A polyester-cotton fabric softener with fluff function and its preparation method and application

Abstract

The present application provides a polyester-cotton fabric softener with a fluffy function, a preparation method and application thereof, and belongs to the technical field of fabric treatment agents.The present application carries out unilateral chlorination on polyethylene glycol and dichlorosulfoxide, carries out nucleophilic substitution reaction with pentaerythritol, and then reacts with diphenyl dimethane diisocyanate, the product further reacts with tris(2-aminoethyl)amine to prepare a hyperbranched intermediate, and then reacts with an end epoxy polyether silicone oil to prepare the polyester-cotton fabric softener with the fluffy function.The polyester-cotton fabric softener with the fluffy function prepared by the present application overcomes the technical problem that traditional softeners are difficult to balance softness and fluffiness through structural innovation, has good effects on polyester-cotton fabrics, improves the hydrophilicity, softness, resilience and fluffiness of the fabric, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of fabric treatment agents, specifically to a softener for polyester-cotton fabrics with a fluffing function, its preparation method, and its application. Background Technology

[0002] Polyester-cotton fabrics refer to a general term for blended fabrics made from polyester and cotton, typically using a blend of 65%-67% polyester yarn and 33%-35% cotton yarn. The characteristics of polyester-cotton fabrics include: highlighting the style of polyester while possessing the comfort of cotton fabrics; good abrasion resistance in both dry and wet conditions; dimensional stability; low shrinkage; and a crisp, wrinkle-resistant, easy-to-wash, and quick-drying nature. However, they are not suitable for high-temperature ironing or boiling water soaking.

[0003] In recent years, the types of block silicone oils have increased, and their applications have become wider. Currently, fabrics treated with common block silicone softeners generally have a limited range of hand feel; a good hand feel on polyester fabrics may not be as good on cotton fabrics, and vice versa, making it difficult to achieve high versatility. With the diversification of fabric types in dyeing and printing, achieving universal finishing for polyester-cotton fabrics often requires the compounding of multiple silicone softeners. Currently, many dyeing plants' setting machines use pipeline conveying, meaning that the combined use of multiple silicone softeners requires more high-level tanks, which is detrimental to space utilization and production formula management. Furthermore, the effect of compounded silicone softeners often fails to reflect the advantages of each individual softener. To reduce fabric finishing costs, dyeing plants are experiencing a significant increase in demand for versatile silicone softeners. Summary of the Invention

[0004] The purpose of this invention is to propose a fabric softener for polyester-cotton fabrics with a fluffy function, its preparation method and application. Through structural innovation, it overcomes the technical problem that traditional softeners cannot achieve both softness and fluffiness, and has a better effect on polyester-cotton fabrics, improving the fabric's hydrophilicity, softness, resilience and fluffiness, and has broad application prospects.

[0005] The technical solution of this invention is implemented as follows: This invention provides a method for preparing a polyester-cotton fabric softener with a fluffy function. Polyethylene glycol and thionyl chloride are subjected to unilateral chlorination, followed by a nucleophilic substitution reaction with pentaerythritol, and then reacted with diphenyl dimethane diisocyanate. The product is further reacted with tris(2-aminoethyl)amine to obtain a hyperbranched intermediate, which is then reacted with terminal epoxy polyether silicone oil to obtain a polyester-cotton fabric softener with a fluffy function.

[0006] As a further improvement to the present invention, the following steps are included: S1. Polyethylene glycol and thionyl chloride are reacted to prepare monochloro polyethylene glycol; S2. Intermediate 1 was prepared by reacting monochloro polyethylene glycol with pentaerythritol, with the following structure: ;in, x = 5 - 12; S3. Intermediate 1 was reacted with diphenyldimethyl diisocyanate to obtain intermediate 2, with the following structure: ;in, ; S4. Intermediate 2 is reacted with tris(2-aminoethyl)amine to prepare a hyperbranched intermediate; S5. A softener for polyester-cotton fabrics with a fluffy function is prepared by reacting a hyperbranched intermediate with terminal epoxy polyether silicone oil.

[0007] As a further improvement of the present invention, the molar ratio of polyethylene glycol and sulfoxide in step S1 is 1:0.9-1, and the general formula of polyethylene glycol is HO(CH2CH2O). x H, where x = 5 - 12.

[0008] As a further improvement of the present invention, the molar ratio of monochloro polyethylene glycol and pentaerythritol in step S2 is 4:0.95-1.

[0009] As a further improvement of the present invention, the molar ratio of intermediate 1 and diphenyl dimethane diisocyanate in step S3 is 1:3.9-4.

[0010] As a further improvement of the present invention, the molar ratio of intermediate 2 and tris(2-aminoethyl)amine in step S4 is 1:3-4.

[0011] As a further improvement of the present invention, the mass ratio of the hyperbranched intermediate and the terminal epoxy polyether silicone oil in step S5 is 3-6:9-12, and the molecular weight of the terminal epoxy polyether silicone oil is 10000-15000.

[0012] This invention further protects a polyester-cotton fabric softener with a fluffy function prepared by the above-described preparation method.

[0013] The present invention further protects the application of the above-mentioned polyester-cotton fabric softener with fluffing function in the fluffing and / or softening finishing of fabrics.

[0014] As a further improvement of the present invention, the fabric is polyester, cotton, or polyester-cotton fabric.

[0015] The present invention has the following beneficial effects: This invention incorporates a highly active polyurea elastic resin with hard segments into a soft silicone chain, developing a highly elastic resin-modified silicone oil that combines both soft and hard segments in its structure. Due to the presence of flexible polyethylene glycol segments in the molecule, the product's high-temperature crosslinking and film-forming properties are improved under the synergistic effect of the polyethylene glycol and polyurethane hard segments, thus enhancing elasticity and bulkiness. Furthermore, as the softener molecules arrange themselves on the fabric surface, the polysiloxane segments exposed on the fabric surface become longer, and the silicone segments are more easily rotated and moved. The fiber surface is adsorbed and coated by the polyurethane hard segments and silicone segments. Under the interaction of the two, softness, elasticity, and bulkiness are improved.

[0016] This invention introduces a large number of amino and ether bonds, solving the problem of the mutual constraint between hydrophilicity and softness in traditional silicone softening agents, thus endowing fabrics with both hydrophilic and soft properties. Furthermore, the rigid diphenyl dimethane diisocyanate of this invention forms rigid nodes in the molecular chain, preventing chain segment collapse and giving the fabric a lasting fluffy resilience; the hyperbranched structure increases the volume occupied by molecules between fibers, producing a 3D support effect, thereby significantly improving the fluffy effect.

[0017] The polyester-cotton fabric softener prepared by this invention overcomes the technical problem of traditional softeners that are difficult to balance softness and fluffiness through structural innovation. It has a good effect on polyester-cotton fabrics, improving the fabric's hydrophilicity, softness, resilience and fluffiness, and has broad application prospects. Detailed Implementation

[0018] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] The molecular weight of the epoxy polyether silicone oil is 10,000. Example 1

[0020] This embodiment provides a method for preparing a polyester-cotton fabric softener with a fluffy function, including the following steps: S1. Dissolve 0.1 mol polyethylene glycol [HO(CH2CH2O)5H] in 200 mL of dichloromethane, add 50 mL of dichloromethane solution containing 0.09 mol sulfoxide, stir at room temperature for 2 h, remove the solvent under reduced pressure, recrystallize from ethanol to obtain monochloro polyethylene glycol; ESI-MS calculated value: C 10 H 22 ClO5(M+H) +257.73, measured value: 257.7, yield: 90%. 1H NMR results: 1 H NMR (400MHz, CDCl3) δ3.67-3.71 (m, 4H), 3.57-3.62 (m, 16H), 2.0 (br, 1H).

[0021] Synthesis route: ; S2. 0.4 mol of monochloro polyethylene glycol and 0.095 mol of pentaerythritol were added to acetonitrile, followed by 1.2 mol of triethylamine. The mixture was heated to 65°C and stirred for 3 hours. The solvent was removed under reduced pressure, and the mixture was recrystallized from acetone to obtain intermediate 1. ESI-MS calculated value: C 45 H 93 O 24 (M+H) + 1018.2, measured value: 1018.2, yield: 83%. 1H NMR results: 1 H NMR (400MHz, CDCl3) δ3.72 (t, 8H), 3.29 (s, 8H), 3.51-3.55 (m, 72H) 2.5 (br, 4H).

[0022] Synthesis route: ; S3. 0.1 mol of intermediate 1 and 0.39 mol of diphenyldimethane diisocyanate were mixed and added to 300 mL of acetonitrile. The mixture was heated to 60 °C and reacted under nitrogen protection for 1 h. The mixture was then cooled to obtain intermediate 2. ESI-MS calculated value: C 105 H 133 N8O 32 (M+H) + 2018.21, Measured value: 2018.2, Yield: 62%. 1H NMR results: 1 H NMR (400MHz, CDCl3) δ8.0 (br, 4H), 7.55 (m, 8H), 7.02-7.1 (m, 24H), 4.25 (t, 8H), 3.82 (s, 8H), 3.65 (t, 8H), 3.59-3.62 (m, 64H), 3.32 (s, 8H).

[0023] Synthesis route: ; S4. Add 0.1 mol of intermediate 2 to 200 mL of dichloromethane, add 0.3 mol of tris(2-aminoethyl)amine under nitrogen protection, stir at room temperature for 1 h, remove the solvent under reduced pressure to obtain the hyperbranched intermediate; S5. Mix 3g of hyperbranched intermediate, 1g of acetic acid, 9g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 7h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function.

[0024] The infrared spectrum analysis is as follows: the vibrational peaks of -OH and -NH are at 3355 cm⁻¹. -1 Overlapping, 1727cm -1 It is the stretching vibration peak of -C=O in carbamate, 1559 cm⁻¹. -1 The peak represents a mixed vibration of CN and NH, at 1261 cm⁻¹. -1 It is the deformation vibration peak of Si-CH3, 1095 cm⁻¹ -1 and 1031cm -1 The peak at 805 cm⁻¹ corresponds to the stretching vibration peak of Si-O-Si, and also to the stretching vibration peak of COC. -1 The peaks are characteristic of the stretching vibrations of Si-C, and are highest in the 2250-2275 cm⁻¹ range. -1 There is no longer a -NCO stretching vibration peak at 900-910 cm⁻¹. -1 The absence of absorption vibration peaks for epoxy groups indicates that the product structure contains polyurethane, amino, silicone, and polyether segments. Example 2

[0025] This embodiment provides a method for preparing a polyester-cotton fabric softener with a fluffy function, including the following steps: S1. Dissolve 0.1 mol polyethylene glycol [HO(CH2CH2O)7H] in 200 mL of dichloromethane, add 50 mL of dichloromethane solution containing 0.1 mol dichloro sulfoxide, stir the reaction at room temperature for 4 h, remove the solvent under reduced pressure, recrystallize from ethanol to obtain monochloro polyethylene glycol; S2. Add 0.4 mol of monochloro polyethylene glycol and 0.1 mol of pentaerythritol to acetonitrile, add 1.2 mol of triethylamine, heat to 65°C, stir for 5 h, remove solvent under reduced pressure, recrystallize from acetone to obtain intermediate 1; S3. Mix 0.1 mol of intermediate 1 and 0.4 mol of diphenyl dimethane diisocyanate and add them to 300 mL of acetonitrile. Heat to 65 °C and react under nitrogen protection for 3 h. Cool down to obtain intermediate 2. S4. Add 0.1 mol of intermediate 2 to 200 mL of dichloromethane, add 0.4 mol of tris(2-aminoethyl)amine under nitrogen protection, stir at room temperature for 3 h, remove solvent under reduced pressure to obtain hyperbranched intermediate; S5. Mix 6g of hyperbranched intermediate, 2g of acetic acid, 12g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 10h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function. Example 3

[0026] This embodiment provides a method for preparing a polyester-cotton fabric softener with a fluffy function, including the following steps: S1. Add 0.1 mol of polyethylene glycol [HO(CH2CH2O)] 10 [H] was dissolved in 200 mL of dichloromethane, and 50 mL of dichloromethane solution containing 0.095 mol of dichloro sulfoxide was added dropwise. The mixture was stirred at room temperature for 3 h, the solvent was removed under reduced pressure, and the mixture was recrystallized from ethanol to obtain monochloro polyethylene glycol. S2. Add 0.4 mol of monochloro polyethylene glycol and 0.097 mol of pentaerythritol to acetonitrile, add 1.2 mol of triethylamine, heat to 65°C, stir for 4 h, remove solvent under reduced pressure, recrystallize from acetone to obtain intermediate 1; S3. Mix 0.1 mol of intermediate 1 and 0.395 mol of diphenyl dimethane diisocyanate and add them to 300 mL of acetonitrile. Heat to 62 °C and react under nitrogen protection for 2 h. Cool down to obtain intermediate 2. S4. Add 0.1 mol of intermediate 2 to 200 mL of dichloromethane, add 0.35 mol of tris(2-aminoethyl)amine under nitrogen protection, stir at room temperature for 2 h, remove solvent under reduced pressure to obtain hyperbranched intermediate; S5. Mix 4.5g of hyperbranched intermediate, 1.5g of acetic acid, 10g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 8h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function.

[0027] Comparative Example 1 Compared with Example 3, the difference is that steps S1 and S2 were not performed, and in step S3, polyethylene glycol was directly reacted with diphenyl dimethane diisocyanate.

[0028] Includes the following steps: S1. Add 0.1 mol of polyethylene glycol [HO(CH2CH2O)] 10H] and 0.2 mol of diphenyldimethane diisocyanate were mixed and added to 300 mL of acetonitrile. The mixture was heated to 62 °C and reacted under nitrogen protection for 2 h. The mixture was then cooled to obtain product 1. S2. Add 0.1 mol of product 1 to 200 mL of dichloromethane. Under nitrogen protection, add 0.35 mol of tris(2-aminoethyl)amine, stir at room temperature for 2 h, remove the solvent under reduced pressure, and obtain branched intermediate 1. S3. Mix 4.5g of branched intermediate 1, 1.5g of acetic acid, 10g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 8h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function.

[0029] Comparative Example 2 The difference from Example 3 is that in step S4, tris(2-aminoethyl)amine is replaced with N,N-dimethylaminopropylamine.

[0030] Includes the following steps: S1. Add 0.1 mol of polyethylene glycol [HO(CH2CH2O)] 10 [H] was dissolved in 200 mL of dichloromethane, and 50 mL of dichloromethane solution containing 0.095 mol of dichloro sulfoxide was added dropwise. The mixture was stirred at room temperature for 3 h, the solvent was removed under reduced pressure, and the mixture was recrystallized from ethanol to obtain monochloro polyethylene glycol. S2. Add 0.4 mol of monochloro polyethylene glycol and 0.097 mol of pentaerythritol to acetonitrile, add 1.2 mol of triethylamine, heat to 65°C, stir for 4 h, remove solvent under reduced pressure, recrystallize from acetone to obtain intermediate 1; S3. Mix 0.1 mol of intermediate 1 and 0.395 mol of diphenyl dimethane diisocyanate and add them to 300 mL of acetonitrile. Heat to 62 °C and react under nitrogen protection for 2 h. Cool down to obtain intermediate 2. S4. Add 0.1 mol of intermediate 2 to 200 mL of dichloromethane. Under nitrogen protection, add 0.35 mol of N,N-dimethylaminopropylamine. Stir the reaction at room temperature for 2 h. Remove the solvent under reduced pressure to obtain branched intermediate 2. S5. Mix 4.5g of branched intermediate 2, 1.5g of acetic acid, 10g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 8h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function.

[0031] Comparative Example 3 Compared with Example 3, the difference is that steps S1 and S2 are not performed, polyethylene glycol is directly reacted with diphenyl dimethyl diisocyanate in step S3, and tris(2-aminoethyl)amine is replaced with N,N-dimethylaminopropylamine in step S4.

[0032] Includes the following steps: S1. Add 0.1 mol of polyethylene glycol [HO(CH2CH2O)] 10 H] and 0.2 mol of diphenyldimethane diisocyanate were mixed and added to 300 mL of acetonitrile. The mixture was heated to 62 °C and reacted under nitrogen protection for 2 h. The mixture was then cooled to obtain product 1. S2. Add 0.1 mol of product 1 to 200 mL of dichloromethane. Under nitrogen protection, add 0.2 mol of N,N-dimethylaminopropylamine. Stir the reaction at room temperature for 2 h. Remove the solvent under reduced pressure to obtain product 3. S3. Mix 4.5g of product 3, 1.5g of acetic acid, 10g of terminal epoxy polyether silicone oil and 15mL of isopropanol evenly, heat to 80℃ under nitrogen protection, stir and react for 8h, cool to room temperature, remove solvent under reduced pressure to obtain a polyester-cotton fabric softener with fluffy function.

[0033] Test Example 1 The polyester-cotton fabric softener with fluffing function prepared in Examples 1-3 and Comparative Examples 1-3 was used to finish the polyester-cotton fabric. The process involved one dip and one nip (20-30 g / L of polyester-cotton fabric softener with fluffing function, 20% solid content, and 80% nip rate) → baking (150-170℃, 45-60 s).

[0034] Twenty professional hand feel assessment experts were selected to evaluate the fabric using a touch method. The finished fabric was allowed to rehydrate at room temperature for 2 hours, and the experts evaluated it from three aspects: softness, fluffiness, and elasticity. A 1-5 rating system was used, with 1 being the worst and 5 being the best, and the average value was taken.

[0035] Rubbing fastness: Tested in accordance with GB / T3920-1997 "Textiles - Tests for color fastness to rubbing".

[0036] Wash fastness: Tested in accordance with GB / T3921.1-1997 "Textiles - Tests for color fastness - Wash fastness".

[0037] The results are shown in Table 1.

[0038] Table 1

[0039] As can be seen from the table above, the polyester-cotton fabric softener with fluffing function prepared in Examples 1-3 of the present invention significantly improves the elasticity, fluffiness, softness, and rubbing fastness of polyester-cotton fabrics after finishing them.

[0040] Test Example 2 The polyester-cotton fabric softeners with fluffy properties prepared in Examples 1-3 were subjected to stability tests.

[0041] 1. Storage stability After filling the softener into a wide-mouth bottle and sealing it, leave it at room temperature for 3 months and observe whether the emulsion separates into layers or breaks down.

[0042] Centrifugal stability Place a certain amount of softener in a centrifuge tube, put it in a centrifuge, and centrifuge at 3000 r / min for 30 min. Observe whether there is any layering.

[0043] Alkali resistance Take a certain amount of softener and place it in an Erlenmeyer flask. Adjust the pH value to 11 with 5% NaOH solution. Heat at 50℃ for 10 minutes. After cooling, observe the stability of the emulsion.

[0044] Electrolyte stability Take 2g of sodium sulfate and 1g of soda ash, dilute with water to 100g, and prepare an electrolyte solution. Add 5g of softener to 95g of electrolyte solution, mix well, heat at 50℃ for 10min, and observe for any layering or precipitation after cooling.

[0045] The results are shown in Table 2.

[0046] Table 2

[0047] As can be seen from the table above, the polyester-cotton fabric softeners with fluffy function prepared in Examples 1-3 have good stability.

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a polyester-cotton fabric softener with a fluffy function, characterized in that, Polyethylene glycol and thionyl chloride are subjected to unilateral chlorination, followed by nucleophilic substitution with pentaerythritol, and then reacted with diphenyldimethyl diisocyanate. The product is further reacted with tris(2-aminoethyl)amine to obtain a hyperbranched intermediate, which is then reacted with terminal epoxy polyether silicone oil to obtain a polyester-cotton fabric softener with a fluffy function; including the following steps: S1. Polyethylene glycol and sulfoxide are reacted to prepare monochloro polyethylene glycol; the molar ratio of polyethylene glycol to sulfoxide is 1:0.9-1, and the general formula of polyethylene glycol is HO(CH2CH2O). x H, where x = 5 - 12; S2. Intermediate 1 was prepared by reacting monochloro polyethylene glycol with pentaerythritol, with the following structure: ;in, x=5-12; the molar ratio of the monochloro polyethylene glycol and pentaerythritol is 4:0.95-1; S3. Intermediate 1 was reacted with diphenyldimethyl diisocyanate to obtain intermediate 2, with the following structure: ;in, The molar ratio of intermediate 1 and diphenyl dimethane diisocyanate is 1:3.9-4. S4. Intermediate 2 and tris(2-aminoethyl)amine are reacted to prepare a hyperbranched intermediate; the molar ratio of intermediate 2 to tris(2-aminoethyl)amine is 1:3-4; S5. A softener for polyester-cotton fabrics with a fluffy function is prepared by reacting a hyperbranched intermediate with terminal epoxy polyether silicone oil; the mass ratio of the hyperbranched intermediate to the terminal epoxy polyether silicone oil is 3-6:9-12, and the molecular weight of the terminal epoxy polyether silicone oil is 10000-15000.

2. A fabric softener for polyester-cotton fabrics with a fluffy function, prepared by the method described in claim 1.

3. The application of a polyester-cotton fabric softener with a fluffing function as described in claim 2 in the fluffing and / or softening finishing of fabrics.

4. The application according to claim 3, characterized in that, The fabric is made of polyester, cotton, or polyester-cotton blend.

Images