阅读说明：本技术 超支化氨基有机硅保强力增手感型甲醛捕捉剂的合成方法及其应用 (Synthesis method and application of hyperbranched amino organic silicon hand-holding-strength-enhancing formaldehyde trapping agent ) 是由 王海峰 高艳娥 段志豪 徐杨 鲍杰 王涛 于 2020-07-08 设计创作，主要内容包括：本发明公开了一种超支化氨基有机硅保强力增手感型甲醛捕捉剂的合成方法及其应用,包括如下步骤：步骤一、分子量为800的端含氢硅油的合成；步骤二、LDE-EPS(硅油800)的合成；步骤三、HBP-ABP甲醛捕捉剂的合成。本发明合成具有保持强力、改善手感、兼具甲醛捕捉功能的整理剂,采用超支化结构引入大量可与甲醛反应的伯氨基和仲氨基,并接入适当的有机硅,从而改善织物手感,同时可作为强力保护剂,降低强力损伤。(The invention discloses a synthesis method and application of hyperbranched amino organic silicon hand-holding-force-increasing formaldehyde scavenger, comprising the following steps: step one, synthesizing hydrogen-terminated silicone oil with molecular weight of 800; step two, synthesizing LDE-EPS (silicone oil 800); step three, synthesizing the HBP-ABP formaldehyde capture agent. The invention synthesizes the finishing agent which has the advantages of keeping strong force, improving hand feeling and having the function of capturing formaldehyde, adopts a hyperbranched structure to introduce a large amount of primary amino groups and secondary amino groups which can react with the formaldehyde, and is added with proper organic silicon, thereby improving the hand feeling of fabrics, and simultaneously can be used as a strong protective agent to reduce strong damage.)

1. A method for synthesizing hyperbranched amino organic silicon hand-holding-strength-enhanced formaldehyde scavenger is characterized by comprising the following steps: the method comprises the following steps:

step one, synthesizing hydrogen-terminated silicone oil with molecular weight of 800:

with hydrogen-containing double end sockets and octamethylcyclotetrasiloxane (D)₄) Synthesizing hydrogen-terminated silicone oil with molecular weight of 800 by using concentrated sulfuric acid as a catalyst;

step two, synthesizing LDE-EPS (silicone oil 800):

(a) a device is set up, and a stirrer, a thermometer, a constant-pressure separating funnel and a condensing reflux pipe are matched with the four-mouth flask and stably set up;

(b) adding hydrogen-terminated silicone oil (molecular weight 800) and epoxy allyl glycidyl ether (molecular weight 600) into a four-neck flask according to a certain proportion, heating to a certain fixed reaction temperature, dropwise adding a metered catalyst into a system after the temperature is stable, and carrying out heat preservation reaction for a certain time;

(c) after the reaction is finished, adding a certain amount of allyl glycidyl ether AGE, heating to a certain reaction temperature, and continuously reacting for a period of time to obtain light yellow transparent LDE-EPS;

step three, synthesizing the HBP-ABP formaldehyde capture agent:

synthesizing HBP-ABP by taking LDE-EPS and diethylenetriamine as raw materials and controlling the ratio of reaction materials, the reaction temperature and the reaction time through nucleophilic addition reaction;

adding LDE-EPS and diethylenetriamine into a four-neck flask in proportion, heating to 50 ℃ firstly, reacting for 30min to fully mix the two raw materials to generate a monomer A and a monomer B, heating to a specified temperature, reacting for a period of time, and taking out to obtain the light yellow transparent HBP-ABP formaldehyde scavenger.

2. The method for synthesizing the hyperbranched amino-silicone retention-strength-enhancing hand-feeling formaldehyde trapping agent according to claim 1, wherein the method comprises the following steps: in the second step (b), the fixed reaction temperature is 80 ℃, the catalyst is chloroplatinic acid, the dosage of the catalyst is 0.2 percent of the total amount of reactants, and the heat preservation reaction time is 3 hours.

3. The method for synthesizing the hyperbranched amino-silicone retention-strength-enhancing hand-feeling formaldehyde trapping agent according to claim 1, wherein the method comprises the following steps: in the second step (b), the mass ratio of the terminal hydrogen-containing silicone oil (molecular weight 800) to the epoxy allyl glycidyl ether (molecular weight 600) is 1: 2.05, and 96.89 percent.

4. The method for synthesizing the hyperbranched amino-silicone retention-strength-enhancing hand-feeling formaldehyde trapping agent according to claim 1, wherein the method comprises the following steps: and in the second step (c), 5% of allyl glycidyl ether AGE with the molar mass of hydrogen-containing silicone oil is added, the reaction temperature is 90-95 ℃, the reaction time is 6.5 hours, and after the reaction is finished, the excessive allyl glycidyl ether and micromolecules are removed by decompression and suction filtration.

5. The method for synthesizing the hyperbranched amino-silicone retention-strength-enhancing hand-feeling formaldehyde trapping agent according to claim 1, wherein the method comprises the following steps: in the third step, the raw material n (LDE-EPS): n (diethylenetriamine) is 1:1.4, the reaction temperature is 70 ℃, the reaction time is 8h, the epoxy group conversion rate approaches 100 percent, the epoxy groups are basically and completely reacted, and the viscosity of a product system is 3960mpa · s.

6. The application of the hyperbranched amino organic silicon formaldehyde scavenger with the functions of protecting strength and increasing hand feeling is characterized in that: adding the HBP-ABP formaldehyde catching agent into a fabric finishing agent to prepare the fabric finishing agent, wherein the specific formula of the fabric finishing agent is as follows:

7. the application of the hyperbranched amino-organosilicon formaldehyde scavenger with the retention force and the hand feeling enhanced according to claim 6 is characterized in that: the process flow of the fabric finishing agent is as follows: two-dipping and two-rolling, wherein the rolling liquid rate is 95% -110% → pre-baking, the temperature is 105 ℃, the time is 2min → baking, and the temperature is 150-.

Technical Field

The invention particularly relates to a synthesis method and application of a hyperbranched amino organic silicon hand-holding-force-increasing formaldehyde scavenger.

Background

A formaldehyde scavenger: the formaldehyde acceptor is utilized to reduce the formaldehyde beam, and generally, a substance which is easy to react with formaldehyde is selected, so that the aim of removing the redundant formaldehyde of the mobile phone can be fulfilled. Compounds with an ═ N-H group are currently used. At present, most of the substances are urea, carbohydrazide and the like, but the substances are easy to remain in an aqueous solution after treatment, so that the nitrogen content in sewage is influenced, the application is very cautious at present, and the nitrogen content is required to be less than 30ppm by the textile dyeing and finishing industrial water pollutant discharge standard (GB 4278-. The hyperbranched aminoorganosilicon used in the subject contains a large amount of N-H groups and-NH groups₂And because formaldehyde belongs to micromolecular substances, the space bit group is small, the reaction is easy to occur, and the formaldehyde removal effect is good. Meanwhile, the scavenger is added with the finishing agent at the same time, and the catcher is non-alkaline, so that an acid catalyst cannot be passivated, and the pH value cannot be greatly reduced, so that the formaldehyde cannot be released by water.

The breaking strength, tearing strength and the like are obviously reduced in conventional finishing, the hand feeling is hard, a method of adding a softening agent is generally adopted, the friction coefficient of yarns in the fabric is reduced, the mobility of the yarns in the fabric is improved, uneven internal stress is reduced, more yarns bear the tensile force together, and the tearing strength and the breaking strength of the fabric are improved.

Therefore, the product is of an organic silicon structure, has a soft function, and can achieve multiple functions of maintaining strength, increasing hand feeling and reducing formaldehyde release.

Disclosure of Invention

The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides a synthesis method and application of a hyperbranched amino organic silicon hand-holding-force-increasing type formaldehyde trapping agent.

The technical scheme is as follows: a method for synthesizing hyperbranched amino organic silicon hand-holding-strength-enhanced formaldehyde scavenger comprises the following steps:

step one, synthesizing hydrogen-terminated silicone oil with molecular weight of 800:

with hydrogen-containing double end sockets and octamethylcyclotetrasiloxane (D)₄) Synthesizing hydrogen-terminated silicone oil with molecular weight of 800 by using concentrated sulfuric acid as a catalyst;

step two, synthesizing LDE-EPS (silicone oil 800):

(a) a device is set up, and a stirrer, a thermometer, a constant-pressure separating funnel and a condensing reflux pipe are matched with the four-mouth flask and stably set up;

(b) adding hydrogen-terminated silicone oil (molecular weight 800) and epoxy allyl glycidyl ether (molecular weight 600) into a four-neck flask according to a certain proportion, heating to a certain fixed reaction temperature, dropwise adding a metered catalyst into a system after the temperature is stable, and carrying out heat preservation reaction for a certain time;

(c) after the reaction is finished, adding a certain amount of allyl glycidyl ether AGE, heating to a certain reaction temperature, and continuously reacting for a period of time to obtain light yellow transparent LDE-EPS;

step three, synthesizing the HBP-ABP formaldehyde capture agent:

synthesizing HBP-ABP by taking LDE-EPS and diethylenetriamine as raw materials and controlling the ratio of reaction materials, the reaction temperature and the reaction time through nucleophilic addition reaction;

adding LDE-EPS and diethylenetriamine into a four-neck flask in proportion, heating to 50 ℃ firstly, reacting for 30min to fully mix the two raw materials to generate a monomer A and a monomer B, heating to a specified temperature, reacting for a period of time, and taking out to obtain the light yellow transparent HBP-ABP formaldehyde scavenger.

Further, in the second step (b), the fixed reaction temperature is 80 ℃, the catalyst is chloroplatinic acid, the dosage of the catalyst is 0.2 percent of the total amount of reactants, and the heat preservation reaction time is 3 hours.

Further, in the second step (b), the ratio of the terminal hydrogen-containing silicone oil (molecular weight 800) to the epoxy allyl glycidyl ether (molecular weight 600) is 1: 2.05, and 96.89 percent.

Further, in the second step (c), 5% of allyl glycidyl ether AGE with the molar mass of hydrogen-containing silicone oil is added, the reaction temperature is 90-95 ℃, the reaction time is 6.5 hours, and after the reaction is finished, the excessive allyl glycidyl ether and micromolecules are removed by pressure reduction and suction filtration.

Further, in the third step, the raw material n (LDE-EPS): n (diethylenetriamine) is 1:1.4, the reaction temperature is 70 ℃, the reaction time is 8h, the epoxy group conversion rate approaches 100 percent, the epoxy groups are basically and completely reacted, and the viscosity of a product system is 3960mpa · s.

An application of hyperbranched amino organosilicon hand-feeling-protecting and hand-feeling-increasing formaldehyde scavenger is characterized in that the HBP-ABP formaldehyde scavenger is added into a fabric finishing agent to prepare the fabric finishing agent, and the specific formula of the fabric finishing agent is as follows:

80-100g/L of dihydroxymethyl dihydroxy ethylene urea (2D resin);

NaH₂PO₄1％-2％；

20% -50% of HBP-ABP formaldehyde catching agent;

(2D resin dosage can be adjusted according to the hand feeling requirement)

And the penetrating agent JFC is 1-2 g/L.

Further, the process flow of the fabric finishing agent is as follows: two-dipping and two-rolling, wherein the rolling liquid rate is 95% -110% → pre-baking, the temperature is 105 ℃, the time is 2min → baking, and the temperature is 150-.

Has the advantages that: the invention synthesizes the finishing agent which has the advantages of keeping strong force, improving hand feeling and having the function of capturing formaldehyde, adopts a hyperbranched structure to introduce a large amount of primary amino groups and secondary amino groups which can react with the formaldehyde, and is added with proper organic silicon, thereby improving the hand feeling of fabrics, and simultaneously can be used as a strong protective agent to reduce strong damage.

Drawings

FIG. 1 is an infrared spectrum of a hydrogen-containing double head and a hydrosilylation product of the present invention;

FIG. 2 is an infrared spectrum of the hydrogen-containing double head and subsequent reaction of the product of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.