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

Abstract

The invention discloses preparation of low-yellowing polyether modified amino silicon oil and a fabric finishing agent containing the low-yellowing polyether modified amino silicon oil, and relates to amino silicon oil and application thereof. Original primary amino groups are converted into secondary amino groups on the basis of traditional amino silicon oil by adopting octamethylcyclotetrasiloxane and 3-piperazinyl propyl methyl dimethoxy silane as key raw materials, and meanwhile, the molecular mass control of the modified amino silicon oil is emphasized, so that the chemical stability and the oxidation resistance of the silicon oil are remarkably improved, and the service life of the silicon oil is prolonged. Allyl epoxy polyether is used for secondary modification, so that amino silicon oil which is not hydrophilic originally obtains certain hydrophilicity, and the self-emulsifying capacity of the silicon oil and the stability of the emulsion are remarkably improved. Through the modification, finally, silicone oil molecular chain segments can be continuously, alternately, repeatedly and directionally arranged on the fiber surface in a polyether and polysiloxane structure, and a fabric finished by the finishing agent is endowed with good hydrophilicity, softness and washability.

Description

Technical Field

[0001] The invention relates to amino silicone oil and application thereof, in particular to the preparation of low-yellowing polyether-modified amino silicone oil and a fabric finishing agent containing the same. Background Art

[0002] Among the commercial aminopolysiloxane polyether modified silicone oils, more than 90% are aminoethyliminopropylpolysiloxanes, which have two amino groups (primary and secondary amino groups) on its side chain and contain three active hydrogen atoms. Due to the presence of amino groups, especially primary amino groups, this structural form will be oxidized under the influence of heating and ultraviolet rays to form chromophores, causing yellowing. When softening colored fabrics, it often causes the fabric to fail to maintain its original color or color, causing the fabric to turn yellow or slightly yellow, which brings great trouble to the finishing after dyeing. The degree of yellowing increases with the increase of ammonia value. At present, the modification of aminosilicone oil mainly includes cationic modification, polyether modification, amidation modification, alkylation modification, etc. Although the modified products have a certain degree of suppression on the problem of aminosilicone oil's easy yellowing, they all have certain defects. Some of them greatly reduce the softness of aminosilicone oil, such as polyether modification, cationic modification, and amidation modification; some of them greatly reduce the hydrophilicity of silicone oil, such as alkylation modification.

[0003] Aiming at the disadvantage that aminopolysiloxane polyether modified silicone oil is easy to yellow as a fabric finishing agent, the present invention proposes to change the primary amino group to a secondary amino group, control the molecular weight of polysiloxane, effectively reduce the number of active hydrogen, prevent the oxidation of the primary amino group, and reduce yellowing. By selecting an appropriate modifier 3-piperazine propyl methyl dimethoxy silane, the modified aminopolysiloxane polyether silicone oil is synthesized to be used as a textile softener to reduce yellowing. Summary of the invention

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

[0005] In order to solve the above technical problems, the present invention provides the following technical scheme: a low-yellowing polyether-modified amino silicone oil, wherein the low-yellowing polyether-modified amino silicone oil uses octamethylcyclotetrasiloxane and 3-piperazinepropylmethyldimethoxysilane as reaction raw materials and tetramethylammonium hydroxide as initiator, and the modified amino silicone oil is synthesized by hydrolysis reaction and condensation reaction, and then reacted with allyl epoxy polyethers of different molecular weights to obtain the low-yellowing polyether-modified amino silicone oil.

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

[0007] (1) Add 3-piperazinepropylmethyldimethoxysilane and deionized water into a reaction kettle, slowly add octamethylcyclotetrasiloxane, raise the temperature to 80-90° C., keep the temperature for 1-2 hours, and evacuate to remove excess water and by-products;

[0008] (2) adding tetramethylammonium hydroxide, heating to 105-115° C., keeping the temperature for 3-4 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

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

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

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

[0012] Furthermore, in the step (1), the addition time of octamethylcyclotetrasiloxane is 30 to 40 minutes.

[0013] Furthermore, the amount of tetramethylammonium hydroxide used in step (2) 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 the allyl epoxy polyether is 0.1 to 0.5:1.

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

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

[0017] A fabric finishing agent comprises, by weight, 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 micropowder and 60-70 parts of water.

[0018] Furthermore, the modified porous carbon micropowder is prepared by hydroxylating the porous carbon micropowder and reacting it with a certain amount of olefinic coupling agent.

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

[0020] The finishing agent prepared by the present invention forms a filling effect of the polyether chain segment inside the fiber and a coating effect of the external hydroxyl bonding with the fiber, so that the hydrophilicity of the finished fiber can be maintained with good durability. At the same time, the modified porous carbon micropowder and the low-yellowing polyether-modified amino silicone oil are cross-linked with double bonds to form a network film layer on the surface of the fabric, which can reduce the friction coefficient of the fabric surface. In addition, the modified porous carbon micropowder is affected by the particle size and deposited on the fiber surface. Since the hardness of the modified porous carbon micropowder is relatively high, the film layer is more wear-resistant and has the effect of resisting pilling. In addition, the porous structure of the modified porous carbon micropowder and the hydrophilic groups it carries 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 aminosilicone oil, which mainly uses octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane as key raw materials. By introducing piperazine groups into the silane chain, a significant change in the chemical structure is achieved on the basis of traditional aminosilicone oil, and the original primary amino group is converted into a secondary amino group. At the same time, the molecular weight control of the modified aminosilicone oil is focused on. By precisely controlling the reaction conditions and the raw material ratio, the molecular weight of the modified aminosilicone 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 occurrence of yellowing of traditional aminosilicone oil.

[0023] (2) The present invention utilizes modified amino silicone oil and allyl epoxy polyether to combine through chemical bonds to obtain polyether modified amino silicone oil, wherein the piperazine group of the modified amino silicone oil and the epoxy group of the allyl epoxy polyether undergo a ring-opening reaction, thereby introducing a polyether segment. This process enables the amino silicone oil, which originally does not have hydrophilicity, to acquire a certain degree of hydrophilicity, and significantly improves the self-emulsification ability of the silicone oil and the stability of the emulsion. Through this modification, the silicone oil molecular segments can be continuously and repeatedly alternating and directional arranged in the form of polyether and polysiloxane structures on the fiber surface, giving the finishing agent-finished fabric good hydrophilicity, softness and washability.

[0024] (3) The present invention uses piperazinyl and allyl epoxy polyether to perform dual modification on silicone oil. Through this method, silicone oil not only has the characteristics of piperazinyl amino silicone oil, but also incorporates the components of block silicone oil. The emulsion prepared in this way has the dual advantages of amino silicone oil and block silicone oil. This dual modification technology significantly improves the stability of the emulsion system and makes full use of the respective advantages of amino silicone oil and block silicone oil, thereby showing excellent comprehensive performance in practical applications. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 30 minutes, heat to 80°C, keep warm for 1 hour, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.2; the deionized water is 0.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0028] (2) adding tetramethylammonium hydroxide in an amount of 0.01% of the mass of octamethylcyclotetrasiloxane, heating to 105° C., keeping the temperature for 3 h, then heating to 140° C., keeping the temperature for 30 min, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0029] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 300, and isopropanol into the reactor, wherein 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 powder was placed in a 6 mol / L potassium hydroxide solution and soaked for 2 h, then washed with deionized water for 3 times and dried at 60 °C for 6 h to obtain a hydroxylated porous carbon powder;

[0031] (5) 0.02 g of methacryloyloxymethyltrimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0032] (6) Add 10 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0033] Example 2

[0034] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 32 minutes, heat to 80°C, keep warm for 1 hour, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.3; the deionized water is 0.8 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0035] (2) adding tetramethylammonium hydroxide in an amount of 0.02% of the mass of octamethylcyclotetrasiloxane, heating to 105° C., keeping the temperature for 3 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0036] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 450, and isopropanol into the reactor, wherein 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 powder was placed in a 6 mol / L potassium hydroxide solution and soaked for 2 h, then washed with deionized water for 3 times and dried at 60 °C for 6 h to obtain a hydroxylated porous carbon powder;

[0038] (5) 0.02 g of methacryloyloxymethyltrimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0039] (6) Add 12 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0040] Example 3

[0041] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 35 minutes, heat to 85°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4; the deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0042] (2) adding tetramethylammonium hydroxide in an amount of 0.03% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0043] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

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

[0045] (5) 0.02 g of allyldimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetic stirring was performed at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0046] (6) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0047] Example 4

[0048] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 37 minutes, heat to 88°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.5; the deionized water is 1.1 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0049] (2) adding tetramethylammonium hydroxide in an amount of 0.04% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0050] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 1000, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

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

[0052] (5) 0.02 g of 3-butenetriethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0053] (6) Add 18 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0054] Example 5

[0055] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 40 minutes, heat to 90°C, keep warm for 2 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.7; the deionized water is 1.5 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0056] (2) adding tetramethylammonium hydroxide in an amount of 0.05% of the mass of octamethylcyclotetrasiloxane, heating to 115° C., keeping the temperature for 4 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0057] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 1500, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

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

[0059] (5) 0.02 g of 3-butenetriethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0060] (6) Add 20 parts of emulsifier by weight to an 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 a fabric finishing agent.

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

[0062] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 35 minutes, heat to 85°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4; the deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0063] (2) adding tetramethylammonium hydroxide in an amount of 0.03% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

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

[0065] (4) 0.02 g of allyldimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0066] (5) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

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

[0068] (1) Adding common amino silicone oil, allyl epoxy polyether with an average molecular weight of 550, and isopropanol into a reactor, wherein 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, and after mixing evenly, reacting at 80°C for 2h to obtain modified amino silicone oil;

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

[0070] (3) 0.02 g of allyldimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; the hydroxylated porous carbon powder was added to the modifier system, and magnetically stirred at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain a modified porous carbon powder;

[0071] (4) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0072] Comparative Example 3 (Porous Carbon Powder is Not Hydroxylated)

[0073] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 35 minutes, heat to 85°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4; the deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0074] (2) adding tetramethylammonium hydroxide in an amount of 0.03% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0075] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

[0076] (4) 0.02 g of allyldimethoxysilane was dissolved in 40 ml of 99.9% pure ethanol to obtain a modifier system; porous carbon powder was added to the modifier system, and magnetic stirring was performed at 45° C. and 80 rpm for 1 h. After the modification was completed, the modified porous carbon powder was washed with ethanol and dried at 100° C. to obtain modified porous carbon powder;

[0077] (5) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0078] Comparative Example 4 (Porous Carbon Powder Modified Without Coupling Agent)

[0079] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 35 minutes, heat to 85°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4; the deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0080] (2) adding tetramethylammonium hydroxide in an amount of 0.03% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0081] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

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

[0083] (5) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

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

[0085] (1) Add 3-piperazinylpropylmethyldimethoxysilane and deionized water into the reaction kettle, slowly add octamethylcyclotetrasiloxane, the addition time is 35 minutes, heat to 85°C, keep warm for 1.5 hours, evacuate, and remove excess water and by-products; the molar ratio of octamethylcyclotetrasiloxane to 3-piperazinylpropylmethyldimethoxysilane is 1:0.4; the deionized water is 1.0 times the total mass of octamethylcyclotetrasiloxane and 3-piperazinylpropylmethyldimethoxysilane;

[0086] (2) adding tetramethylammonium hydroxide in an amount of 0.03% of the mass of octamethylcyclotetrasiloxane, heating to 110° C., keeping the temperature for 3.5 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil;

[0087] (3) Add modified amino silicone oil, allyl epoxy polyether with an average molecular weight of 550, and isopropanol into the reactor, wherein 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 h to obtain low-yellowing polyether-modified amino silicone oil;

[0088] (4) Add 15 parts of emulsifier by weight to an 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 a fabric finishing agent.

[0089] Performance Testing

[0090] Application process of finishing agent:

[0091] Processed fabric: polyester cotton twill,

[0092] Treatment process: dosage 30g / L, one dip and one roll (rolling rate: 75%) → drying and shaping (140℃×60S) → cooling and moisture regain → performance evaluation;

[0093] 1. Hand feel: Touch the finished fabric with eyes closed, and make ratings in groups of 10. Rating the hand feel of the printed fabric according to different hand feels. The specific evaluation method is: Rating the hand feel from the two aspects of softness and smoothness, divided into 5 levels, with level 1 being the worst, the fabric feels hard and has a poor smooth feeling. Level 5 is the best, the fabric feels soft and smooth;

[0094] 2. Whiteness: measured by a whiteness meter, the smaller the difference with the original cloth, the better the yellowing resistance; the value of the original cloth is 91.2;

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

[0096] 4. Stability

[0097] (1) Heat resistance and stability

[0098] The test method is as follows: put a certain amount of finishing agent emulsion into a sealed container, place it in a constant temperature water bath at 80°C, keep it warm for 6 hours, and observe the appearance of the emulsion. If there is no bleaching oil or stratification, it means that the finishing agent emulsion has good heat resistance and stability. If there is a small amount of bleaching oil and stratification, it means that the heat resistance and stability of the finishing agent emulsion are average. If there is bleaching oil and stratification, it means that the heat resistance and stability of the finishing agent emulsion are poor.

[0099] (2) Freeze stability

[0100] The test method is as follows: put a certain amount of finishing agent emulsion into a sealed container, place it in a constant temperature water bath at -20℃, keep it warm for 6 hours, and after natural thawing, observe and record its state changes. If there is no floating oil or stratification, it means that the finishing agent emulsion has good freezing stability. If there is a small amount of floating oil and stratification, it means that the finishing agent emulsion has average freezing stability. If there is a large amount of floating oil and stratification, it means that the finishing agent emulsion has poor freezing stability.

[0101] (3) Acid resistance and stability

[0102] The test method is as follows: put a certain amount of finishing agent emulsion into a sealed container, add 50 times the weight of hydrochloric acid aqueous solution with a pH value of 3, leave it still for 1 day, observe and record its state changes, no floating oil and stratification phenomenon indicates that the finishing agent emulsion has good acid resistance and stability, a small amount of floating oil and stratification phenomenon indicates that the finishing agent emulsion has average acid resistance and stability, and the presence of floating oil and stratification phenomenon indicates that the finishing agent emulsion has poor acid resistance and stability.

[0103] (4) Alkali resistance stability

[0104] The test method is as follows: put a certain amount of finishing agent emulsion into a sealed container, add 50 times the weight of sodium hydroxide aqueous solution with a pH value of 12, leave it still for 1 day, observe and record its state changes, and the absence of oil floating and stratification indicates that the finishing agent emulsion has good alkali resistance and stability, a small amount of oil floating and stratification indicates that the finishing agent emulsion has average alkali resistance and stability, and the presence of oil floating and stratification indicates that the finishing agent emulsion has poor alkali resistance and stability.

[0105] 5. Washability

[0106] After washing the fabric 100 times, observe the color of the fabric and the evaluation method is: if the color of the fabric remains more than 96% of that before washing, it means that the fabric has good washability; if the color of the fabric remains 80-95% of that before washing, it means that the fabric has average washability; if the color of the fabric remains less than 80% of that before washing, it means that the fabric has poor washability.

[0107] 6. Anti-pilling

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

[0109] Table 1 Performance test results

[0110]

[0111]

[0112] It can be seen from the above data that the low-yellowing polyether-modified amino silicone oil and finishing agent provided by the present invention have excellent hand feel, stable performance, anti-pilling, yellowing resistance and certain hydrophilicity. In addition, the preparation method of the present invention has simple process, convenient operation and control, stable quality, high production efficiency, and can be mass-produced industrially.

[0113] It will be apparent to those skilled in the art that the 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 the spirit or essential features of the invention. 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, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

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-piperazinepropylmethyldimethoxysilane as reaction raw materials and tetramethylammonium hydroxide as an initiator, synthesizing the modified amino silicone oil through hydrolysis reaction and polycondensation reaction, and then reacting with allyl epoxy polyethers of different molecular weights.

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-piperazinepropylmethyldimethoxysilane and deionized water into a reaction kettle, slowly add octamethylcyclotetrasiloxane, raise the temperature to 80-90° C., keep the temperature for 1-2 hours, and evacuate to remove excess water and by-products; (2) adding tetramethylammonium hydroxide, heating to 105-115° C., keeping the temperature for 3-4 hours, then heating to 140° C., keeping the temperature for 30 minutes, and evacuating the system for 30 minutes to remove the decomposed tetramethylammonium hydroxide and excess low-boiling substances in the reaction system, thereby obtaining a modified amino silicone oil; (3) Add modified amino silicone oil, allyl epoxy polyether and solvent into the reactor, mix well, and react at 70-85° C. for 1-3 hours to obtain low-yellowing polyether modified amino silicone oil.

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

7.

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

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

6. The low-yellowing polyether-modified amino silicone oil according to claim 2, characterized in that: The amount of tetramethylammonium hydroxide used in step (2) 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 the step (3), the solvent is isopropanol, and the mass ratio of the solvent to the 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: In parts by weight, it comprises 20-40 parts of the low-yellowing polyether-modified amino silicone oil as described in any one of claims 1 to 8, 10-20 parts of an emulsifier, 0.01-0.1 parts of an initiator, 0.4-2.5 parts of acetic acid, 1-5 parts of modified porous carbon powder, and 60-70 parts of water.

10. The low-yellowing polyether-modified amino silicone oil according to claim 9, characterized in that: The modified porous carbon micropowder is prepared by hydroxylating the porous carbon micropowder and reacting it with a certain amount of olefinic coupling agent.

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