Preparation of low-yellowing polyether-modified amino silicone oil and fabric finishing agent containing same

Abstract

The application discloses a preparation of low-yellowing polyether modified amino silicone oil and a fabric finishing agent containing the same, and relates to amino silicone oil and application thereof. The application uses octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane as key raw materials, converts original primary amino groups into secondary amino groups on the basis of traditional amino silicone oil, simultaneously pays attention to control of the molecular mass of the modified amino silicone oil, significantly improves the chemical stability and oxidation resistance of the silicone oil, and secondarily modifies the silicone oil by using allyl epoxy polyether, so that the originally non-hydrophilic amino silicone oil obtains certain hydrophilicity, and the self-emulsifying ability of the silicone oil and the stability of the emulsion are significantly improved. Through the modification, the final silicone oil molecular chain segment can be repeatedly and directionally arranged on the fiber surface in the form of alternating polyether and polysiloxane structure, so that the finishing agent has good hydrophilicity, softness and washability for finishing fabrics.

Description

Technical Field

[0001] This invention relates to amino silicone oil and its uses, specifically to the preparation of a low-yellowing polyether modified amino silicone oil and a fabric finishing agent containing it. Background Technology

[0002] Currently, over 90% of commercially available amino-polysiloxane polyether-modified silicone oils are aminoethyliminopropyl polysiloxanes, which have two amino groups (primary and secondary amino groups) on their side chains and contain three active hydrogen atoms. Due to the presence of amino groups, especially primary amino groups, this structure is prone to oxidation under heating and ultraviolet light, forming chromophores and causing yellowing. When softening colored fabrics, this often results in the fabric losing its original color or luster, causing yellowing or a slight yellowish sheen, which greatly complicates post-dyeing finishing. The degree of yellowing increases with increasing ammonia value. Current modifications to amino silicone oils mainly include cationic modification, polyether modification, amidation modification, and alkylation modification. While these modifications somewhat suppress the yellowing problem of amino silicone oils, they all have certain drawbacks. Some significantly reduce the softness of amino silicone oils, such as polyether modification, cationic modification, and amidation modification; others greatly reduce the hydrophilicity of silicone oils, such as alkylation modification.

[0003] To address the drawback of amino-polysiloxane polyether modified silicone oils being prone to yellowing when used as fabric finishing agents, this invention proposes changing the primary amine to a secondary amine and controlling the molecular weight of the polysiloxane to effectively reduce the amount of active hydrogen, prevent the oxidation of the primary amine, and reduce yellowing. By selecting an appropriate modifier, 3-piperazinylpropylmethyldimethoxysilane, modified amino-polysiloxane polyether silicone oils are synthesized for use as textile softeners, reducing yellowing. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing low-yellowing polyether-modified amino silicone oil and a fabric finishing agent containing it, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a low-yellowing polyether modified amino silicone oil, wherein the low-yellowing polyether modified amino silicone oil is prepared by using octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane as reaction raw materials and tetramethylammonium hydroxide as initiator, through hydrolysis reaction and polycondensation reaction to synthesize modified amino silicone oil, and then reacting it with allyl epoxy polyethers of different molecular weights.

[0006] Furthermore, the low-yellowing polyether modified amino silicone oil includes the following preparation steps:

[0007] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, slowly add octamethylcyclotetrasiloxane, heat to 80-90℃, keep warm for 1-2 hours, vacuum, and remove excess water and by-products.

[0008] (2) Add tetramethylammonium hydroxide, heat to 105-115℃, keep warm for 3-4 hours, then heat to 140℃, keep warm for 30 minutes, and vacuum for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0009] (3) Add modified amino silicone oil, allyl epoxy polyether and solvent to the reactor, mix evenly, and react at 70-85℃ for 1-3 hours to obtain low yellowing polyether modified amino silicone oil.

[0010] Furthermore, in step (1), the molar ratio of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane is 1:0.2 to 0.7.

[0011] Furthermore, in step (1), the deionized water is 0.5 to 1.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0012] Furthermore, the feeding time of octamethylcyclotetrasiloxane in step (1) is 30-40 min.

[0013] Furthermore, in step (2), the amount of tetramethylammonium hydroxide used is 0.01% to 0.05% of the mass of octamethylcyclotetrasiloxane.

[0014] Furthermore, in step (3), the solvent is isopropanol, and the mass ratio of the solvent to allyl epoxy polyether is 0.1 to 0.5:1.

[0015] Furthermore, the propyl epoxy polyether has the structural formula CH2=CHCH2O(PO). m (EO) n CH2(CHCH2)O has an average molecular weight of 300-1500.

[0016] Furthermore, the mass ratio of the modified amino silicone oil to the allyl epoxy polyether is 1:0.8 to 1.1.

[0017] A fabric finishing agent, by weight, comprises 20-40 parts of low-yellowing polyether modified amino silicone oil, 10-20 parts of emulsifier, 0.01-0.1 parts of initiator, 0.4-2.5 parts of acetic acid, 1-5 parts of modified porous carbon micro powder, and 60-70 parts of water.

[0018] Furthermore, the modified porous carbon micropowder is prepared by reacting porous carbon micropowder with a certain amount of alkenylating coupling agent after hydroxylation.

[0019] Furthermore, the porous carbon micropowder has a particle size of 0.5–3 μm and a specific surface area of ​​1189–3150 m². 2 / g, pore volume of 0.55~2.30cm 3 / g.

[0020] The finishing agent prepared in this invention forms a polyether chain segment filling effect inside the fiber and an external hydroxyl bond coating effect with the fiber, thereby maintaining the good durability of the hydrophilicity of the finished fiber. At the same time, the modified porous carbon micro powder and the low yellowing polyether modified amino silicone oil are cross-linked by double bonds, thereby forming a network film layer on the fabric surface, which can reduce the friction coefficient of the fabric surface. In addition, the modified porous carbon micro powder is affected by the particle size and deposited on the fiber surface. Due to the high hardness of the modified porous carbon micro powder, the film layer is more wear-resistant and has the effect of resisting pilling. Furthermore, the porous structure of the modified porous carbon micro powder and its own hydrophilic groups can indirectly improve the hydrophilicity of the finishing agent.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] (1) This invention relates to the preparation of an innovative modified amino silicone oil, which mainly uses octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane as key raw materials. By introducing piperazine groups into the silane chain, a significant change in chemical structure is achieved on the basis of traditional amino silicone oil, converting the original primary amino group into a secondary amino group. At the same time, attention is paid to the molecular weight control of the modified amino silicone oil. By precisely controlling the reaction conditions and raw material ratio, the molecular weight of the modified amino silicone oil is successfully adjusted, thereby effectively reducing the number of active hydrogen atoms, significantly improving the chemical stability and oxidation resistance of the silicone oil, and effectively preventing the yellowing phenomenon of traditional amino silicone oil.

[0023] (2) This invention utilizes modified amino silicone oil and allyl epoxy polyether to obtain polyether-modified amino silicone oil through chemical bonding. The piperazine group of the modified amino silicone oil undergoes a ring-opening reaction with the epoxy group of the allyl epoxy polyether, thereby introducing polyether segments. This process imparts a certain degree of hydrophilicity to the originally non-hydrophilic amino silicone oil and significantly improves the self-emulsifying ability of the silicone oil and the stability of the emulsion. Through this modification, the final silicone oil molecular segments can continuously and directionally arrange themselves on the fiber surface in alternating polyether and polysiloxane structures, endowing the finished fabric with good hydrophilicity, softness, and wash resistance.

[0024] (3) This invention employs piperazine-based and allyl epoxy polyethers to perform dual modification treatment on silicone oil. Through this method, the silicone oil not only possesses the characteristics of piperazine-based amino silicone oil but also incorporates the components of block silicone oil. The resulting emulsion combines the advantages of both amino and block silicone oils. This dual modification technology significantly improves the stability of the emulsion system and fully utilizes the respective advantages of amino and block silicone oils, thus exhibiting excellent comprehensive performance in practical applications. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1

[0027] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 30 min. Heat the reactor to 80°C and keep it at that temperature for 1 h. Then, apply a vacuum to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.2. The amount of deionized water is 0.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0028] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.01% of the mass of octamethylcyclotetrasiloxane, heat to 105°C, keep warm for 3 hours, then heat to 140°C, keep warm for 30 minutes, and vacuum for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0029] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 300 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.1:1 and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.8. After mixing evenly, react at 70°C for 1 hour to obtain low yellowing polyether modified amino silicone oil.

[0030] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0031] (5) Dissolve 0.02g of methacryloyloxymethyltrimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder;

[0032] (6) By weight, add 10 parts of emulsifier to the emulsifier, add 20 parts of low yellowing polyether modified amino silicone oil in 5 portions, stir for 5 minutes, add 0.4 parts of acetic acid, stir for 3 minutes, add 60 parts of water in 6 portions, stir for 5 minutes, add 1 part of modified porous carbon powder, stir for 1 minute, and finally add 0.01 parts of initiator to obtain the fabric finishing agent.

[0033] Example 2

[0034] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane. The feeding time is 32 min. Heat to 80℃ and keep warm for 1 h. Vacuum the reactor and remove excess water and by-products. The molar ratio of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane is 1:0.3. The amount of deionized water is 0.8 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0035] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.02% of the mass of octamethylcyclotetrasiloxane, heat to 105°C, keep warm for 3 hours, then heat to 140°C, keep warm for 30 minutes, and vacuum for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0036] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 450 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.2:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 70°C for 1 hour to obtain low yellowing polyether modified amino silicone oil.

[0037] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0038] (5) Dissolve 0.02g of methacryloyloxymethyltrimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder;

[0039] (6) By weight, add 12 parts of emulsifier to the emulsifier, add 25 parts of low yellowing polyether modified amino silicone oil in 5 portions, stir for 5 minutes, add 0.9 parts of acetic acid, stir for 3 minutes, add 63 parts of water in 7 portions, stir for 5 minutes, add 2 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.01 parts of initiator to obtain the fabric finishing agent.

[0040] Example 3

[0041] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 35 min. Heat the reactor to 85°C and keep it at that temperature for 1.5 h. Then, vacuum the reactor to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4. The amount of deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0042] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.03% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0043] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.3:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 80°C for 2 hours to obtain low yellowing polyether modified amino silicone oil.

[0044] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0045] (5) Dissolve 0.02g of allyl dimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder.

[0046] (6) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of low yellowing polyether modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, add 3 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0047] Example 4

[0048] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane. The feeding time is 37 min. Raise the temperature to 88℃ and keep it at that temperature for 1.5 h. Vacuum the reactor and remove excess water and by-products. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.5. The amount of deionized water is 1.1 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0049] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.04% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0050] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 1000 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.4:1 and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:1.0. After mixing evenly, react at 80°C for 2 hours to obtain low yellowing polyether modified amino silicone oil.

[0051] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0052] (5) Dissolve 0.02g of 3-butenetriethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder;

[0053] (6) By weight, add 18 parts of emulsifier to the emulsifier, add 35 parts of low yellowing polyether modified amino silicone oil in 5 portions, stir for 5 minutes, add 2.0 parts of acetic acid, stir for 3 minutes, add 66 parts of water in 6 portions, stir for 5 minutes, add 4 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0054] Example 5

[0055] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane. The feeding time is 40 min. Heat to 90℃ and keep warm for 2 h. Vacuum the reactor and remove excess water and by-products. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.7. The amount of deionized water is 1.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0056] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.05% of the mass of octamethylcyclotetrasiloxane, heat to 115°C, keep warm for 4 hours, then heat to 140°C, keep warm for 30 minutes, and vacuum for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0057] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 1500 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.5:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:1.1. After mixing evenly, react at 85°C for 3 hours to obtain low yellowing polyether modified amino silicone oil.

[0058] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0059] (5) Dissolve 0.02g of 3-butenetriethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder;

[0060] (6) By weight, add 20 parts of emulsifier to the emulsifier, add 40 parts of low yellowing polyether modified amino silicone oil in 8 portions, stir for 5 minutes, add 2.5 parts of acetic acid, stir for 3 minutes, add 70 parts of water in 5 portions, stir for 5 minutes, add 5 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.01-0.1 parts of initiator to obtain the fabric finishing agent.

[0061] Comparative Example 1 (without allyl epoxy polyether)

[0062] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 35 min. Heat the reactor to 85°C and keep it at that temperature for 1.5 h. Then, vacuum the reactor to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4. The amount of deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0063] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.03% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0064] (3) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0065] (4) Dissolve 0.02g of allyl dimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder.

[0066] (5) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, add 3 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0067] Comparative Example 2 (using ordinary amino silicone oil)

[0068] (1) Add ordinary amino silicone oil, allyl epoxy polyether with an average molecular weight of 550 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.3:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 80°C for 2 hours to obtain modified amino silicone oil.

[0069] (2) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0070] (3) Dissolve 0.02g of allyl dimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add hydroxylated porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder.

[0071] (4) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, add 3 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0072] Comparative Example 3 (no hydroxylation treatment was performed on the porous carbon micropowder)

[0073] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 35 min. Heat the reactor to 85°C and keep it at that temperature for 1.5 h. Then, vacuum the reactor to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4. The amount of deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0074] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.03% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0075] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.3:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 80°C for 2 hours to obtain low yellowing polyether modified amino silicone oil.

[0076] (4) Dissolve 0.02g of allyl dimethoxysilane in 40ml of 99.9% pure ethanol to obtain a modifier system; add porous carbon micro powder to the modifier system, stir magnetically at 45℃ and 80rpm for 1h, after modification, wash with ethanol and dry at 100℃ to obtain modified porous carbon micro powder.

[0077] (5) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of low yellowing polyether modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, add 3 parts of modified porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0078] Comparative Example 4 (Porous carbon micropowder was not modified using a coupling agent)

[0079] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 35 min. Heat the reactor to 85°C and keep it at that temperature for 1.5 h. Then, vacuum the reactor to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4. The amount of deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0080] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.03% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0081] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.3:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 80°C for 2 hours to obtain low yellowing polyether modified amino silicone oil.

[0082] (4) The porous carbon micro powder was soaked in 6 mol / L potassium hydroxide solution for 2 h, then washed 3 times with deionized water and dried at 60 °C for 6 h to obtain hydroxylated porous carbon micro powder.

[0083] (5) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of low yellowing polyether modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, add 3 parts of hydroxylated porous carbon powder, stir for 1 minute, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0084] Comparative Example 5 (without added modified porous carbon powder)

[0085] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, and slowly add octamethylcyclotetrasiloxane over a period of 35 min. Heat the reactor to 85°C and keep it at that temperature for 1.5 h. Then, vacuum the reactor to remove excess water and byproducts. The molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4. The amount of deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

[0086] (2) Add tetramethylammonium hydroxide, the amount of tetramethylammonium hydroxide is 0.03% of the mass of octamethylcyclotetrasiloxane, heat to 110°C, keep warm for 3.5h, then heat to 140°C, keep warm for 30min, and vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system to obtain modified amino silicone oil.

[0087] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550 and isopropanol to the reactor. The mass ratio of isopropanol to allyl epoxy polyether is 0.3:1, and the mass ratio of modified amino silicone oil to allyl epoxy polyether is 1:0.9. After mixing evenly, react at 80°C for 2 hours to obtain low yellowing polyether modified amino silicone oil.

[0088] (4) By weight, add 15 parts of emulsifier to the emulsifier, add 30 parts of low yellowing polyether modified amino silicone oil in 6 portions, stir for 5 minutes, add 1.6 parts of acetic acid, stir for 3 minutes, add 65 parts of water in 5 portions, stir for 5 minutes, and finally add 0.05 parts of initiator to obtain the fabric finishing agent.

[0089] Performance testing

[0090] Application process of finishing agents:

[0091] Fabric treated: Polyester-cotton twill,

[0092] Processing procedure: dosage 30g / L, one dip and one roll (roll-off rate: 75%) → drying and shaping (140℃×60S) → cooling and rehydration → performance evaluation;

[0093] 1. Hand Feel: After processing, the fabric is touched with eyes closed. Groups of 10 people are assigned a rating based on the feel of the printed fabric. The rating method is as follows: the fabric is rated based on softness and smoothness, with a total of 5 levels. Level 1 is the worst, indicating a stiff fabric with poor smoothness. Level 5 is the best, indicating a soft and smooth fabric.

[0094] 2. Whiteness: Measured with a whiteness meter, the smaller the difference between the whiteness and the original fabric, the better the resistance to yellowing; the original fabric's whiteness is 91.2.

[0095] 3. Hydrophilicity: Use a standard dropper to drop a drop of water onto the fabric surface from a certain height and observe the time required for the water droplet to completely wet and penetrate the fabric surface. The shorter the time, the better the hydrophilicity.

[0096] 4. Stability

[0097] (1) Heat resistance stability

[0098] The test method is as follows: Place a certain amount of finishing agent emulsion into a sealed container and place it in a constant temperature water bath at 80℃ for 6 hours. Observe the appearance of the emulsion. If there is no oil floating or layering, it indicates that the finishing agent emulsion has good heat resistance stability. If there is a small amount of oil floating or layering, it indicates that the finishing agent emulsion has average heat resistance stability. If there is oil floating or layering, it indicates that the finishing agent emulsion has poor heat resistance stability.

[0099] (2) Freezing stability

[0100] The test method is as follows: A certain amount of finishing agent emulsion is placed in a sealed container and placed in a constant temperature water bath at -20℃ for 6 hours. After natural thawing, its state changes are observed and recorded. No oil floating or layering indicates that the finishing agent emulsion has good freeze resistance stability. A small amount of oil floating or layering indicates that the finishing agent emulsion has average freeze resistance stability. A large amount of oil floating or layering indicates that the finishing agent emulsion has poor freeze resistance stability.

[0101] (3) Acid resistance

[0102] The test method is as follows: Put a certain amount of finishing agent emulsion into a sealed container, add 50 times its weight of hydrochloric acid aqueous solution with a pH of 3, let it stand for 1 day, observe and record its state changes. No oil floating or layering indicates that the finishing agent emulsion has good acid resistance stability. A small amount of oil floating or layering indicates that the finishing agent emulsion has average acid resistance stability. Oil floating or layering indicates that the finishing agent emulsion has poor acid resistance stability.

[0103] (4) Alkali resistance

[0104] The test method is as follows: Place a certain amount of finishing agent emulsion into a sealed container, add 50 times its weight of sodium hydroxide aqueous solution with a pH of 12, let it stand for 1 day, observe and record its state changes. No oil floating or layering indicates that the finishing agent emulsion has good alkali resistance stability. A small amount of oil floating or layering indicates that the finishing agent emulsion has average alkali resistance stability. Oil floating or layering indicates that the finishing agent emulsion has poor alkali resistance stability.

[0105] 5. Washability

[0106] After washing the fabric 100 times, observe its color. Evaluation method: if the fabric retains more than 96% of its original color, it indicates good washability; if the fabric retains 80-95% of its original color, it indicates average washability; if the fabric retains less than 80% of its original color, it indicates poor washability.

[0107] 6. Anti-pilling properties

[0108] The pilling grade of the fabric was tested according to GB / T4802.1-2008 "Textiles - Determination of pilling properties - Part 1: Circular trajectory method". The fabric was washed 100 times according to the household washing and drying procedure in GB / T8629-2017, and then the pilling grade was tested again.

[0109] Table 1 Performance Test Results

[0110]

[0111]

[0112] As can be seen from the above data, the low-yellowing polyether-modified amino silicone oil and finishing agent provided by this invention have excellent hand feel, stable performance, anti-pilling, yellowing resistance, and a certain degree of hydrophilicity. Furthermore, the preparation method of this invention is simple, easy to operate and control, produces stable quality, has high production efficiency, and can be mass-produced industrially.

[0113] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A low-yellowing polyether-modified amino silicone oil, characterized in that, The low-yellowing polyether modified amino silicone oil is prepared by using octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane as reactants and tetramethylammonium hydroxide as initiator, through hydrolysis and polycondensation reactions to synthesize the modified amino silicone oil, which is then reacted with allyl epoxy polyethers of different molecular weights. The low-yellowing polyether modified amino silicone oil is used to prepare a fabric finishing agent containing modified porous carbon micropowder, wherein the modified porous carbon micropowder is prepared by reacting porous carbon micropowder with an alkenylation coupling agent after hydroxylation.

2. The low-yellowing polyether-modified amino silicone oil according to claim 1, characterized in that, The low-yellowing polyether modified amino silicone oil comprises the following preparation steps: (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water to the reactor, slowly add octamethylcyclotetrasiloxane, heat to 80~90℃, keep warm for 1~2h, vacuum, and remove excess water and byproducts. (2) Add tetramethylammonium hydroxide, heat to 105~115℃, keep warm for 3~4h, then heat to 140℃, keep warm for 30min, vacuum for 30min to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, and obtain modified amino silicone oil. (3) Add modified amino silicone oil, allyl epoxy polyether and solvent to the reactor, mix evenly, and react at 70~85℃ for 1~3h to obtain low yellowing polyether modified amino silicone oil.

3. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, In step (1), the molar ratio of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane is 1:0.2~0.

7.

4. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, In step (1), the amount of deionized water is 0.5 to 1.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane.

5. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, In step (1), the feeding time of octamethylcyclotetrasiloxane is 30-40 min.

6. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, In step (2), the amount of tetramethylammonium hydroxide used is 0.01% to 0.05% of the mass of octamethylcyclotetrasiloxane.

7. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, In step (3), the solvent is isopropanol, and the mass ratio of the solvent to allyl epoxy polyether is 0.1~0.5:

1.

8. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that, The mass ratio of the modified amino silicone oil to the allyl epoxy polyether is 1:0.8~1.

1.

9. A fabric finishing agent, characterized in that, By weight, it comprises 20-40 parts of the low-yellowing polyether modified amino silicone oil as described in any one of claims 1-8, 10-20 parts of emulsifier, 0.01-0.1 parts of initiator, 0.4-2.5 parts of acetic acid, 1-5 parts of modified porous carbon micro powder, and 60-70 parts of water.

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