CN102504264B - Preparation method of flame retarding antibacterial agent - Google Patents

Abstract

The invention relates to a preparation method of a flame retarding antibacterial agent. The preparation method comprises the following steps: adding distilled water in 3-aminopropyltriethoxysilane for conducting hydrolysis reaction, then conducting polycondensation, adding dicyandiamide into the obtained ivory-white emulsion, conducting condensation and backflow on the mixture, then adding phosphorus pentoxide and finally obtaining colorless and transparent solution. The main product of the colorless and transparent solution is the flame retarding antibacterial agent. The flame retarding antibacterial agent can perform finishing to the cotton fabrics, so that the fabrics have double functions of bacteria resistance and flame retarding; and the obtained flame retarding antibacterial agent is safe and environment-friendly and is a novel dyeing and finishing auxiliary.

Description

A kind of preparation method of flame retardant type antibacterial agent

Technical field:

The invention relates to a preparation method of a flame-retardant antibacterial agent, and belongs to the technical field of development of new dyeing and finishing auxiliaries. It can be used as a functional finishing agent for cotton fabrics, endowing pure cotton fabrics with dual functions.

Background technique:

The invention adopts 3-aminopropyltriethoxysilane and dicyandiamide as raw materials, and uses phosphorus pentoxide hydrolyzed to phosphoric acid as an esterification agent to synthesize a silicon-containing antibacterial flame-retardant compound. The synthesized compound contains not only silicon, phosphorus, nitrogen and other flame retardant elements, but also antibacterial guanidine molecular structure, so as to obtain a multifunctional finishing agent, which endows the fabric with dual functions of antibacterial and flame retardant.

At present, domestic research on flame retardants has gradually turned to halogen-free flame retardants. Although halogen-containing flame retardants have high flame retardant properties and are added in a small amount, they have been widely used for a long time. However, when a fire breaks out, the decomposition and combustion of these materials will produce a large amount of irritating and corrosive hydrogen halide gas, which not only seriously hinders the evacuation of personnel and fire fighting, but also corrodes instruments and equipment, causing "secondary disasters" and burning The product has a long atmospheric life, seriously pollutes the atmospheric environment, and even destroys the ozone layer. At the same time, halogenated flame retardants may release halogenated diphenyldioxins and diphenylfurans during fire and incineration, which will damage the immune and regeneration systems of the human body. . Therefore, such flame retardants have been phased out and replaced by halogen-free flame retardants.

Silicon-based flame retardants have extremely high thermal stability, oxygen stability, and good flexibility due to the silicon-containing group, and can be introduced into the main chain and side chain of the fiber by polymerization, grafting, and cross-linking techniques. , and the products after thermal decomposition are mainly carbon dioxide, water vapor and silicon dioxide, so silicone flame retardants are considered to be a new generation of non-halogenated flame retardants that are efficient, eco-friendly, anti-melt droplet and smoke-suppressing. Flame retardant elements such as silicon, phosphorus, and nitrogen introduced in the present invention are in line with the development trend of flame retardants in my country.

Guanidine antibacterial agents are a kind of environmentally friendly antibacterial agents with good antibacterial properties. Since most organic antibacterial agents have toxic and side effects, they can cause skin diseases and are harmful to the human body (even some monomers have carcinogenic effects), poor heat resistance, It is easy to decompose, smelly, and has a short service life. After being treated with guanidine antibacterial agents on textiles, it is not only non-toxic (no carcinogenicity, mutagenesis, and teratogenicity to the human body), tasteless, non-irritating, high temperature resistance, and antibacterial. Good, and the washability is also very good, and the antibacterial effect is long-lasting. The guanidine group in the guanidine compound is an effective active group, which can interact with groups or elements in microorganisms and destroy its normal substance and energy metabolism. It is considered to be a better antibacterial finishing agent currently used. The method of using the guanidine structure introduced in the present invention as an antibacterial element conforms to the development trend of antibacterial agents and belongs to the development of environment-friendly reagents.

With the improvement of people's requirements for the wearability of textiles and their attention to functionality, textiles are increasingly developing towards multi-functionality. Multi-component and functionalization have become the mainstream of current textile product research and development. So far, there is no fiber that can fully satisfy people's multi-level and multi-functional needs for fabrics, so the research and development of new multi-functional textile fabrics for clothing has become a trend. The synthetic product involved in the present invention belongs to the reactive antibacterial flame retardant, has good durability, conforms to the current domestic research status on antibacterial flame retardants, and can endow the fabric with dual functions of antibacterial and flame retardant after functional finishing of pure cotton fabrics.

At present, domestic and foreign patents and documents have not reported the preparation and finishing method of the flame-retardant guanidine antibacterial agent involved in the present invention, and this finishing agent has wide application value and prospect in textile finishing.

Invention content:

The invention aims at synthesizing a novel multifunctional dyeing and finishing auxiliary agent, provides a method for synthesizing a flame-retardant antibacterial agent and finishing a cotton fabric, and can endow the cotton fabric with dual functions of antibacterial and flame retardancy.

The synthetic method of fire-retardant type antibacterial agent of the present invention operates as follows:

1. Take 1 times the molar amount of 3-aminopropyltriethoxysilane, put it into a three-necked flask, add 4.4 times the molar amount of distilled water in an ice-water bath (temperature 0-5°C), and drop dilute acetic acid to adjust the pH = 4-5, stir evenly to make it carry out hydrolysis reaction, the reaction time is 20min, obtain colorless transparent liquid A, gradually warm up to room temperature, add 1M NaOH solution to adjust PH = 8-9, add 0.05 times the molar amount of buffer agent CaCO ₃ Protect the silanol group, carry out the polycondensation reaction, the reaction time is 120min, obtain milky white emulsion, and its main product is B. The main reaction equation is as follows:

2. Adjust the pH of the product B solution to 7, weigh 2 times the molar amount of dicyandiamide, add it to the above-mentioned three-neck flask and stir evenly, fix it in a constant temperature water bath with an iron stand, under the protection of nitrogen, the temperature of the water bath is Keep at 60°C, condense and reflux for 60 minutes, add 4 times the molar amount of phosphorus pentoxide, and stir continuously during the reaction to make the reaction uniform. The reaction time is 50 minutes, and a colorless and transparent solution is obtained. The main product is C. Flammable antibacterial agent. The main reaction equation is as follows:

3, the flame retardant type antibacterial agent that the main product of synthesis is C is applied to pure cotton fabric as finishing liquid and is finished, and the pure cotton fabric of 1 weight part is immersed in the finishing liquid of 50 weight parts, constantly stirs with glass rod, makes Cotton fiber fully reacts with the finishing liquid, the treatment time is 30min, and then rolled with a small bench-type pneumatic electric padding machine, adjusting the pressure of the padding machine to 0.4Mpa, so that the excess rolling rate is 80%, two dipping and two rolling, at 80 ℃ Dry it in an oven for 3 minutes, then bake it at 160°C for 4 minutes, take it out, wash it with water, and then dry it. After finishing, the fabric can be endowed with dual functions of antibacterial and flame retardant.

Detailed ways

Example 1:

1. Fix a three-necked 200ml flask with an iron stand, install a nitrogen circulation protection device, take 10ml (0.04mol) of 3-aminopropyltriethoxysilane, put it into a three-necked flask, and place it in an ice-water bath (temperature 0-5 Add 40ml of distilled water under the temperature of ℃), add dilute acetic acid dropwise to adjust PH=4-5, stir evenly to make it undergo hydrolysis reaction, reaction time is 20min, and obtain colorless transparent liquid A, gradually warm up to room temperature, add 1M NaOH solution dropwise to adjust PH =8-9, add 0.2g buffer CaCO ₃ to protect silanol, carry out polycondensation reaction, reaction time 120min, obtain milky white emulsion, its main product is B.

2. Adjust the pH of the product B solution to 7, weigh 6.8g of dicyandiamide, add it to the above-mentioned three-neck flask and stir evenly, fix it in a constant temperature water bath with an iron stand, and keep the temperature of the water bath at 60°C, after reflux for 60 minutes, add 17.0g of phosphorus pentoxide, and stir continuously during the reaction to make the reaction go on evenly. The reaction time is 50 minutes, and a colorless and transparent solution is obtained. The main product is a flame-retardant antibacterial agent of C .

3, the flame retardant type antibacterial agent that the main product of synthesis is C is applied to pure cotton fabric as finishing liquid and finishes, bath ratio is 1: 50 (mass ratio of fabric and finishing liquid), constantly stirs with glass rod, makes cotton Fully react the fibers with the finishing solution, the treatment time is 30min, and then use a bench-top pneumatic electric small rolling machine to roll, adjust the rolling pressure to 0.4Mpa, so that the rolling rate is 80%, two dipping and two rolling, in the oven at 80 Dry it inside for 3 minutes, then bake it at 160°C for 4 minutes, take it out, wash it with water, and then dry it.

4. According to GB/T5455-1997 Textile Flame Retardant Performance Test Oxygen Index Method Test the limit oxygen index of the finished fabric. The antibacterial performance was tested according to GB/T20944.1-2007 Evaluation method of textile antibacterial performance.

Antibacterial performance test (qualitative):

H=(D-d)/2

H ----- the width of the antibacterial zone;

D ----- the average value of the outer diameter of the antibacterial zone;

d------sample diameter.

It can be seen from the data that the bacteriostatic zone width H=1-1.5mm was tested by using Gram-negative Escherichia coli to test the sample after finishing. The bacteriostatic zone width H=1mm of the sample after Gram-positive Staphylococcus aureus treatment. According to GB/T 20944.1-2007, the width of the antibacterial zone is greater than or equal to 1mm, and there is no bacterial reproduction under the sample, indicating that the antibacterial effect is good.

Inhibition rate Escherichia coli 97% Staphylococcus aureus 96%

According to GB/T20944.2-2007 Evaluation of antibacterial properties of textiles Part 2: Absorption method, use Gram-negative Escherichia coli to test the finished sample, and the antibacterial rate is 97%. The bacteriostatic rate of the sample treated with Gram-positive Staphylococcus aureus was 96%.

Flame retardant performance test:

According to GB/T 5454-1997, when the LOI ≥ 26% belongs to the flame retardant material, the limiting oxygen index LOI of the sample after finishing is 45.7%, indicating that after the cotton fabric is treated with the auxiliary agent of the present invention, the fabric has higher flame retardancy performance.

Example 2:

1. Fix a three-necked 200ml flask with an iron stand, install a nitrogen circulation protection device, take 10ml (0.04mol) of 3-aminopropyltriethoxysilane, put it into a three-necked flask, and place it in an ice-water bath (temperature 0-5 Add 40ml of distilled water under the temperature of ℃), add dilute acetic acid dropwise to adjust PH=4-5, stir evenly to make it undergo hydrolysis reaction, reaction time is 20min, and obtain colorless transparent liquid A, gradually warm up to room temperature, add 1M NaOH solution dropwise to adjust PH =8-9, add 0.2g buffer CaCO ₃ to protect silanol, carry out polycondensation reaction, reaction time 120min, obtain milky white emulsion, its main product is B.

2. Adjust the pH of the product B solution to 7, weigh 6.8g of dicyandiamide, add it to the above-mentioned three-neck flask and stir evenly, fix it in a constant temperature water bath with an iron stand, and keep the temperature of the water bath at 60°C, after reflux for 60 minutes, add 8.5g of phosphorus pentoxide, and stir continuously during the reaction to make the reaction go on evenly. The reaction time is 50 minutes, and a colorless and transparent solution is obtained. The main product is a flame-retardant antibacterial agent of C .

3. The flame-retardant antibacterial agent whose main product is synthesized is C as a finishing liquid and applied to pure cotton fabrics for finishing. The bath ratio is 1:50 (mass ratio of fabric to finishing agent), and it is constantly stirred with a glass rod to make the cotton fabric Fully react the fibers with the finishing solution, the treatment time is 30min, and then use a bench-top pneumatic electric small rolling machine to roll, adjust the rolling pressure to 0.4Mpa, so that the rolling rate is 80%, two dipping and two rolling, in the oven at 80 Dry it inside for 3 minutes, then bake it at 160°C for 4 minutes, take it out, wash it with water, and then dry it.

4. According to GB/T5455-1997 Textile Flame Retardant Performance Test Oxygen Index Method Test the limit oxygen index of the finished fabric. The antibacterial performance was tested according to GB/T20944.1-2007 Evaluation method of textile antibacterial performance.

Antibacterial performance test (qualitative):

H=(D-d)/2

H ----- the width of the antibacterial zone;

D ----- the average value of the outer diameter of the antibacterial zone;

d------sample diameter.

It can be seen from the data that the bacteriostatic zone width H=1-1.25mm was tested by using Gram-negative Escherichia coli to test the sample after finishing. The bacteriostatic zone width H=1mm of the sample after Gram-positive Staphylococcus aureus treatment. According to GB/T20944.1-2007, the width of the antibacterial zone is greater than or equal to 1mm, and there is no bacterial reproduction under the sample, indicating that the antibacterial effect is good.

Inhibition rate Escherichia coli 95% Staphylococcus aureus 94%

According to GB/T20944.2-2007 Evaluation of Antibacterial Properties of Textiles Part 2: Absorption Method, Gram-negative Escherichia coli was used to test the finished sample, and the antibacterial rate was 95%. The bacteriostatic rate of the sample treated with Gram-positive Staphylococcus aureus was 94%.

Flame retardant performance test:

After finishing the sample Blank cotton sample LOI 30% 19% Smoldering length 20mm burn out

According to GB/T 5454-1997, when the LOI ≥ 26% is a flame retardant material, the limiting oxygen index LOI of the sample after finishing is 30%, indicating that after the cotton fabric is treated with the auxiliary agent of the present invention, the fabric has higher flame retardancy performance.

Claims (1)

1. a preparation method of flame-retardant type antibacterial agent, is characterized in that: The first step: Take 1 times the molar amount of 3-aminopropyltriethoxysilane, put it into a three-necked flask, add 4.4 times the molar amount of distilled water in an ice-water bath at 0°C, and add dilute acetic acid dropwise to adjust the pH=4- 5. Stir evenly to carry out the hydrolysis reaction. The reaction time is 20 minutes to obtain a colorless transparent liquid A. Gradually warm up to room temperature, add 1M NaOH solution to adjust the pH = 8-9, and add 0.05 times the molar amount of buffer CaCO ₃ to protect the silanol group , carry out polycondensation reaction, reaction time 120min, obtain milky white emulsion, its main product is B; Main reaction equation is as follows: Step 2: Adjust the pH of the product B solution to 7, weigh 2 times the molar amount of dicyandiamide, add it into the above-mentioned three-neck flask and stir evenly, fix it in a constant temperature water bath with an iron stand, and place it in a water bath under the protection of nitrogen. The temperature of the pot was kept at 60°C. After condensing and refluxing for 60 minutes, 4 times the molar amount of phosphorus pentoxide was added, and stirring was continued during the reaction to make the reaction proceed evenly. The reaction time was 50 minutes, and a colorless and transparent solution was obtained. The main product was C flame retardant antibacterial agent; the main reaction equation is as follows:

The third step: the flame retardant antimicrobial agent whose main product is C is applied to the pure cotton fabric as the finishing liquid for finishing, and the pure cotton fabric of 1 weight part is immersed in the finishing liquid of 50 parts by weight, and constantly stirred with a glass rod , to make the cotton fiber fully react with the finishing solution, the treatment time is 30min, and then use a desktop pneumatic electric small paddle to press, adjust the pressure of the paddle to 0.4Mpa, so that the excess rate is 80%, two dipping and two rolling, at 80 Dry in an oven at ℃ for 3 minutes, then bake at 160℃ for 4 minutes, take it out, wash it with water, and then dry it.