CN101435160A - A kind of organosilicon-fluorine multifunctional fabric finishing agent and preparation method thereof - Google Patents

Abstract

The present invention discloses an organosilicon-fluorine multifunctional fabric finishing agent. Aiming at the problems existing in the currently commercially available organosilicon finishing agents, a small amount of organofluorine groups are introduced into the organosilicon finishing agent, and the smoothness of the finishing agent is further improved without changing the original effect of the organosilicon finishing agent. At the same time, the water and oil repellent effect is increased to a certain extent. The present invention is non-toxic, non-polluting, cost-effective, and has broad application prospects. The present invention also discloses a preparation method of the organosilicon-fluorine multifunctional fabric finishing agent, which has simple process operation, strong stability of the prepared emulsion, is not easy to demulsify, does not delaminate during long-term storage, is simple to use, significantly improves the feel of the textile, and increases the added value.

Description

A kind of organosilicon-fluorine multifunctional fabric finishing agent and preparation method thereof

technical field

The invention relates to a fabric finishing agent, in particular to an organosilicon-fluorine multifunctional fabric finishing agent and a preparation method thereof.

Background technique

Silicone emulsion is an important finishing agent in the post-treatment process of fabrics. It can significantly improve the hand feel of fabrics, making them smooth, soft and plump. Early silicone fabric finishing agents were mainly mechanical mixtures of dimethyl silicone oil and hydrogen-containing silicone oil. Due to the lack of active groups, this silicone has poor bonding fastness to fabrics and is easy to fall off, and the treated fabric feels relatively soft. Difference. Subsequently, soft and smooth finishing agents with high-viscosity hydroxyl silicone oil as the main component appeared, but the application effect of this kind of finishing agent is average, and there are disadvantages such as poor emulsion stability, easy delamination, and easy demulsification, etc., which have high requirements for the use environment. Oil drifts easily and can damage textiles. In recent years, more and more fabric softening and smoothing agents based on amino silicone oil have been sold on the market. Although they have achieved a good softening effect, their smoothness is not enough. At the same time, several kinds of silicone emulsions were compounded to form a multifunctional additive, which achieved good results.

Contents of the invention

The present invention provides an organosilicon-fluorine multifunctional finishing agent and its preparation process aiming at the deficiencies of the existing organosilicon textile finishing technology. In the organosilicon finishing agent, a small amount of organic fluorine If it is effective, it further improves the slipperiness of the finishing agent, and at the same time increases the effect of water and oil repellency to a certain extent.

To achieve the above object, the present invention takes the following technical solutions:

An organosilicon-fluorine multifunctional fabric finishing agent, by weight percentage, consists of the following components:

Amino silicone oil: 5-20%

Long carbon chain modified amino silicone oil: 5-20%

Fluorine-containing modified silicone oil: 5-20%

Emulsifier: 3～10%

Co-emulsifier: 1～10%

Glacial acetic acid: 0.5～1%

The balance is deionized water;

Described amino silicone oil is:

R _{is CH2CH2CH2NHCH2CH2NH2} ; m1= ₁₀ ～2000, _{n1 =} 1～200 _;

Described long carbon chain modified amino silicone oil is:

R ₁ is CH ₂ (CH ₂ ) _q CH ₃ ;

m2=10～2000, n2=1～200, p2=1～200, q=1～20;

Described fluorine-containing modified silicone oil is:

_{R2 is CH2CH2CH2NHCH2CH2NHCF2CF} ( _CF3 )O- _{[CF2CF ( CF3} ) _O ] _{n - H} ;

m3=10-2000, n3=1-200, p3=1-200, n=0-9.

All three ingredients can be prepared by yourself, and the preparation method is as follows:

Preparation of amino silicone oil: D ₄ (octamethylcyclotetrasiloxane) or DMC (mixture based on D ₄ ), aminosilane coupling agent N-β-aminoethyl-γ-aminopropylmethyl Dimethoxysilane, H ₂ O, catalyst KOH and accelerator dimethyl sulfoxide react at a temperature of 80-150°C for 1-15 hours, and then neutralize with an equimolar amount of inorganic acid or organic acid to obtain Amino silicone oil. Its feeding mole can be compared as: _D4 or DMC: aminosilane coupling agent: _H2O : catalyst KOH: accelerator = 1: (0.05～0.45): (0.02～0.35): (0.001～0.008): (0.0009～ 0.008), the inorganic acid used for neutralization is dilute hydrochloric acid or dilute sulfuric acid, and the organic acid is formic acid, acetic acid, propionic acid, butyric acid or valeric acid. The ammonia value range of the obtained amino silicone oil is: 0.1-0.9, and the viscosity is 2000-200000mPS.

Preparation of long carbon chain modified amino silicone oil: _D4 or DMC, aminosilane coupling agent N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, long carbon chain silane coupling agent ten Dialkylmethyldimethoxysilane, H ₂ O, catalyst KOH and accelerator dimethyl sulfoxide, react at a temperature of 80-150°C for 1-15 hours, and then use an equimolar amount of inorganic acid or organic acid Neutralize to obtain long carbon chain modified amino silicone oil. Its feeding molar ratio can be: DMC: aminosilane coupling agent: long carbon chain silane coupling agent: _H2O : catalyst: accelerator = 1: (0.05～0.45): (0.05～0.45): (0.02～0.35 ):(0.001～0.008):(0.0009～0.008), the inorganic acid used for neutralization is dilute hydrochloric acid or dilute sulfuric acid, the organic acid is formic acid, acetic acid, propionic acid, butyric acid or valeric acid, and the obtained long carbon chain modified The range of ammonia value of amino silicone oil is: 0.2~0.8, viscosity 5000~100000mP.S.

Preparation of fluorine-containing modified silicone oil: First, prepare amino silicone oil according to the above method, then add amino silicone oil, perfluoropropylene oxide, isopropanol and catalyst KOH into the reaction bottle, pressurize for 3-12 hours, and neutralize with glacial acetic acid catalyst, and the solvent was removed by rotary evaporation to obtain fluorine-containing modified silicone oil.

The emulsifier is a composite emulsifier, which is any two of fatty alcohol polyoxyethylene ether-3 (AEO-3), fatty alcohol polyoxyethylene ether-9 (AEO-9), and isomeric alcohol polyoxyethylene ether As long as the HLB value of the compound emulsifier is close to the HLB value of the emulsified system; all the above emulsifiers can be commercially available products, such as the XP series and XL series of isomeric alcohol polyoxyethylene ethers. It is preferably a mixture of fatty alcohol polyoxyethylene ether-3 and fatty alcohol polyoxyethylene ether-9, or a mixture of fatty alcohol polyoxyethylene ether-3 and isomeric alcohol polyoxyethylene ether XL50.

The co-emulsifier is mainly C ₂ -C ₈ alcohols, such as propylene glycol, n-pentanol, n-hexanol, etc., and the dosage is 1-10%, preferably 2-5%, of the total weight of the finishing agent.

The preparation process of the above-mentioned organosilicon-fluorine multifunctional fabric finishing agent includes: firstly, adding amino silicone oil, long carbon chain modified amino silicone oil, fluorine-containing modified silicone oil, emulsifier and co-emulsifier to the reaction kettle and mixing evenly, stirring for 10 minutes , then first add part of deionized water, stir for 20 minutes, add glacial acetic acid to adjust the pH value to 6-7, then add the rest of deionized water, stir for 1-2 hours to obtain a microemulsion.

Compared with existing silicone finishing agents, the present invention has the following advantages:

(1) Long carbon chain modified amino silicone oil is added to the fabric finishing agent, which further enhances the slippery effect while ensuring the soft effect.

(2) The organic fluorine group is introduced into the fabric finishing agent, which has excellent water and oil repellent effect. Although the price is high, in the present invention, the application amount is less, and only a small amount is used, and the effect can be obtained Significantly improved.

(3) The preparation process is simple to operate, the emulsion has strong stability, is not easy to demulsify, does not separate after long-term storage, is simple to use, obviously improves the hand feeling of textiles, and increases the added value.

Detailed ways

Example 1

In parts by weight, 20 parts of amino silicone oil, 5 parts of long carbon chain modified amino silicone oil, 5 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and AEO-9 is 1:1), positive 3 parts of butanol, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 0.5 parts of glacial acetic acid to adjust the pH value to 6-7, added deionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 2

In parts by weight, 15 parts of amino silicone oil, 10 parts of long carbon chain modified amino silicone oil, 5 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-9 and XP50 is 2:1), 3 parts of n-hexanol parts, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 0.5 parts of glacial acetic acid to adjust the pH value to 6-7, added deionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 3

In parts by weight, 10 parts of amino silicone oil, 15 parts of long carbon chain modified amino silicone oil, 5 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and AEO-9 is 2:3), positive 3 parts of butanol, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 0.7 parts of glacial acetic acid to adjust the pH value to 6-7, added deionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 4

In parts by weight, 5 parts of amino silicone oil, 20 parts of long carbon chain modified amino silicone oil, 5 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and AEO-9 is 1:2), positive 3 parts of amyl alcohol, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 0.6 parts of glacial acetic acid to adjust the pH value to 6-7, added deionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 5

In parts by weight, 5 parts of amino silicone oil, 15 parts of long carbon chain modified amino silicone oil, 10 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and XL50 is 3:5), n-butanol 3 parts, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 1 part of glacial acetic acid to adjust the pH value to 6-7, added deionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 6

In parts by weight, 5 parts of amino silicone oil, 10 parts of long carbon chain modified amino silicone oil, 15 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and XL50 is 1:1), 3 parts of propylene glycol , stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 0.5 parts of glacial acetic acid to adjust the pH value to 6-7, added ionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Example 7

In parts by weight, 5 parts of amino silicone oil, 5 parts of long carbon chain modified amino silicone oil, 20 parts of fluorine-containing modified silicone oil, 10 parts of emulsifier (the mass ratio of AEO-3 and XL50 is 2:1), n-butanol 3 parts, stirred for 10 minutes, then added 30 parts of deionized water, stirred for 20 minutes, added 1 part of glacial acetic acid to adjust the pH value to 6-7, added ionized water to 100 parts, stirred for 1-2 hours, and emulsified to obtain a transparent emulsion.

Performance Testing:

The emulsions prepared in each of the above examples were formulated into 40g/L solutions respectively, and the bath ratio was 1:20. The effect test was carried out on cotton fiber fabrics through the two-dipping and two-rolling process. After drying at 100°C and baking at 160°C for 3 minutes, Use the WSB-2 whiteness meter to measure the whiteness of the fabric; ask experts to feel the hand feeling blindly, and evaluate the grade (among them, grade 6 is the best and grade 1 is the worst).

The results are as follows:

Table 1 Performance of organosilicon-fluorine multifunctional finishing agent

Claims (6)

1. An organosilicon-fluorine multifunctional fabric finishing agent, which consists of the following components by weight percentage: Amino silicone oil: 5-20% Long carbon chain modified amino silicone oil: 5-20% Fluorine-containing modified silicone oil: 5-20% Emulsifier: 3～10% Co-emulsifier: 1～10% Glacial acetic acid: 0.5～1% The balance is deionized water; Described amino silicone oil is: R is CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ; m1=10-2000, n1=1-200; the long carbon chain modified amino silicone oil is: R ₁ is CH ₂ (CH ₂ ) _q CH ₃ ; m2=10～2000, n2=1～200, p2=1～200, q=1～20; Described fluorine-containing modified silicone oil is:

_{R2 is CH2CH2CH2NHCH2CH2NHCF2CF} ( _CF3 )O- _{[CF2CF ( CF3} ) _O ] _{n - H} ; m3=10-2000, n3=1-200, p3=1-200, n=0-9. 2. The organosilicon-fluorine multifunctional fabric finishing agent according to claim 1, characterized in that: the emulsifier is fatty alcohol polyoxyethylene ether-3, fatty alcohol polyoxyethylene ether-9, isomeric alcohol polyoxyethylene ether A mixture of any two of oxyethylene ethers. 3. The organosilicon-fluorine multifunctional fabric finishing agent according to claim 1, characterized in that: the emulsifier is a mixture of fatty alcohol polyoxyethylene ether-3 and fatty alcohol polyoxyethylene ether-9, or fatty A mixture of alcohol ethoxylates-3 and isomeric alcohol ethoxylates XL50. 4. The organosilicon-fluorine multifunctional fabric finishing agent according to claim 1, characterized in that: the co-emulsifier is a C ₂ -C ₈ alcohol. 5. The organosilicon-fluorine multifunctional fabric finishing agent according to claim 1 or 4, characterized in that the amount of the co-emulsifier accounts for 2-5% of the total weight of the organosilicon-fluorine multifunctional finishing agent. 6. The method for preparing the organosilicon-fluorine multifunctional fabric finishing agent as claimed in claim 1, comprising: uniformly mixing amino silicone oil, long carbon chain modified amino silicone oil, fluorine-containing modified silicone oil, emulsifier and co-emulsifier, Stir for 10 minutes, then add part of deionized water, stir for 20 minutes, add glacial acetic acid to adjust the pH value to 6-7, then add the rest of deionized water, and stir for 1-2 hours.