Low-yellowing hydrophilic hydroxyl modified amino silicone oil and preparation method thereof

Abstract

The invention discloses low-yellowing hydrophilic hydroxyl modified amino silicon oil and a preparation method thereof, and the preparation method comprises the following steps: firstly, preparing a low-yellowing amino coupling agent, a basic catalyst, alpha, omega-hydroxyl polydimethylsiloxane and a basic catalyst, and then adding the prepared amino silicon oil into a reaction kettle to obtain the low-yellowing hydrophilic hydroxyl modified amino silicon oil. And reacting 2-chloroethoxyethanol with amino groups to obtain the hydroxyl modified amino silicon oil. And the emulsified textile has the characteristics of low yellowing, hydrophilicity, smoothness, softness and the like. In the quaternary ammoniation modification process of the amino silicon oil, reactive hydrogen on amino in the amino silicon oil is closed, so that the decomposition probability of the reactive hydrogen on the amino is reduced, the possibility that the amino and hydrogen atoms are oxidized and decomposed into chromophoric groups under a high-temperature condition is reduced, and the yellowing of the product is obviously reduced. In addition, a hydrophilic group hydroxyl is introduced during quaternary ammoniation modification, and compared with a traditional competitive product only subjected to quaternary ammoniation hydrophilic modification, the product is more obvious in hydrophilic effect.

Description

Technical Field

[0001] The invention relates to a low-yellowing hydrophilic hydroxyl-modified amino silicone oil and a preparation method thereof, belonging to the technical field of organic silicon. Background Art

[0002] In the textile field, silicone softener has always played an important role. It can make fibers and fabrics soft and smooth, improve the feel and comfort of clothing, and make wearing more comfortable. In addition, it plays an important role in increasing the hydrophilicity of fabrics, reducing static electricity generation, increasing fabric wear resistance and extending service life, improving dyeing effects, and improving air permeability. It is widely used in finishing processes. It is also widely used in the finishing of textiles such as cotton, polyester, rayon, silk and wool. This type of product has been accepted by people and has become an important application scenario for amino silicone oil. However, the two amino groups (primary amino group and secondary amino group) on the diamine coupling agent have lone pairs of electrons, which are easily oxidized and decomposed into chromophores with hydrogen atoms under high temperature conditions. At the same time, the diamine structure has the effect of synergistically accelerating oxidation, which will promote the formation of chromophores, resulting in yellowing or color change of the finished fabric. In addition, amino groups are hydrophobic groups, and the improvement of hydrophobicity is not helpful for dyeing and finishing processes, and the air permeability of the fabric has a significant impact.

[0003] In order to improve the yellowing problem after amino silicone oil finishing, the effective methods generally include: 1. Use a monoamine coupling agent to reduce the synergistic oxidation of diamine, 2. Use secondary or tertiary amine to reduce the reactivity with active hydrogen. 3. Block the active hydrogen on the amino group in the amino silicone oil or introduce active hydrogen on the polysiloxane main chain to reduce the probability of active hydrogen decomposition on the amino group. In order to improve the hydrophilicity of amino silicone oil after finishing, it is generally improved by block polyether modified ternary copolymer softener, that is, hydrophilic softener is prepared by using hydrogen-containing silicone oil, allyl active polyether or allyl glycidyl ether, polyether amine, etc. Or the hydrophilicity is improved by polyether modified amino silicone oil, that is, hydrophilic epoxy polyether is used to react with amino silicone oil. However, both methods have the problems of long reaction time and large amount of organic solvent used. Moreover, due to the partial shielding effect of polyether chain segments on polysiloxane chain segments, it is difficult for the softener to have both hydrophilicity and soft feel. Summary of the invention

[0004] The purpose of the present invention is to obtain hydroxyl-modified amino silicone oil by reacting 2-chloroethoxyethanol with amino groups, and to provide a method for preparing low-yellowing, hydrophilic amino silicone oil, which has the characteristics of simple preparation process, easy emulsification, and good hand feel and hydrophilicity for textile finishing after emulsification and low yellowing.

[0005] A low-yellowing hydrophilic hydroxy-modified amino silicone oil is characterized in that when 2-chloroethoxyethanol is excessive and the coupling agent is different, the structural formula is as follows: , ,

[0007]

[0008] n = 10-10000; When 2-chloroethoxyethanol is insufficient, the structural formula is as follows:

[0009] n=10-10000.

[0010] The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil comprises the following steps: A: To prepare low-yellowing hydrophilic hydroxy-modified amino silicone oil, firstly, the raw materials are mixed according to mass percentage: 90%-95% of α,ω-hydroxy polydimethylsiloxane, 0.1%-5% of amino coupling agent, and 0.001%-0.01% of alkaline catalyst, and then the mixture is heated to 100-140°C under the protection of nitrogen, and the vacuum degree is 500-1000 mbar, and the reaction is carried out for 1-6 hours, and then the amino silicone oil is prepared after acid neutralization.

[0011] B: Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: stir the amino silicone oil prepared above with 2-chloroethoxyethanol under a vacuum of 100-300 mbar to obtain hydroxy-modified amino silicone oil. The molar ratio is 1:1-1:3; c: Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: uniformly mix the above hydroxy-modified amino silicone oil with an emulsifier and an emulsifier at room temperature, then stir under the stirring and shearing action of a homogenizer and drop deionized water into the system to obtain a hydrophilic hydroxy-modified amino silicone oil emulsion.

[0012] The average viscosity of α, ω-hydroxy polydimethylsiloxane at 25°C is 5 to 500 mPa·s The alkaline catalyst is 10% tetramethylammonium hydroxide ethanol solution, 10-60% potassium hydroxide, tetramethylammonium hydroxide, sodium hydroxide aqueous solution.

[0013] The neutralizing acid is one of acetic acid, phosphoric acid, ethanol and DMC in a ratio of 1:1-1:10.

[0014] The amino coupling agent is one or more of the following: γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-aminopropyltriethoxysilane.

[0015] When the amino silicone oil reacts with 2-chloroethoxyethanol, the solvent is tetrahydrofuran.

[0016] The technical solution of the present invention utilizes hydroxy polydimethylsiloxane, amino coupling agent, and alkaline coupling agent to synthesize amino silicone oil, and then performs hydroxyl modification on this basis. The two steps are relatively independent, and the adjustment of the ammonia value of the modified amino silicone oil, the mono-amino type and the di-amino type of the amino coupling agent can be adjusted in the first step. In the process of quaternization modification of the amino silicone oil after the first step, the active hydrogen on the amino group in the amino silicone oil is blocked, so that the probability of decomposition of the active hydrogen on the amino group is reduced, and the possibility of oxidation and decomposition of the amino group and hydrogen atoms into chromophore groups under high temperature conditions is reduced, which significantly reduces the yellowing of the product. At the same time as the quaternization modification, the hydrophilic group hydroxyl group is introduced. Compared with the traditional competing products that only perform quaternary hydrophilic modification, the hydrophilic effect of this product is more obvious. For details, see Table 1 Sample Performance Comparison. DETAILED DESCRIPTION

[0017] The present invention is further explained below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and do not limit the present invention. In addition, it should be understood that after reading this invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

[0018] Embodiment 1: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropyltriethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0019] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0020] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A1.

[0021] Embodiment 2: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropylmethyldiethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0022] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0023] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A2.

[0024] Embodiment 3: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of phenylaminomethyl triethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0025] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0026] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A3.

[0027] Embodiment 4: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of N-aminoethyl-methyldiethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0028] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0029] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A4.

[0030] Embodiment 5: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0031] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0032] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A5.

[0033] Embodiment 6: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 60 g of γ-aminopropyltriethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0034] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0035] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A6.

[0036] Embodiment 7: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropyltriethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0037] (2) Place 1000 g of amino silicone oil and 280 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0038] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A7.

[0039] Embodiment 8: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropyltriethoxysilane and 0.5 g of 20% sodium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0040] (2) Place 1000 g of amino silicone oil and 70 g of 2-chloroethoxyethanol in a three-necked flask, add 1000 ml of tetrahydrofuran as solvent, react at 80 °C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0041] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A8.

[0042] Embodiment 9: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropyl triethoxysilane and 1 g of 10% tetramethylammonium hydroxide ethanol solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0043] (2) Place 1000 g of amino silicone oil and 140 g of 2-chloroethoxyethanol in a three-necked flask, use 1000 ml of tetrahydrofuran as solvent, react at 80°C for 6 h, and condense and evaporate the solvent at 100 mbar to obtain hydroxy-modified amino silicone oil.

[0044] (3) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion A9.

[0045] Comparative Example 1: (1) Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: Preparation of low-yellowing amino silicone oil: 1000 g of α, ω-hydroxy polydimethylsiloxane (silicone linear body) and 30 g of γ-aminopropyltriethoxysilane and 0.5 g of 20% potassium hydroxide aqueous solution were reacted at 100 ° C and a vacuum degree of 700 mbar for 3 hours, and then neutralized with acetic acid ethanol solution (1:10) to obtain amino silicone oil.

[0046] (2) After mixing 1000 g of hydroxy-modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion B1.

[0047] Comparative Example 2 (1) Purchase Dow Corning OFX-7700 hydrophilic self-emulsifying amino silicone oil from the market.

[0048] (2) After mixing 1000 g of a competitor's modified amino silicone oil with 15 g of acetic acid, 2000 g of deionized water was gradually added dropwise at 25 °C and stirred for 1 h to obtain emulsion B2.

[0049] Example comparison The emulsion prepared by the low yellowing hydrophilic hydroxyl modified amino silicone oil prepared by the above method was prepared into a finishing liquid of 6.67 g / L, and the process conditions of double dipping and double padding and drying and setting at 150°C for 90 seconds were adopted. The products obtained in the embodiment and the comparative example were used to soften and finish 20×20 cm pure cotton cloth.

[0050] Evaluation method: The hand feel is mainly evaluated from the aspects of softness and smoothness. Several experts are busy touching. Level 5 is the best and level 1 is the worst. In addition, the softness is evaluated from the activity rate through the fabric style meter (YG821L), and the slipperiness is evaluated from the dynamic friction coefficient. The higher the activity rate, the better the softness, and the lower the dynamic friction coefficient, the better the slipperiness.

[0051] The hydrophilicity of a fabric is defined by measuring the time in seconds (s) for a drop of water to be completely absorbed by the fabric.

[0052] The emulsion stability was mainly evaluated by storing it in an oven at 50°C for 15 days, observing whether there was drift or stratification, and using a multiple light scattering instrument (TURBISCAN CLASSIC 2) to evaluate the emulsion stability coefficient. The smaller the emulsion stability index, the more stable the emulsion.

[0053] Fabric whiteness: The whiteness value is tested by a whiteness colorimeter (DRK-130B). The greater the whiteness, the less yellowing.

[0054] Table 1 Comparison of sample performance

[0055] It can be seen from the table that the low-yellowing hydrophilic amino silicone oil of the present invention, after being prepared into an emulsion, has the characteristics of low yellowing, good hydrophilicity, soft hand feeling, etc. when used on cotton fabrics. Its preparation process is simple and has the characteristics of being scalable and easy to scale up. It has broad prospects.

Claims

1. A low-yellowing hydrophilic hydroxyl-modified amino silicone oil characterized by: Depending on the coupling agent, the structural formula includes the following: 、 、 、 、 ; where n=10-10000.

2. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 1, characterized in that The following steps are involved: a: Preparation of low yellowing hydrophilic hydroxyl modified amino silicone oil, firstly mix the raw materials according to the mass percentage: α, ω-hydroxy polydimethylsiloxane, amino coupling agent, alkaline catalyst, heated to 100-140°C under nitrogen protection, vacuum degree 500-1000 mbar, reacted for 1-6 hours, and then neutralized with acid to prepare amino silicone oil; b: Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: stirring the amino silicone oil prepared above with 2-chloroethoxyethanol under a solvent under a vacuum of 100-300 mbar to obtain hydroxy-modified amino silicone oil; c: Preparation of low-yellowing hydrophilic hydroxy-modified amino silicone oil: uniformly mix the above hydroxy-modified amino silicone oil with an emulsifier and an emulsifier at room temperature, then stir under the stirring and shearing action of a homogenizer and drop water into the system to obtain a hydrophilic hydroxy-modified amino silicone oil emulsion.

3. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: The mass fraction of α,ω-hydroxy polydimethylsiloxane is 90%-95%, the mass fraction of amino coupling agent is 0.1%-5%, and the mass fraction of alkaline catalyst is 0.001%-0.01%.

4. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: The average viscosity of the α,ω-hydroxy polydimethylsiloxane at 25° C. is 5 to 500 mPa·s.

5. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: The alkaline catalyst includes 5-10% by mass of tetramethylammonium hydroxide ethanol solution, 5-10% by mass of potassium hydroxide, 5-10% by mass of tetramethylammonium hydroxide, and 5-10% by mass of sodium hydroxide aqueous solution.

6. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: The neutralizing acid is acetic acid or phosphoric acid in a solvent to form a solution, and the solvent is ethanol or DMC; the mass ratio of acetic acid or phosphoric acid to the solvent is 1:1-1:

10.

7. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: The amino coupling agent is one or more of the following: γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-aminopropyltriethoxysilane.

8. The method for preparing the low-yellowing hydrophilic hydroxy-modified amino silicone oil according to claim 2, characterized in that: When the amino silicone oil reacts with 2-chloroethoxyethanol, the solvent is tetrahydrofuran.

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