; Step 2: adding N-butyldiethanolamine and 1,4-butanediol to the organosilicon-modified polyurethane prepolymer, reacting, and obtaining a polyurethane intermediate after the reaction is completed; Step 3: Add acetonitrile to the polyurethane intermediate, stir and disperse, then add diethyl iminodiacetate and triethylamine, react, and after the reaction is completed, rotary evaporate, wash, filter, and dry to obtain polyurethane; Step 4: adding polyurethane to chloroform, stirring and dissolving, adding bromobutyl, reacting, and after the reaction is completed, rotary evaporation, and then adding deionized water for purification and separation to obtain a cationic polyurethane solution; Step 5: Add acrylamide to the cationic polyurethane solution, stir and mix, heat to a set temperature, dropwise add initiator solution, react, and after the reaction is completed, cool to obtain a dyed fabric wet friction fastness enhancer.

2. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 1, characterized in that: In the step 1, the mass ratio of diisocyanate, polytetramethylene ether glycol, hydroxyl-terminated vinyl fluorosilicone oil, and dibutyltin dilaurate is (38-42):(10-15):(12-16):(0.1-0.3), and the reaction conditions are 85-95° C. for 2-3 hours; The diisocyanate includes hexamethylene diisocyanate.

3. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 1, wherein: The hydroxyl-terminated vinyl fluorosilicone oil in step 1 is prepared by the following steps: The trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane and hexamethylcyclotrisiloxane are mixed, deionized water, an alkali catalyst and cyclodextrin are added, and the mixture is reacted. After the reaction is completed, the mixture is neutralized and purified to obtain a hydroxyl-terminated vinyl fluorosilicone oil.

4. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 3, characterized in that: The mass ratio of the trifluoropropylmethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethylcyclotrisiloxane, deionized water, base catalyst, and cyclodextrin is 46.9:(8-12):(10-15):(3-6):(0.03-0.05):(0.005-0.01), and the reaction conditions are 40-60° C. for 1-3 hours; The base catalyst includes potassium hydroxide.

5. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 1, characterized in that: In the step 2, the mass ratio of the silicone-modified polyurethane prepolymer, N-butyldiethanolamine, and 1,4-butanediol is (130-150):(1-2):(0.5-1), and the reaction conditions are 45-55° C. for 1-3 hours.

6. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 1, characterized in that: In the step 4, the mass ratio of polyurethane, bromobutyl and chloroform is 100:(15-20):(800-1200), the reaction conditions are reflux reaction at 60-80° C. for 2-4 hours, and the amount of deionized water added is 1-2 times the mass of chloroform.

7. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 1, characterized in that: In the step 5, the mass ratio of the cationic polyurethane solution, acrylamide, and initiator solution is 100:(2-4):(3-5), the initiator solution is added dropwise for 30-60 minutes, and the reaction conditions are to react at a set temperature for 1-3 hours; The set temperature is 60-80°C.

8. The method for preparing a dyed fabric wet rubbing fastness improving agent according to claim 7, characterized in that: The initiator solution includes an aqueous solution of azobisisobutylamidine hydrochloride, and the aqueous solution of azobisisobutylamidine hydrochloride includes a 0.5 wt % aqueous solution of azobisisobutylamidine hydrochloride.

9. A dyed fabric wet rubbing fastness improving agent prepared by the method for preparing a dyed fabric wet rubbing fastness improving agent according to any one of claims 1 to 8.

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