CN103074759B - The preparation method of metal ion flame retardant modification cotton fabric - Google Patents

Abstract

The invention relates to a method for preparing flame-retardant modified cotton fabrics using metal ions. (1) introducing metal ions into cotton fabrics by chemical means can obtain durable flame-retardant cotton fabrics; (2) using physical means to make The metal compound is adsorbed on the cotton fabric, which has the advantages of wide variety of flame retardants, easy availability, simple operation of flame retardant modification, and obvious flame retardant effect. Even ordinary people can use this method to process cotton fabrics (clothes, quilts, bed sheets, etc.) when encountering a fire, to obtain flame-retardant and fire-resistant protective products, and to reduce fire damage to personal property. The present invention uses metal ions or metal compounds as flame retardants for cotton fabrics, which is a brand-new flame retardant method and technology, which can avoid the use of traditional phosphorus, nitrogen and halogen flame retardants, and reduce the production process and use process. And possible environmental pollution problems after disposal.

Description

Preparation method of metal ion flame retardant modified cotton fabric

technical field

The invention belongs to the technical field of flame-retardant textiles, in particular to a preparation method of metal ion flame-retardant modified cotton fabrics.

Background technique

Cotton fabric is a natural, renewable and environmentally friendly textile and clothing material. It has the advantages of good skin contact, comfortable wearing, and good hygroscopicity. Therefore, it is still irreplaceable by synthetic fiber fabrics in the fields of textile and clothing. But cotton fabric is very flammable, and it is easy to become a fire point to cause a fire, especially as cotton products such as clothing and bed sheets used by children, the elderly and patients, which are more likely to cause personal injury when encountering a fire. The fires caused by it are also increasing, so countries have successively proposed flame-retardant requirements for cotton textiles.

The flame retardant of cotton fabric is mainly modified by post-finishing method, which is widely used. The technological process of the post-finishing flame-retardant modification method is relatively simple, and it has been applied to commercial production in various textiles. The flame retardants used in the traditional flame retardant modification of cotton fabrics are basically compounds containing elements such as phosphorus, nitrogen, and halogen. At present, the most famous flame-retardant cotton fabric products in the international market are PROBAN and PYROVATEX. PROBAN flame-retardant cotton fabric is mainly obtained by treating cotton fabric with low-molecular-weight preshrunk product of tetrakishydroxymethyl phosphorus chloride and amide, and then treated with ammonia fumigation. PYROVATEX flame retardant cotton fabric is treated with Pyrovatex CP flame retardant N-hydroxymethyl-3-(dimethoxyphosphono)propionamide and its technology. These two flame-retardant cotton fabrics have the advantages of good flame-retardant effect, strong flame-retardant durability, and washing resistance, but also have disadvantages such as formaldehyde content, fabric feel, and loss of strength. Domestic invention patent applications CN100494557C, CN102162188A, etc. all adopt flame retardants containing phosphorus and nitrogen. Although these flame retardant technologies all use non-halogen flame retardants, due to the use of phosphorus flame retardants, there are also environmental pollution problems in the production process, fire burning and disposal. Such as the eutrophication caused by phosphorus in the water body, and the possibility of entering the human body through the food chain and so on. Emphasis on environmental issues and the development of environmentally friendly flame retardants and flame retardant technologies are also the development direction of the flame retardant field. In recent years, some new silicon-based and boron-based flame retardants have also appeared. CN101413214A introduces silicon into the phosphorus/nitrogen flame retardant. The synergistic effect of silicon flame retardant can reduce the amount of phosphorus flame retardant, but it does not Fundamentally solve the problem of using phosphorus flame retardants.

Contents of the invention

The present invention proposes a brand-new idea and method, abandons the traditional flame retardants containing halogen, phosphorus, nitrogen, sulfur, etc., and invents a new method and new technology of metal ion flame-retardant modified cotton fabric. The present invention introduces metal ions into the cotton fabric through chemical or physical means, and the metal ions act as flame retardants to endow the cotton fabric with a good flame retardant effect without adding any traditional flame retardants.

In order to achieve the purpose of the above invention, the flame-retardant modification method of cotton fabric provided by the present invention, that is, the method of introducing metal ions into cotton fabric, includes chemical means and physical means.

The chemical means of the present invention is to carry out alkalization and carboxymethylation treatment on the cotton fabric, and the metal ions are grafted onto the cotton macromolecules through chemical bonds, so as to achieve the purpose of introducing metal ions into the cotton fabric, and the obtained flame-retardant cotton fabric has durability. The chemical flame-retardant modification steps of metal ion flame-retardant cotton fabrics include: first carry out surface alkalization of cotton fabrics in ethanol solution of sodium hydroxide, add monochloroacetic acid in the solution after alkalization for etherification, and sodium ions Grafted to the cotton macromolecular chain, and then washed and vacuum-dried to obtain a sodium ion flame-retardant cotton fabric product. The prepared sodium ion flame-retardant cotton fabric is ion-exchanged with other metal ions in ethanol solution to obtain other metal ion flame-retardant cotton fabric products. What the present invention is used for ion exchange can be metal ion compound, as chloride, hydroxide and carbonate etc., used metal comprises sodium, potassium, calcium, magnesium, aluminum, zinc, barium, iron, cobalt, copper etc. Wait.

The physical means of the present invention is to directly adsorb the metal compound on the cotton fabric, and the chemical flame-retardant modification step of the metal ion flame-retardant cotton fabric includes: first dissolving the metal compound in water, and configuring it as a flame-retardant treatment liquid; then the cotton fabric Soaking in flame retardant treatment liquid, dipping and padding, and then drying to obtain metal ion flame retardant cotton fabric products. Metal compound flame retardants can be metal salts, metal hydroxides, metal oxides, etc. Metal salts can be inorganic or organic. The metal ions used may be sodium, potassium, calcium, magnesium, aluminum, zinc, iron, barium, iron, cobalt, copper and the like.

Compared with the prior art, the present invention has a wide variety of metal compound flame retardants, is easy to obtain, and is easy to operate. Even ordinary people can use this method to soak cotton fabrics (clothes, quilts, bed sheets, etc.) In the aqueous solution of sodium carbonate (soda, edible soda ash) commonly used at home, it is easy to obtain practical flame-retardant and fire-resistant protective products to reduce fire damage to personal property.

detailed description

The present invention will be described in more detail and effect description below in conjunction with specific embodiments, it should be pointed out that the embodiments listed here are only illustrative and do not mean to limit the scope of the present invention. requirements and their equivalents.

Example 1:

Add 25g of cotton fabric to 400mL of sodium hydroxide (0.05g/mL) in ethanol solution, and alkalize the fabric at 60°C for 4h. After the alkalization was completed, 20 g of chloroacetic acid was added into the reaction vessel, and stirred to dissolve it. After etherification at 65°C for 3 hours, add 10g of sodium hydroxide for secondary alkalinization, after 2 hours of reaction, neutralize with acetic acid to pH = 7, wash twice with 70% ethanol aqueous solution, and wash with 90% ethanol Once, a flame-retardant cotton fabric with a sodium ion content of 4.40% was obtained after drying. The flame-retardant cotton fabric is ignited with a fire source, and extinguished after leaving the fire source. The limiting oxygen index is 27.0%.

Example 2:

Add 25g of cotton fabric to 400mL of sodium hydroxide (0.08g/mL) in ethanol solution, and alkalize the fabric at 60°C for 4h. After alkalization was completed, 30 g of chloroacetic acid was added into the reaction vessel, and stirred to dissolve it. After etherification at 65°C for 3 hours, add 15g of sodium hydroxide for secondary alkalinization, after 2 hours of reaction, neutralize with acetic acid to pH = 7, wash twice with 70% ethanol aqueous solution, and wash with 90% ethanol Once, a flame-retardant cotton fabric with a sodium ion content of 6.39% was obtained after drying. The flame-retardant cotton fabric is ignited with a fire source, and extinguished after leaving the fire source. The limiting oxygen index is 35.0%.

Example 3:

Take 25g of the cotton fabric modified by sodium ion flame retardant in Example 2, use 400mL of ethanol as the medium, add 30g of calcifying agent and stir to dissolve it, react at 60°C for 4h, wash twice with 70% ethanol aqueous solution, 90 % ethanol, washed once, and dried to obtain a flame-retardant cotton fabric with a calcium ion content of 2.27%. It is ignited with a fire source and self-extinguishes after leaving the fire source. The limiting oxygen index is 28.5%.

Example 4:

Take 25g of the cotton fabric modified by sodium ion flame retardant in Example 2, use 400mL of ethanol as the medium, add 30g of magnesium chloride and stir to dissolve it, react at 60°C for 4h, wash twice with 70% ethanol aqueous solution, wash with 90% ethanol % ethanol was washed once, and the cotton fabric modified by magnesium ion flame retardancy was obtained after drying. Ignited with a fire source, smoldering after leaving the fire source for a period of time, the limiting oxygen index is 24.5%.

Example 5:

Take 25g of the sodium ion flame-retardant cotton fabric in Example 2, use 400mL of ethanol as the medium, add 30g of aluminum chloride and stir to dissolve it, react at 60°C for 4 hours, wash twice with 70% ethanol aqueous solution, wash with 90% After washing with ethanol once, the cotton fabric modified by aluminum ion was obtained after drying. Ignited with a fire source, smoldering after leaving the fire source for a period of time, the limiting oxygen index is 25.2%.

Embodiment 6:

Add 25g of cotton fabric to 400mL of potassium hydroxide (0.05g/mL) ethanol solution, and alkalize the fabric for 4 hours at 60°C. After the alkalization is completed, add 20g of chloroacetic acid to the reaction vessel and stir to dissolve it. After etherification at 65°C for 3 hours, add 10g of potassium hydroxide for secondary alkalinization, and after 2 hours of reaction, neutralize with acetic acid to pH = 7, then wash twice with 70% ethanol aqueous solution, 90% Washed once with ethanol, then suction filtered and dried in vacuum to obtain a flame-retardant cotton fabric with 0.97% potassium ions. It is ignited with a fire source and extinguished after leaving the fire source. The limiting oxygen index is 28.1%.

Embodiment 7:

Weigh 15g of sodium carbonate and prepare 300mL of sodium carbonate aqueous solution as a flame retardant finishing solution. Soak 10g of cotton fabric in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, and soak for 30 minutes at 75°C, one dip and one press, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 27%.

Embodiment 8:

Weigh 30g of sodium carbonate and make 300ml of sodium carbonate aqueous solution as flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 75°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 30%.

Embodiment 9:

Weigh 40g of sodium formate and make 300ml of sodium formate aqueous solution as a flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 60°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 28%.

Example 10:

Weigh 30g of potassium formate and make 300ml of potassium formate aqueous solution as flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 60°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 50° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 27%.

Example 11:

Weigh 20g of calcium chloride and prepare 300mL of calcium chloride aqueous solution as a flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 60°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 31%.

Example 12:

Weigh 40g of calcium chloride and make it into 300mL of calcium chloride aqueous solution as a flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 60°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 38%.

Example 13:

Take by weighing 40g of magnesium chloride, be made into 300ml of magnesium chloride aqueous solution, as flame retardant finishing solution. Soak 10g of cotton cloth in the above-mentioned flame-retardant finishing solution at a bath ratio of 1:30, soak for 30 minutes at 60°C, dip and press once, and the squeeze rate is 85%. Then the cotton cloth was dried in an oven at 60° C. for 2 hours to obtain a flame-retardant cotton fabric with a limiting oxygen index of 36%.

Claims (1)

1. the preparation method of flame-proof cotton fabric one kind metal ion-modified, it is characterised in that: comprised the following steps successively by chemical means its preparation method:

Step 1, taking bafta 25g, and be placed in the alcoholic solution containing 400mL sodium hydroxide to carry out surface alkalization, alkalization temperature is 60 DEG C, and alkalization time is 4h；

Step 2, connecing step 1, after having alkalized, add 30g chloroacetic acid and carry out etherificate in the solution after above-mentioned alkalization, etherification temperature is 65 DEG C, etherification time is 3h；

After step 3, etherificate complete, add 15g sodium hydroxide and carry out double alkalisation, after reaction 2h, be neutralized to pH=7 with acetic acid, sequentially pass through washing, vacuum drying obtains the flame-proof cotton fabric that sodium ion modifiies；Its limited oxygen index of obtained flame-retardant bafta is 35.0%.