CN105780453B - One kind is based on antiflaming finishing agent, its preparation method and its application of montmorillonite/DNA hydrosols - Google Patents

Abstract

The invention discloses a flame retardant finishing agent based on montmorillonite/DNA hydrosol. The content of each component in the flame retardant finishing agent is as follows in parts by weight: 1 part by weight of montmorillonite, 0.1- 10 parts by weight of DNA, 0.1-10 parts by weight of coupling agent. The preparation method of the above flame retardant finishing agent comprises: the montmorillonite is treated with hydrogen peroxide, centrifuged and treated with sodium carbonate solution to obtain a stripped montmorillonite sample; the stripped montmorillonite is dispersed in an ethanol aqueous solution, and then coupled agent to obtain modified montmorillonite; the modified montmorillonite is mixed with DNA to obtain a composite hydrosol. The composite hydrosol prepared above is used as a flame-retardant finishing agent in the post-finishing of polyester-cotton fabrics. The montmorillonite platelets in the composite hydrosol are assembled on the surface of polyester-cotton fibers, so that the polyester-cotton fabrics after finishing have certain flame-retardant properties. combustion function. The flame retardant finishing agent can reduce the addition amount of the flame retardant in the flame retardant system, and guarantee the mechanical properties of the material while ensuring the flame retardant effect.

Description

A kind of flame retardant finishing agent based on montmorillonite/DNA hydrosol, its preparation method and its application

technical field

The invention relates to the field of functional textiles, in particular to a flame retardant finishing agent based on montmorillonite/DNA hydrosol, its preparation method and its application.

Background technique

Due to the complementary physical and chemical properties of polyester and cotton components, polyester-cotton blended fabrics not only have the advantages of high strength, good abrasion resistance, high color fastness, good acid and heat resistance, but also have excellent hygroscopicity, air permeability and soft hand feeling. Comfortable and other wearing properties, widely used in the clothing industry and decoration fields. However, due to the high flammability of polyester-cotton fabrics due to the "wick effect" when burning, once it catches fire, it is difficult to extinguish, and it is easy to cause fires, leaving a lot of safety hazards in daily life, so its application is limited. According to the combustion and flame retardant mechanism of cotton fiber and polyester, the purpose of flame retardant is generally achieved by performing flame retardant post-treatment on the fabric.

Foreign polyester-cotton blended fabric flame retardants can be classified into the following two categories: phosphorus and nitrogen-containing flame retardant series, flame retardant series with halogen (bromine) added to phosphorus and nitrogen-containing flame retardants, and antimony and bromine-containing compounds Flame retardant series. Commonly used phosphorus nitrogen flame retardants are N-methylol compounds (such as DMDHEU), tetrakis hydroxymethyl phosphonium chloride (THPC), trimethylol melamine (TMM), trimethyl phosphate (TMP ), THPN (pre-condensation of tetrahydroxymethylphosphonium salt THPS and ammonia), etc. When the 50/50 polyester-cotton blended fabric is finished by THPN, urea and TMM, when the application amount reaches 20-30%, high flame retardancy can be obtained, but at this time the fabric feels a little hard, and it is difficult to adapt to the use requirements of various aspects . Halogenated flame retardants are currently the most widely used flame retardants for polyester-cotton blended fabrics, including bromine and chlorine, and bromine-antimony composite flame retardants are commonly used. Commonly used bromides include decabromodiphenyl ether, hexabromocyclododecane, etc., and antimony compounds are mainly antimony trioxide and antimony pentoxide. Derivatives of bromine compounds and antimony trioxide act synergistically, and the padding and baking process is used to obtain fabrics with LOI ≥ 27%, damage length < 150 cm, after-flame time ≤ 5s, and smoldering time ≤ 5s, which has good Flame retardant effect. However, the disadvantage of these flame retardants is that they generate a large amount of smoke when they burn, and produce toxic, harmful, and strongly corrosive halides.

For a long time, the developed polyester-cotton fabric flame retardant finishing technology and its flame retardant properties are difficult to meet the requirements of some applications. The existing problems are mainly that the fabric feel or mechanical strength after finishing are not satisfactory, and secondly, the production ecology needs to be improved. The application of the present invention is based on the requirements of environmental protection and sustainable development. The halogen-free flame retardant system has very broad development prospects. The naturally occurring layered clay-montmorillonite belongs to the inorganic nano flame retardant and is widely distributed in the earth's crust. With excellent mechanical properties, gas barrier and flame retardant effects, it can be used as a new generation of textile flame retardants.

Contents of the invention

Aiming at the deficiencies in the prior art, the present invention proposes a flame retardant finishing agent based on montmorillonite/DNA hydrosol, its preparation method and its application in the finishing of polyester-cotton fabrics, the flame retardant finishing agent can reduce the The amount of flame retardant added to the flame retardant system can ensure the mechanical properties of the material while ensuring the flame retardant effect.

The technical solution adopted by the present invention to solve the technical problem is: a flame retardant finishing agent based on montmorillonite/DNA hydrosol, the flame retardant finishing agent mainly includes the following components: montmorillonite, DNA, coupling agent; In terms of parts by weight, the content of each component in the flame retardant finishing agent is as follows: 1 part by weight of montmorillonite, 0.1-10 parts by weight of DNA, and 0.1-10 parts by weight of coupling agent.

Further, the montmorillonite is commercialized montmorillonite which is stripped and modified to obtain nano-montmorillonite; the average wafer thickness of the modified nano-montmorillonite is less than 25nm. The thickness of the modified nano-montmorillonite sheet becomes smaller, and it can be more evenly coated on the surface of the fabric after finishing, which improves the uniformity of the distribution of the montmorillonite platelets on the surface of the fabric, and is more conducive to the coating of montmorillonite. The improvement of the binding force between the film and the fiber has a certain flame-retardant and heat-insulating effect on the polyester-cotton fabric when the flame contacts it.

Further, the coupling agent is at least one of a silane coupling agent or a titanate coupling agent. The role of the coupling agent is to improve the interface between inorganic and organic substances, thereby greatly improving the performance of composite materials, such as physical properties, electrical properties, thermal properties, optical properties, etc.

Preferably, the silane coupling agent is KH550, KH560, and the titanate coupling agent is HY311.

DNA, also known as deoxyribonucleic acid, is a molecule with a double-stranded structure composed of deoxyribonucleotides (composition: deoxyribose, phosphoric acid and four nitrogenous bases). DNA is a double helix structure, which is called B-type water-binding DNA. DNA contains a large number of polar groups such as amino groups and carboxyl groups, and a large number of hydrogen bonds are formed during the combination of modified montmorillonite and fabrics. A large amount of phosphorus and nitrogen elements in the DNA molecule play a synergistic role in flame retardancy when subjected to heat attack. In the phosphorus-nitrogen composite system, phosphorus is used as an acid source. Nitrogen is used as a gas source to release non-combustible gas during thermal decomposition, which can make the above-mentioned charcoal layer expand and foam, and finally form an expanded charcoal layer. The expanded carbon layer can effectively isolate material exchange and heat exchange, so as to achieve a good flame retardant effect.

A preparation method of a flame retardant finishing agent based on montmorillonite/DNA hydrosol, the preparation method mainly includes the following steps:

1) Add 1 part by weight of montmorillonite to 10-100 parts by weight of 30% hydrogen peroxide, react at -10-30°C for 24-100 h, and centrifuge at 3000-9000 r/min for 5-60 minutes , the separated precipitate was redispersed in 5-30% sodium carbonate solution, stirred for 2-20 hours, ultrasonically treated at 5-50KHz for 0.5-10 hours, and centrifuged at 3000-9000 r/min to obtain the stripped Montmorillonite samples;

2) Disperse 1 part by weight of the stripped montmorillonite obtained in 1) in 5-150 parts by weight of 75% ethanol aqueous solution, stir evenly, heat to 30-80°C, and then add 0.1-10 parts by weight of Coupling agent, stirred and reacted for 1 to 6 hours to obtain a modified montmorillonite sample;

3) Mix 1 part by weight of modified montmorillonite obtained in 2) with 0.1-10 parts by weight of DNA, and stir at 0-60°C for 0.5-6 hours to prepare a composite hydrosol of montmorillonite and DNA, which is Flame retardant finishing agent based on montmorillonite/DNA hydrosol.

An application of a flame retardant finishing agent based on montmorillonite/DNA hydrosol, the flame retardant finishing agent is mainly used in the post-finishing process of polyester-cotton fabrics. The application of the flame retardant finishing agent mainly includes the following steps: in parts by weight, 1 part of polyester cotton cloth washed with acetone is immersed in 30 to 150 parts of montmorillonite and DNA composite hydrosol under a certain tension condition, Dry at ~50°C to promote the assembly of montmorillonite platelets in the composite hydrosol on the surface of polyester-cotton fibers, and obtain polyester-cotton fabrics with a certain flame-retardant function.

The beneficial effects of the present invention are: compared with the prior art, the present invention selects a kind of green, environment-friendly composite sol prepared by stripping and modifying montmorillonite and DNA, and adds a coupling agent to improve the montmorillonite Composite with DNA; when finishing on polyester-cotton fabrics, it can achieve a better flame-retardant effect with a small amount, which meets the needs of the development of green finishing agents. At the same time, it has little impact on the mechanical properties of the material, improving the flame-retardant effect while It can also maintain the better strength of the fabric.

Detailed ways

The present invention will be further described below in conjunction with embodiment. The consumption of each material in the following examples is all in parts by weight.

Example 1

Disperse 1 part of montmorillonite in 30 parts of 30% hydrogen peroxide, let stand at 4°C for 72 h, centrifuge at 5000 r/min for 20 min, and redisperse the separated precipitate in 10% sodium carbonate solution , stirred for 20 h, ultrasonicated at 20KHz for 6 h, and centrifuged at 6000 r/min to obtain a stripped montmorillonite sample; 1 part of stripped montmorillonite was dispersed in 50 parts of 75% ethanol aqueous solution, stirred Evenly, heat to 70°C, then add 0.1 part of KH560 silane coupling agent, stir and react for 3 hours to obtain a modified montmorillonite sample; mix 1 part of modified montmorillonite with 2 parts of DNA, and stir at 60°C 2 h, the composite hydrosol of montmorillonite and DNA was prepared. One part of polyester-cotton cloth washed with acetone was immersed in 50 parts of composite hydrosol under certain tension conditions, and dried at 30 °C to promote the assembly of montmorillonite platelets on the surface of polyester-cotton fibers to obtain composite hydrosol-treated polyester-cotton fabrics. fabric.

Example 2

Disperse 1 part of montmorillonite in 40 parts of 30% hydrogen peroxide, let it stand at 4°C for 72 h, centrifuge at 5000 r/min for 20 min, and redisperse the separated precipitate in 10% sodium carbonate solution , stirred for 20 h, ultrasonicated at 20KHz for 6 h, and centrifuged at 6000 r/min to obtain a stripped montmorillonite sample; 1 part of stripped montmorillonite was dispersed in 50 parts of 75% ethanol aqueous solution, stirred uniform, heated to 70°C, then added 0.2 parts of HY311 coupling agent, stirred and reacted for 3 h to obtain a modified montmorillonite sample; mixed 1 part of modified montmorillonite with 2 parts of DNA, and stirred at 60°C for 2 h, Composite hydrosol of montmorillonite and DNA was prepared. 1 part of polyester-cotton cloth washed with acetone is immersed in 100 parts of composite hydrosol under a certain tension condition, and dried at 40°C to promote the assembly of montmorillonite platelets on the surface of polyester-cotton fibers, and obtain composite hydrosol-treated polyester-cotton fabrics. fabric.

Example 3

The difference from Example 1 is that 1 part of polyester cotton cloth washed with acetone is immersed in 100 parts of composite hydrosol under certain tension conditions, and the rest of the steps are the same as in Example 1.

Example 4

Disperse 1 part of montmorillonite in 50 parts of 30% hydrogen peroxide, let stand at 4°C for 72 h, centrifuge at 5000 r/min for 20 min, and redisperse the separated precipitate in 5% sodium carbonate solution , stirred for 20 h, ultrasonicated at 20KHz for 6 h, and centrifuged at 6000 r/min to obtain a stripped montmorillonite sample; disperse 1 part of stripped montmorillonite in 100 parts of 75% ethanol aqueous solution, stir Evenly, heat to 80°C, then add 0.2 parts of KH560 silane coupling agent, stir and react for 3 hours to obtain a modified montmorillonite sample; mix 1 part of modified montmorillonite with 2 parts of DNA, and stir at 60°C 2 h, the composite hydrosol of montmorillonite and DNA was prepared. 1 part of polyester-cotton cloth washed with acetone is immersed in 100 parts of composite hydrosol under a certain tension condition, and dried at 40°C to promote the assembly of montmorillonite platelets on the surface of polyester-cotton fibers, and obtain composite hydrosol-treated polyester-cotton fabrics. fabric.

Taking the polyester-cotton fabric gained in Example 4 as an example to carry out material performance characterization, as follows:

Preparation and after-finishing process conditions are all identical with embodiment 4 under the situation, test one is to investigate the carbonized area of the polyester-cotton fabric after burning before and after finishing with the composite finishing agent of different montmorillonite content, test two is to investigate the effect of different montmorillonite content The tensile strength at break of polyester-cotton fabrics before and after finishing with composite finishing agent, see Table 1 and Table 2 for specific comparative test data.

Table 1 The carbonization area of polyester-cotton fabrics after being assembled with different contents of montmorillonite and DNA

From the data in Table 1, it can be seen that the carbonized area of the polyester-cotton raw fabric is 58.44 cm², and the fabric sample is more damaged; the carbonized area of the fabric assembled with 0.1g montmorillonite and 0.2g DNA is 21.59 cm², which is relatively larger than the original fabric. Good flame retardant effect; when the content of montmorillonite gradually increased to 0.5g and 0.9g, the carbonized area decreased to 14.21 cm² and 6.57 cm² respectively, indicating that the ability of the finished fabric to resist flame combustion is gradually enhanced, that is, Within a certain range, the higher the content of montmorillonite in the composite finishing agent, the better the flame retardant effect.

Tensile strength at break of polyester-cotton fabrics after table 2 treatment and before treatment

Numbering Montmorillonite content (g) DNA content (g) Average tensile strength (N) Strength change rate (%) A / / 478.2±5.0 / C 0.1 0.2 479.4±5.2 0.24% D. 0.5 0.2 501.9±4.9 4.94% E. 0.9 0.2 527.3±4.1 10.25%

It can be seen from Table 2 that the polyester-cotton fabric assembled with 0.1g montmorillonite and 0.2g DNA has no obvious change in strength compared with the untreated polyester-cotton fabric; when the montmorillonite content gradually increases to 0.5g and 0.9g , the average strength of polyester-cotton fabrics is slightly improved. It can be seen that the composition and process of the finishing agent explored in the present invention will not have a great impact on the strength of the fabric during use.

The above embodiments are only used to illustrate the present invention, but not to limit the present invention. Those of ordinary skill in the relevant technical field can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all Equivalent technical solutions also belong to the category of the present invention, and the scope of patent protection of the present invention should be defined by the claims.

Claims (3)

1. A flame retardant finishing agent based on montmorillonite/DNA hydrosol, characterized in that: the flame retardant finishing agent mainly comprises the following components: montmorillonite, DNA, coupling agent; in parts by weight, The contents of each component in the flame retardant finishing agent are as follows: 1 part by weight of montmorillonite, 0.1 to 10 parts by weight of DNA, and 0.1 to 10 parts by weight of coupling agent; the montmorillonite is The commercialized montmorillonite is stripped and modified to obtain nano-montmorillonite; the average wafer thickness of the modified nano-montmorillonite is less than 25nm; the coupling agent is a silane coupling agent or a titanate At least one of the coupling agents; the silane coupling agent is KH550, KH560, the titanate coupling agent is HY311; the flame retardant finishing agent based on montmorillonite/DNA hydrosol The preparation method mainly comprises the following steps: 1) Add 1 part by weight of montmorillonite to 10-100 parts by weight of 30% hydrogen peroxide, react at -10-30°C for 24-100 h, and centrifuge at 3000-9000 r/min for 5-60 minutes , the separated precipitate was redispersed in 5-30% sodium carbonate solution, stirred for 2-20 hours, ultrasonically treated at 5-50KHz for 0.5-10 hours, and centrifuged at 3000-9000 r/min to obtain the stripped Montmorillonite samples; 2) Disperse 1 part by weight of the stripped montmorillonite obtained in 1) in 5-150 parts by weight of 75% ethanol aqueous solution, stir evenly, heat to 30-80°C, and then add 0.1-10 parts by weight of Coupling agent, stirred and reacted for 1 to 6 hours to obtain a modified montmorillonite sample; 3) Mix 1 part by weight of modified montmorillonite obtained in 2) with 0.1-10 parts by weight of DNA, and stir at 0-60°C for 0.5-6 hours to prepare a composite hydrosol of montmorillonite and DNA, which is Flame retardant finishing agent based on montmorillonite/DNA hydrosol. 2. An application of the flame retardant finishing agent based on montmorillonite/DNA hydrosol as claimed in claim 1, characterized in that: the flame retardant finishing agent is mainly used in the post-finishing process of polyester-cotton fabrics. 3. the application of the flame retardant finishing agent based on montmorillonite/DNA hydrosol as claimed in claim 2, is characterized in that, the application of described flame retardant finishing agent mainly comprises the following steps: in parts by weight, acetone One part of washed polyester-cotton cloth is immersed in 30-150 parts of montmorillonite and DNA composite hydrosol under a certain tension condition, and dried at 20-50 ° C to promote the montmorillonite platelets in the composite hydrosol Fiber surface assembly to obtain a polyester-cotton fabric with a certain flame-retardant function.