CN102505496B - Amino silicone oil durable hydrophilic synergist and preparation method and application thereof - Google Patents

Abstract

The invention discloses an amino silicone oil durable hydrophilic synergist and a preparation method and application thereof. The preparation method comprises the following steps: under the anaerobic condition, methyl hydrogen-containing silicone oil, terminal allyl terminal epoxy compound and allyl polyether are reacted under the action of a platinum catalyst to obtain the amino silicone oil durability hydrophilic synergist. The method has the advantages of simple reaction steps, mild reaction conditions, simplicity and feasibility. The amino silicone oil durability hydrophilic synergist can be used independently before and after the traditional amino silicone oil is soft finished, and can also be used together with the traditional amino silicone oil emulsion in a bath.

Description

A kind of amino silicone oil durable hydrophilic synergist and its preparation method and application

technical field

The invention belongs to the technical field of textile chemical industry, and in particular relates to an amino silicone oil (emulsion) durable hydrophilic synergist and its preparation method and application.

Background technique

Amino-modified silicone oil has been produced and applied in my country for more than 20 years. At present, it is still a dominant variety in softening finishing auxiliaries. Amino silicone oil can be widely used in the soft finishing of various natural fibers and synthetic fibers. The fabrics treated with it have the advantages of softness, smoothness, plumpness and washability. Traditional amino silicone oils can give fabrics a good feel, but there are also Congenital deficiency, in addition to the ordinary amino silicone oil emulsion will cause demulsification and oil floating due to factors such as alkali on the cloth surface or long-term shearing during use, the fabric after ordinary amino silicone oil emulsion finishing will be It is hydrophobic, which makes the wearing comfort worse, and leads to serious color flowers due to poor penetration and uneven absorption when the fabric is repaired and re-dyeing, so it cannot be repaired directly, and a special silicone oil stripper must be used to remove it. Thoroughly remove the amino silicone oil before restaining. In addition, due to the poor hydrophilicity of amino silicone oil, the antistatic performance of the finished fabric is also poor, and various problems caused by static electricity are prone to occur. Therefore, the hydrophilic modification of ordinary amino silicone oil has become a hot spot in the research of silicone softeners. At present, there are three main types of hydrophilic silicone softeners, namely polyether modified silicone oil, hydrophilic polyether modified amino silicone oil and Linear polyether amino block silicone oil.

The representative product of polyether modified silicone oil is CGF developed by Chenguang Chemical Research Institute of the former Ministry of Chemical Industry. It is characterized by good hydrophilicity, general hand feeling and poor washability. Hydrophilic polyether modified amino silicone oil is to introduce amino group and hydrophilic polyether segment into the side chain of polysiloxane molecule at the same time, so that the hydrophilicity of the fabric can be improved while maintaining the hand feeling of amino silicone oil to a certain extent. The traditional amino silicone oil has the problems that it cannot be repaired after dyeing, poor wearing comfort and difficult to clean. The biggest problem with hydrophilic polyether-modified amino silicone oil is that when the hydrophilicity is better improved, the hand feel is often not as soft and comfortable as amino-modified silicone oil, and vice versa, there is a contradictory relationship between the two. In addition, this type of silicone oil, Such as Dow Corning's DC8600 and GE Toshiba's TEX180 have the problem that the hydrophilicity is not durable. The Chinese invention patent with the publication number CN 1919896A discloses a method for preparing hydrophilic silicone oil, which uses low-hydrogen silicone oil and polyether to react under the action of a chain transfer agent and a catalyst, introduces an amino coupling agent, and finally prepares Amino-modified hydrophilic silicone oil is produced, which improves the hydrophilicity of the amino silicone softener, but greatly reduces the handle of the treated fabric. As linear polyether amino block silicone oil is modified by linear polyether amino block, it pushes the hydrophilic silicone fabric finishing agent to a new level, which balances the contradiction between hand feeling and hydrophilicity well. The product has good stability and is excellent in high temperature resistance, high shear resistance, electrolyte resistance and strong acid and alkali resistance, and is suitable for almost all finishing processes. The Chinese invention patent application with the publication number CN 101497967A discloses a method for preparing a fabric softening and finishing agent block water-soluble silicone oil. 1. The preparation of polyorganosiloxane-polyether linear block copolymer and the ammonolysis of block copolymer four preparation steps improve the contradiction between the hand feeling and hydrophilicity of ordinary hydrophilic polyether modified amino silicone oil , but the preparation process is complicated and the cost is high. Such products are represented by special silicone oils such as Magnasoft SRS, Magnasoft JSS and Magnasoft SILQ of Momentive Corporation of the United States. Several domestic companies and research institutions are developing such products. The cost of this type of hydrophilic silicone softener is very high. The price of general amino silicone oil is several times higher, so it is not suitable for application in general products, and as far as the current Momentive products are concerned, the application is selective to fabrics. For example, Magnasoft SRS is especially suitable for soft finishing of polyester and wool products, with excellent hand feeling , poor hydrophilicity.

The current development of traditional amino silicone oil is very mature, and its style and feel are various, including soft, smooth, fluffy and elastic, etc., and its applicable scope includes almost all fabric types (cotton, wool, polyester, etc. and various Blended fabrics), and it has high cost performance, therefore, in a long period of time, traditional amino silicone oil will still be a dominant softener variety, but people have more and more requirements for the hydrophilicity and wearing comfort of fabrics. In this situation, looking for an amino silicone oil synergist with excellent hydrophilicity and durability has become a problem that needs to be solved.

Contents of the invention

The purpose of the present invention is to improve the hydrophilicity of traditional amino silicone oil, provide a kind of amino silicone oil (emulsion) durable hydrophilic synergist and its preparation method.

The structural formula of the amino silicone oil (emulsion) durable hydrophilic synergist provided by the present invention is as shown in formula I:

(Formula I)

In formula I, R is selected from any one of the following groups: -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ and -COCH ₃ ;

a+b+c+d=an integer between 1-20, a≥0, but b and d cannot be 0 at the same time, and c and d cannot be 0 at the same time;

n>m≥0, m+n=an integer between 5-25;

An integer between p+q=0-25, and is divided into the following four cases: 1) when b=c=0 and d≠0, q>p≥0 and p+q=5-25; 2 ) when b=0 and c≠0 and d≠0, q>p≥0 and p+q=5-25; 3) when b≠0 and c=0 and d≠0, p+q=0 -25; 4) when b≠0 and c≠0 and d≠0, p+q=0-25;

That is, the molecular structure must contain both hydrophilic polyether segments and reactive epoxy groups.

The method for preparing the above-mentioned amino silicone oil (emulsion) durable hydrophilic synergist comprises the following steps: under anaerobic conditions, the methyl hydrogen-containing silicone oil and the allyl compound are reacted under the action of a platinum catalyst to obtain the amino silicone oil (Emulsion) Durable hydrophilic synergist.

The method also includes vacuumizing and depressurizing distillation to remove small molecular substances (including low molecular components that have not completely reacted in methyl hydrogen silicone oil and allyl compounds and low boiling point solvents in platinum catalysts) after the reaction is completed. step.

Wherein, the structural formula of the methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO] _A [(CH ₃ )HSiO] _B Si(CH ₃ ) ₃ , wherein A≥0, B≥1 And A+B=1-20;

The allyl compound is composed of any-group substances in the following a)-d):

a) allyl glycidyl ether, allyl-terminated epoxy compound A and allyl polyether;

Wherein, the structural formula of the allyl glycidyl ether is CH ₂ =CHCH ₂ OCH ₂ (CHCH ₂ )O;

The structural formula of the allyl-terminated epoxy compound A is CH ₂ ═CHCH ₂ O(C ₃ H ₆ O) _P (C ₂ H ₄ O) _Q CH ₂ (CHCH ₂ )O, wherein P≥0, Q≥0 and an integer between P+Q=0-25;

The structural formula of the allyl polyether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) _m (C ₂ H ₄ O) _n R, wherein n>m≥0, m+n=5-25 An integer, R is -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ or -COCH ₃ ;

b) the allyl-terminated epoxy compound A and the allyl polyether;

c) the allyl glycidyl ether and the allyl-terminated epoxy compound B;

The structural formula of the allyl-terminated epoxy compound B is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) _P (C ₂ H ₄ O) _Q CH ₂ (CHCH ₂ )O, wherein Q>P≥ 0 and an integer between P+Q=5-25;

d) The allyl-terminated epoxy compound B.

In the above preparation method, the reaction temperature of the reaction is 70-120° C., and the time is 1-12 hours.

In the above preparation method, the material ratio of Si-H in the methyl hydrogen-containing silicone oil to C=C in the allyl compound (including allyl-terminated epoxy compound and allyl polyether) It is 1.0:(1.0-5.0), preferably 1.0:(1.1-1.6).

The platinum catalyst used can specifically be the absolute ethanol or isopropanol solution of platinum chloride, the isopropanol solution of chloroplatinic acid and dimethylsiloxane and 1,3-divinyl-1,1,3, One of the mixtures of 3-tetramethyldisiloxane platinum complexes (dimethylsiloxane is used as a diluent or solvent, mainly for the convenience of the use of platinum catalysts), the amount of platinum catalysts is based on platinum chloride, Chloroplatinic acid or platinum complex is calculated as 10-100ppm of the total mass of reactants, preferably 10-50ppm.

In the above preparation method, the hydrophilic oxirane segment (C ₂ H ₄ O) accounts for 20%-75% of the total mass of the product (through the selection of the allyl compound, including the structure (the ratio of EO to PO) ) and molecular weight, and adjust the ratio of reactants, the main purpose is to adjust the hydrophilic properties of the synthetic product), and the mass fraction of the ethylene oxide segment (C ₂ H ₄ O) in the prepared product is greater than that of the propylene oxide segment (C ₃ H ₆ O); the reactive epoxy group-(CHCH ₂ )O accounts for 1%-10% of the total mass of the prepared product (by controlling the amount of allyl glycidyl ether, terminal allyl The structure and dosage of the epoxy compound at the base end and the proportioning ratio of the reactants are adjusted, etc., the main purpose is to control the reactivity of the synthetic product).

In order to improve the hydrophilicity of traditional amino silicone oil, the invention provides an amino silicone oil (emulsion) durable hydrophilic synergist. The synergist introduces a hydrophilic segment (hydrophilic polyether segment) and a reactive group (epoxy group) into the molecular structure at the same time, and it can be used alone in the traditional amino silicone oil for soft finishing when combined with amino silicone oil (emulsion). Can be used before or after, and can also be used in the bath with traditional amino silicone oil emulsion. In the case of a small amount, it can not only completely retain the soft and smooth feel of traditional amino silicone oil, but also endow the fabric with excellent hydrophilicity and durability. Different from the fabrics treated with simple traditional amino silicone oil, the fabrics treated with durable hydrophilic synergists can be repaired directly without treatment.

The amino silicone oil (emulsion) durable hydrophilic synergist provided by the invention can be used for fabric finishing.

Yet another object of the present invention is to provide a method of finishing fabrics.

When finishing the fabric, the amino silicone oil hydrophilic synergist of the present invention can be used alone before or after the traditional amino silicone oil soft finishing, or used in the same bath with the traditional amino silicone oil emulsion; it should be fully dissolved and mixed evenly before use.

Specifically, the method comprises the following steps: using the amino silicone oil (emulsion) durable hydrophilic synergist provided by the invention to finish the fabric by a dipping and padding method.

The conditions for finishing the fabric by the one-soaking-rolling method are: fabric one-soaking-rolling working liquid, pressure 2-5Kg/cm ² , liquid rolling rate 70-75%; drying at 90-110°C for 60-120s , Bake at 140-160°C for 60-120s;

The working fluid is: 1) the aqueous solution of the amino silicone oil hydrophilic synergist, or 2) the mixed aqueous solution of the amino silicone oil and the amino silicone oil hydrophilic synergist; the amino silicone oil hydrophilic synergist in the working fluid The mass concentration of the agent is 0.05-10%.

When the working solution is the aqueous solution of the amino silicone oil hydrophilic synergist, the method also includes the following 1) or 2): 1) the step of pre-treating the fabric with amino silicone oil; The fabric treated by the method is post-treated with amino silicone oil.

The above-mentioned amino silicone oils include traditional amino silicone oils (such as FK-220C32, FK-220D19, FK-220C33 of Beijing Chinatex Chemical Co. Co., Ltd. FK-220F5) and linear polyether amino block silicone oil (such as Beijing China Textile Chemical Co., Ltd. FK-220F8), etc.

Compared with the prior art, the present invention has the following advantages:

1. The preparation reaction conditions are mild and the reaction process is simple.

2. Good stability, less dosage, low cost, wide application range, simple and easy-to-operate application process, it can be used alone before and after softening with amino silicone oil, or it can be used in the same bath with amino silicone oil emulsion.

3. It can endow the fabric with excellent hydrophilicity, and does not affect the feel of amino silicone oil at all, making up for the defects of traditional amino silicone oil in terms of hydrophilicity. The fabric after finishing can be directly repaired and dyed without treatment.

4. After finishing, it will be more firmly combined with the fabric in the form of chemical bonds, and the hydrophilicity of the fabric is durable.

Description of drawings

Fig. 1 is the infrared spectrogram of the amino silicone oil (emulsion) durable hydrophilic synergist prepared in Example 1.

Fig. 2 is the infrared spectrogram of the amino silicone oil (emulsion) durable hydrophilic synergist prepared in Example 2.

Fig. 3 is the infrared spectrogram of the amino silicone oil (emulsion) durable hydrophilic synergist prepared in Example 3.

Fig. 4 is the infrared spectrogram of the amino silicone oil (emulsion) durable hydrophilic synergist prepared in Example 4.

Fig. 5 is the infrared spectrogram of the amino silicone oil (emulsion) durable hydrophilic synergist prepared in Example 5.

Detailed ways

The present invention will be described below through specific examples, but the present invention is not limited thereto.

The experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.

Applied hydrophilic test method and hand feeling test method and standard are as follows in the following examples:

Hydrophilicity test: AATCC-79 method: Fix the cloth sample (recovered overnight in the air) flatly on the bandage ring, use a burette with a diameter of 1 mm, drop a drop of water at a height of 1 cm from the cloth surface, and start timing. When the reflectivity of the water drops gradually decreases to a completely non-reflective watermark, stop the timing, and take the average value of 3-5 points of the test. The shorter the water droplet penetration and diffusion time, the better the hydrophilic performance.

Hand feel test: hand touch method evaluation, 5 people form a group, touch the finished fabric, and make a rating. Divide the hand feeling into 5 grades, take the unfinished blank cloth as grade 1, and the grade of the best one is stipulated as grade 5, and other fabrics are graded relative to this standard.

Example 1

1. Synthesis of amino silicone oil (emulsion) durable hydrophilic synergist

The mixture of 79.0g methyl hydrogen-containing silicone oil, 17.1g allyl glycidyl ether, 322.8g terminal allyl polyoxyalkylene epoxy ether and 414g allyl polyether is dropped into the reactor, and nitrogen gas And start stirring, heat up to 85 ° C, add 0.238 g of isopropanol solution (mass concentration 10%) of chloroplatinic acid, the amount of catalyst (calculated as chloroplatinic acid) is based on 30 ppm of the total mass of reactants (that is, 3 × 10 ^{− 5} ) Add, heat-retain for 5 hours, and then distill under reduced pressure to remove low-volatile substances, and the obtained transparent liquid is amino silicone oil (emulsion) durable hydrophilic synergist, and its solid content is at least 99%.

In formula I, R is -CH ₃ , a=2, b=3, c=1, d=4, m=4, n=14, p=2, q=7;

The structural formula of methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO] ₂ [(CH ₃ )HSiO] ₈ Si(CH ₃ ) ₃

The structural formula of allyl glycidyl ether is CH ₂ =CHCH ₂ OCH ₂ (CHCH ₂ )O

The structural formula of allyl-terminated polyoxyalkylene epoxy ether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₇ CH ₂ (CHCH ₂ )O

The structural formula of allyl polyether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₄ CH ₃

The infrared spectrum of the synthesized product is shown in Figure 1. It can ^be seen from Figure 1 that 3050cm ^-1 is the stretching vibration peak of CH in the epoxy group, the absorption peak of -CH ₃ and -CH ₂ - groups in the polymer is at 2970 ~ 2887cm ^-1 , and the absorption peak of -CH 3 and -CH 2 - groups in the polymer is The characteristic absorption peak of the C=C bond in excess allyl compounds, 1255cm ^{-1 is} the symmetrical deformation vibration absorption peak of _-CH3 in Si- _CH3 , and the COC stretching vibration and Si-O- The overlapping peaks of Si stretching vibration absorption peaks, near 803cm ^-1 is the stretching vibration absorption peak of Si-C in Si-CH ₃ , 1450cm ^-1 is the bending ^vibration absorption peak of saturated CH bonds, there is no Si- The characteristic absorption peak of H appears, which indicates that Si-H disappears substantially, and the infrared spectrum can verify that the target product has been synthesized.

2. Fabric finishing and performance testing

Add 0.2% of the above-mentioned durable hydrophilic synergist to deionized water, mix well and prepare a working solution (dipping solution), and use a dipping and rolling process to soften the black color of the traditional amino silicone oil emulsion. After finishing the plain cotton woven fabric, it was found that the working solution had a good infiltration and penetration effect on the cotton fabric softened and finished by the traditional amino silicone oil emulsion, the pressure was 3Kg/cm ² , and the squeeze rate was 75%. , Bake at 140°C for 120s.

Five professionals used the hand touch method to evaluate the hand feeling of the fabric, and the hydrophilicity was measured by the water drop penetration method according to the AATCC-79 method. The test results are as follows:

Table 1 Hand feeling and hydrophilicity test result

Black plain cotton woven fabric, Sinospun active black G, dosage 3% o.w.f.; traditional amino silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220C32) and hydrophilic polyether modified amino silicone oil (Beijing China Textile Chemical Co., Ltd. Co., Ltd. FK-220F5) are commercially available products.

Table 2 Restoration and dyeing results

Fabric sample (black plain cotton woven fabric) Exterior Standard deviation value K/S value

After finishing with traditional amino silicone oil (before repair) Uniform, colorless flowers 0.21 8.2 After finishing with traditional amino silicone oil (after repair) Has obvious color flowers 0.95 9.4 After finishing in Example 1 (after repair) Uniform, colorless flowers 0.23 12.6

(The dye used for restoration and dyeing is Sinospin Reactive Black G, dosage 2.5% o.w.f., liquor ratio 1:20; use American Datacolor computer color measurement and color matching instrument to measure surface depth K/S value and standard deviation value, K/S value The larger the value, the darker the color of the sample; the smaller the K/S value, the lighter the color; the larger the standard deviation value, the more uneven the color of the sample, and the smaller the standard deviation value, the more uniform the color)

Example 2

1. Synthesis of amino silicone oil (emulsion) durable hydrophilic synergist

Put a mixture of 41.6g of methyl hydrogen silicone oil, 27.4g of allyl glycidyl ether and 50.6g of allyl polyether into the reactor, blow nitrogen and start stirring, raise the temperature to 95°C, and add platinum chloride 0.05 g of dehydrated ethanol solution (mass concentration 12%), the consumption of catalyst (in terms of platinum chloride) is added according to 50 ppm (that is, 5×10 ^-5 ) of the total mass of reactants, and the reaction is incubated for 7 hours, and then vacuum distillation The low volatile matter is removed, and the transparent liquid obtained is amino silicone oil (emulsion) durable hydrophilic synergist, and its solid content is at least 98%.

In formula I, R is -CH ₂ CH ₂ CH ₂ CH ₃ , a=2, b=1, c=2, d=0, n=7, m=0;

The structural formula of methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO][(CH ₃ )HSiO] ₃ Si(CH ₃ ) ₃

The structural formula of allyl glycidyl ether is CH ₂ =CHCH ₂ OCH ₂ (CHCH ₂ )O

The structural formula of allyl polyether is CH ₂ =CHCH ₂ O(C ₂ H ₄ O) ₇ CH ₂ CH ₂ CH ₂ CH ₃

The infrared spectrum of the synthesized product is shown in Figure 2. It can be seen from Figure 2 that the synthesized product is the target product.

2. Fabric finishing and performance testing

First make 20% of the traditional amino silicone oil emulsion into a 40g/L working solution, then add 0.1% of the above-mentioned durable hydrophilic synergist to the working solution, mix well, and use a dipping and rolling process to The blue pure cotton woven fabric is softened with a pressure of 2.7Kg/cm ² and a squeeze rate of 75%, then dried at 100°C for 120s and baked at 140°C for 120s. Five professionals used the hand touch method to evaluate the hand feeling of the fabric, and the hydrophilicity was measured by the water drop penetration method according to the AATCC-79 method. The result is as follows:

Table 3 feel and hydrophilic test results

samples feel Hydrophilicity/s Hydrophilicity after washing 5 times/s blank (not processed) Level 1 0.8s 0.8s Traditional amino silicone oil Level 5 >120s, not hydrophilic ＞120s, not hydrophilic Linear polyether amino block silicone oil Level 4.5 3.5s 3.5s

Example 2 Level 5 0.9s 0.8s

Blue pure cotton woven fabric; traditional amino silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220D19) and linear polyether amino block silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220F8) are commercially available.

Example 3

1. Synthesis of amino silicone oil (emulsion) durable hydrophilic synergist

Put a mixture of 80.4g of methyl hydrogen-containing silicone oil, 448.8g of terminal allyl polyoxyalkylene epoxy ether and 335g of allyl polyether into the reactor, blow nitrogen and start stirring, and raise the temperature to 92°C , add 0.086g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (mass concentration 15%) in dimethylsiloxane, the consumption of catalyst ( Calculated as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex) at 15ppm (i.e. 1.5×10 ^-5 ) of the total mass of reactants, and keep warm for 6 Hours, then vacuum distillation to remove low volatile substances, the transparent liquid obtained is amino silicone oil (emulsion) durable hydrophilic synergist, and its solid content is at least 99%.

In formula I, R is -COCH ₃ , a=3, b=4, c=0, d=3, m=3, n=9, p=6, q=15;

The structural formula of methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO] ₃ [(CH ₃ )HSiO] ₇ Si(CH ₃ ) ₃

The structural formula of terminal allyl polyoxyalkylene epoxy ether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₆ (C ₂ H ₄ O) ₁₅ CH ₂ (CHCH ₂ )O

The structural formula of allyl polyether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₃ (C ₂ H ₄ O) ₉ COCH ₃

The infrared spectrum of the synthesized product is shown in Figure 3. It can be seen from Figure 3 that the synthesized product is the target product.

2. Fabric finishing and performance testing

First make 25% of the traditional amino silicone oil emulsion into a 40g/L working solution, then add 0.3% of the above-mentioned durable hydrophilic synergist to the working solution, mix well, and use a dipping and rolling process to The red pure cotton knitted fabric is softened, the pressure is 3.5Kg/cm ² , the liquid squeeze rate is 75%, then it is dried at 110°C×90s, and baked at 140°C×90s. Five professionals use the hand touch method to evaluate the hand feeling of the fabric , Hydrophilicity is measured by water drop penetration method according to AATCC-79 method. The result is as follows:

Table 4 hand feel and hydrophilicity test results

samples feel Hydrophilicity/s Hydrophilicity after washing 5 times/s blank (not processed) Level 1 1.2s 1.2s Traditional amino silicone oil Level 5 >120s, not hydrophilic ＞120s, not hydrophilic Hydrophilic polyether modified amino silicone oil level 4 5.3s 5.3s Linear polyether amino block silicone oil Level 4.5 2.1s 2.1s Example 3 Level 5 1.5s 1.6s

Red pure cotton knitted fabric, Sinotex reactive red 3BS, 3% o.w.f.; traditional amino silicone oil (Beijing Sinotex Chemical Co., Ltd. FK-220C33), hydrophilic polyether modified amino silicone oil (Beijing Sinotex Chemical Co., Ltd. FK -220F5) and linear polyether amino block silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220F8) are commercially available.

Table 5 repair dyeing results

Cloth sample (red cotton knitted fabric) Exterior Standard deviation value K/S value Original fabric sample (after repair) Uniform, colorless flowers 0.14 14.8 After finishing with traditional amino silicone oil (after repair) Has obvious color flowers 0.75 10.2 After finishing in Example 3 (after repair) Uniform, colorless flowers 0.17 14.9

(the dye used for restoration and dyeing is Sinospin Reactive Red 3BS, dosage 1% o.w.f., liquor ratio 1:20; use American Datacolor computer color measurement and color matching instrument to measure surface depth K/S value and standard deviation value, K/S value The larger the value, the darker the color of the sample; the smaller the K/S value, the lighter the color; the larger the standard deviation value, the more uneven the color of the sample, and the smaller the standard deviation value, the more uniform the color)

Example 4

1. Synthesis of amino silicone oil (emulsion) durable hydrophilic synergist

The mixture of 91g of methyl hydrogen-containing silicone oil, 37.6g of allyl glycidyl ether and 639.1g of terminal allyl polyoxyalkylene epoxy ether is put into the reactor, nitrogen is blown and stirring is started, and the temperature is raised to 90 ℃, add 0.107g of isopropanol solution of chloroplatinic acid (concentration 18%), the amount of catalyst (in terms of chloroplatinic acid) is added according to 25ppm (ie 2.5×10 ^-5 ) of the total mass of reactants, and keep the reaction for 5 hours , and then decompressed distillation to remove low-volatile substances, and the transparent liquid obtained is amino silicone oil (emulsion) durable hydrophilic synergist, and its solid content is at least 98%.

In formula I, a=2, b=0, c=3, d=7, p=4, q=11;

The structural formula of methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ ) ₂ SiO] ₂ [(CH ₃ )HSiO] ₁₀ Si(CH ₃ ) ₃

The structural formula of allyl glycidyl ether is CH ₂ =CHCH ₂ OCH ₂ (CHCH ₂ )O

The structural formula of allyl-terminated polyoxyalkylene epoxy ether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₁ CH ₂ (CHCH ₂ )O

The infrared spectrum of the synthesized product is shown in Figure 4. It can be seen from Figure 4 that the synthesized product is the target product.

2. Fabric finishing and performance testing

Add 0.25% of the above-mentioned durable hydrophilic synergist to deionized water, mix thoroughly and evenly, and prepare a working solution. Finish the white polyester-cotton woven fabric through a process of dipping and rolling, and dry it after drying. , and then make 20% of the traditional amino silicone oil emulsion into a 30g/L working solution, and then use the working solution to soften and finish the above-mentioned finished polyester-cotton fabric through a process of dipping and rolling, with a pressure of 3Kg/cm ² , Liquid extrusion rate is 71%, drying at 95℃×120s, baking at 150℃×90s. Five professionals used the hand touch method to evaluate the hand feeling of the fabric, and the hydrophilicity was measured by the water drop penetration method according to the AATCC-79 method. The result is as follows:

Table 6 hand feel and hydrophilicity test results

samples feel Hydrophilicity/s Hydrophilicity after washing 5 times/s blank (not processed) Level 1 ＞120s, not hydrophilic ＞120s, not hydrophilic Traditional amino silicone oil Level 5 ＞120s, not hydrophilic ＞120s, not hydrophilic Hydrophilic polyether modified amino silicone oil Level 3.5 10.4s 10.2s Linear polyether amino block silicone oil level 4 30.1s 30.3s Example 4 Level 5 1.3s 1.3s

White twill polyester-cotton woven fabric; traditional amino silicone oil (Beijing Chinatex Chemical Co., Ltd. FK-220D19), hydrophilic polyether modified amino silicone oil (Beijing Chinatex Chemical Co., Ltd. FK-220F5) and linear polyether amino embedded Silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220F8) is commercially available.

Example 5

1. Synthesis of amino silicone oil (emulsion) durable hydrophilic synergist

Put a mixture of 44.4g of methyl hydrogen-containing silicone oil and 150.6g of terminal allyl polyoxyalkylene epoxy ether into the reactor, blow nitrogen gas and start stirring, raise the temperature to 90°C, and add dimethylsiloxane 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (mass concentration 12%) 0.016g, the consumption of catalyst (as 1,3-divinyl -1,1,3,3-tetramethyldisiloxane platinum complex) added according to 10ppm of the total mass of the reactants, kept for 8 hours, and then evaporated under reduced pressure to remove low-volatile substances, and the obtained transparent The liquid is amino silicone oil (emulsion) durable hydrophilic synergist, and its solid content is at least 99%.

In formula I, a=b=c=0, d=1, p=6, q=15;

The structural formula of methyl hydrogen silicone oil is (CH ₃ ) ₃ SiO[(CH ₃ )HSiO]Si(CH ₃ ) ₃

The structural formula of allyl-terminated polyoxyalkylene epoxy ether is CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₇ CH ₂ (CHCH ₂ )O

The infrared spectrum of the synthesized product is shown in Figure 5. It can be seen from Figure 5 that the synthesized product is the target product.

2. Fabric finishing and performance testing

First make 20% of the traditional amino silicone oil emulsion into a 30g/L working solution, then add 0.4% of the above-mentioned durable hydrophilic synergist to the working solution, mix well, and use a dipping and rolling process to The green polyester woven fabric is softened with a pressure of 3.3Kg/cm ² and a squeeze rate of 73%, then dried at 105°C for 60s and baked at 160°C for 90s. Five professionals used the hand touch method to evaluate the hand feeling of the fabric, and the hydrophilicity was measured by the water drop penetration method according to the AATCC-79 method. The result is as follows:

Table 7 hand feel and hydrophilicity test results

samples feel Hydrophilicity/s Hydrophilicity after washing 5 times/s blank (not processed) Level 1 >120s, not hydrophilic ＞120s, not hydrophilic

Traditional amino silicone oil Level 5 >120s, not hydrophilic ＞120s, not hydrophilic Hydrophilic polyether modified amino silicone oil level 4 21.3s 21.6s Linear polyether amino block silicone oil Level 5 44.1s 43.5s Example 5 Level 5 2.7s 2.9s

Green polyester woven fabric; traditional amino silicone oil (Beijing Chinatex Chemical Co., Ltd. FK-220D19), hydrophilic polyether modified amino silicone oil (Beijing Chinatex Chemical Co., Ltd. FK-220F5) and linear polyether amino block silicone oil (Beijing China Textile Chemical Co., Ltd. FK-220F8) are commercially available products.

Claims (12)

1. the amido silicon oil hydrophilic potentiating agent shown in the formula I:

(formula I)

In the formula I, R is selected from any one in the following radicals :-CH ₃,-CH ₂CH ₃,-CH ₂CH ₂CH ₃,-CH ₂CH ₂CH ₂CH ₃With-COCH ₃

Integer between a+b+c+d=1-20, a 〉=0, and b and d can not be that 0, c and d can not be 0 simultaneously simultaneously;

N＞m 〉=0, the integer between the m+n=5-25;

Integer between the p+q=0-25, and minute following situation to p q limit: 1) when b=c=0 and the d ≠ 0, q＞p 〉=0 and p+q=5-25; 2) when b=0 and c ≠ 0 and d ≠ 0, q＞p 〉=0 and p+q=5-25; 3) when b ≠ 0 and c=0 and d ≠ 0, p+q=0-25; 4) when b ≠ 0 and c ≠ 0 and d ≠ 0, p+q=0-25.

2. method for preparing amido silicon oil hydrophilic potentiating agent shown in the claim 1 Chinese style I, comprise the steps: under the oxygen free condition, Methyl Hydrogen Polysiloxane Fluid and allylic cpd are reacted under the platinum catalyst effect, obtain described amido silicon oil hydrophilic potentiating agent;

Wherein, the structural formula of described Methyl Hydrogen Polysiloxane Fluid is (CH ₃) ₃SiO[(CH ₃) ₂SiO] _A[(CH ₃) HSiO] _BSi (CH ₃) ₃, A 〉=0 wherein, the integer between B 〉=1 and the A+B=1-20;

Described allylic cpd by following a)-d) in any one group of material form:

A) glycidyl allyl ether, the epoxy terminated compd A of end-allyl group and allyl polyether;

Wherein, the structural formula of described glycidyl allyl ether is CH ₂﹦ CHCH ₂OCH ₂(CHCH ₂) O;

The structural formula of the epoxy terminated compd A of described end-allyl group is CH ₂﹦ CHCH ₂O(C ₃H ₆O) _P(C ₂H ₄O) _QCH ₂(CHCH ₂) O, P 〉=0 wherein, the integer between Q 〉=0 and the P+Q=0-25;

The structural formula of described allyl polyether is CH ₂﹦ CHCH ₂O(C ₃H ₆O) _m(C ₂H ₄O) _nR, n＞m 〉=0 wherein, the integer between the m+n=5-25, R is-CH ₃,-CH ₂CH ₃,-CH ₂CH ₂CH ₂CH ₃Or-COCH ₃

B) the epoxy terminated compd A of described end-allyl group and described allyl polyether;

C) the epoxy terminated compd B of described glycidyl allyl ether and end-allyl group;

The structural formula of the epoxy terminated compd B of described end-allyl group is CH ₂﹦ CHCH ₂O(C ₃H ₆O) _P(C ₂H ₄O) _QCH ₂(CHCH ₂) O, the wherein integer between Q＞P 〉=0 and the P+Q=5-25;

D) the epoxy terminated compd B of described end-allyl group.

3. method according to claim 2, it is characterized in that: the temperature of reaction of described reaction is 70-120 ℃, the time is 1-12 hour;

In the described reaction, the Si-H in the described Methyl Hydrogen Polysiloxane Fluid and the molar ratio of the C=C in the allylic cpd are 1.0:(1.0-5.0).

4. method according to claim 3, it is characterized in that: in the described reaction, the Si-H in the described Methyl Hydrogen Polysiloxane Fluid and the molar ratio of the C=C in the allylic cpd are 1.0:(1.1-1.6).

5. each described method according to claim 2-4, it is characterized in that: described platinum catalyst is aqueous isopropanol and dimethyl siloxane and 1 of the dehydrated alcohol of platinum chloride or aqueous isopropanol, Platinic chloride, 3-divinyl-1,1, in the mixture of 3,3-tetramethyl disiloxane platinum complex any one; The consumption of described platinum catalyst is counted the 10-100ppm of reactant total mass with platinum chloride, Platinic chloride or platinum complex.

6. method according to claim 5, it is characterized in that: the consumption of described platinum catalyst is counted the 10-50ppm of reactant total mass with platinum chloride, Platinic chloride or platinum complex.

7. method according to claim 2 is characterized in that: among the described preparation method, and hydrophilic oxyethane segment C ₂H ₄The ratio that O accounts for preparation product total mass is 20%-75%, and oxyethane segment C ₂H ₄O accounts for the massfraction of preparation product greater than propylene oxide segment C ₃H ₆O; Has reactive epoxide group-(CHCH ₂) the O ratio that accounts for preparation product total mass is 1%-10%.

8. method according to claim 2 is characterized in that: described method also is included in the step that vacuumizes underpressure distillation after reaction finishes.

9. the application of the described amido silicon oil hydrophilic potentiating agent of claim 1 in textile finishing.

10. the method that fabric is put in order comprises the steps: to adopt the described amido silicon oil hydrophilic potentiating agent of claim 1 by the method for rolling of soaking fabric to be put in order.

11. method according to claim 10 is characterized in that: the condition that described one method of rolling of soaking is put in order fabric is: fabric one soaks one and rolls working fluid, and pressure is 2-5Kg/cm ², mangle expression 70-75%; Bake 60-120s under drying 60-120s, 140-160 ℃ under 90-110 ℃;

Wherein, described working fluid is: the 1) aqueous solution of described amido silicon oil hydrophilic potentiating agent, or 2) mixed aqueous solution of amido silicon oil and described amido silicon oil hydrophilic potentiating agent; The mass concentration of amido silicon oil hydrophilic potentiating agent is 0.05-10% in the described working fluid.

12. method according to claim 11 is characterized in that: described working fluid is the aqueous solution of described amido silicon oil hydrophilic potentiating agent, and described method also comprises following 1) and/or 2):

1) described fabric is carried out the step of pre-treatment with amido silicon oil;

The step of 2) fabric after the described method processing being carried out aftertreatment with amido silicon oil.

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