CN113980216A - Preparation method and application of chain-shaped macromolecular flame retardant - Google Patents

Preparation method and application of chain-shaped macromolecular flame retardant Download PDF

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CN113980216A
CN113980216A CN202111276888.8A CN202111276888A CN113980216A CN 113980216 A CN113980216 A CN 113980216A CN 202111276888 A CN202111276888 A CN 202111276888A CN 113980216 A CN113980216 A CN 113980216A
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retardant
flame
flame retardant
chain macromolecular
real silk
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CN113980216B (en
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程献伟
关晋平
金文杰
朱强
陈国强
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
    • C08G12/12—Ureas; Thioureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
    • C08G12/14—Dicyandiamides; Dicyandiamidines; Guanidines; Biguanidines; Biuret; Semicarbazides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a preparation method and application of a chain macromolecular fire retardant, wherein the preparation method comprises the following steps: performing Schiff base reaction on dialdehyde and diamine to prepare a chain macromolecular fire retardant with an end group containing aldehyde groups, wherein the dialdehyde is terephthalaldehyde or isophthalaldehyde, and the diamine is urea or dicyandiamide; the application is as follows: preparing the chain macromolecular flame retardant into flame-retardant finishing liquid, finishing the real silk or wool product by an impregnation adsorption method, and controlling the impregnation temperature to enable the chain macromolecular flame retardant to be crosslinked with the real silk or wool product to obtain the durable flame-retardant real silk or wool product. The raw materials are easy to obtain, the preparation process is simple, and the prepared flame-retardant real silk or wool fiber product has better flame retardant property and water resistanceThe washing performance can still reach GB/T17591-1The grade requirement has important practical application value.

Description

Preparation method and application of chain-shaped macromolecular flame retardant
Technical Field
The invention belongs to the technical field of functional finishing of textiles, and relates to a preparation method and application of a chain macromolecular flame retardant.
Background
Fires pose a great threat to human life and property. Preliminary statistics shows that 25.2 thousands of fires are reported nationwide in 2020, 1183 dead people and 775 injured people have direct property loss of 40.09 million yuan. 10.9 thousands of residential fires of residents occur all the year round, accounting for 43.4 percent of the total number of the fires, resulting in the death of 917 and the injury of 499 people. The real silk or wool fiber belongs to natural protein fiber, has the characteristics of strong hygroscopicity, softness, comfortable wearing, ecological health care and the like, belongs to high-grade textile raw materials, and is widely applied to the fields of clothing, home decoration, bedding, public transportation decoration and the like. These fields require the use of textiles with certain flame retardant properties. The inherent flame retardant property of real silk or wool fiber can not meet the requirement of the flame retardant grade of textile. Once the real silk or wool fiber product is ignited, the product can burn quickly, and releases a large amount of toxic gases such as carbon monoxide, hydrogen cyanide, nitrogen oxide, ammonia and aldehydes, etc., thereby seriously threatening the safety of life and property of people.
The flame retardant is a functional chemical auxiliary agent which can effectively improve the flame resistance of the flammable polymer. By 2019, the annual demand for global flame retardants has exceeded 120 million tons. The halogen flame retardant is one of the most productive organic flame retardants in the world at present, and achieves the purpose of flame retardance mainly by terminating chain branching reaction. The halogen flame retardant has the advantages of high flame retardant efficiency, small using amount, low cost and the like, but has large smoke generation amount and is easy to generate toxic and corrosive gas in the using process, and serious harm is caused to the living environment of people, so the halogen flame retardant is gradually replaced by a new generation of environment-friendly flame retardant.
The intumescent flame retardant is an environment-friendly flame retardant with high efficiency and low toxicity, and mainly comprises an acid source, a carbon source and a gas source. Wherein the acid source is the most important and is a real flame retardant, and the carbon source and the gas source are synergists. The acid source is typically a mineral acid or a compound that generates an acid in situ during combustion, such as phosphoric acid and phosphoric acid esters. When the high polymer containing the flame retardant is heated to decompose or burn, a uniform porous carbon foam layer can be generated on the surface, the layer can insulate heat and oxygen, volatile combustible substances generated by decomposition of the high polymer can be prevented from entering a gas-phase combustion area from a condensed phase, and the flame retardant also has the functions of inhibiting smoke and preventing molten drops. The intumescent flame retardant meets the requirements of smoke suppression and attenuation of materials at present, and is one of the research hotspots in the field of flame retardance.
However, the existing intumescent flame retardants all contain mainstream flame retardant elements such as phosphorus, and although the existing intumescent flame retardants have excellent and efficient flame retardant performance and are greatly developed in development and application, the existing intumescent flame retardants have certain toxicological effects, are easy to volatilize and enter the environment, and pose threats to ecological stability and human health. Therefore, there is a need to develop an intumescent flame retardant that does not contain mainstream flame retardant elements.
The Schiff base is formed by nucleophilic addition reaction of aldehyde group and amino group, and has wide application in sterilization, metal ion chelation, fluorescent monomer and other aspects, and the Schiff base reaction is commonly adopted in the prior art to prepare the flame retardant. The invention patent CN 110698620A discloses a vanillin-based Schiff base-containing covalent organic framework flame retardant and a preparation method thereof, wherein vanillin and a bidentate amine compound are subjected to Schiff base amine aldehyde condensation reaction to prepare the covalent organic framework flame retardant, and then the covalent organic framework flame retardant is reacted with a phosphorus-containing compound and a sulfur-containing compound to prepare a solid flame retardant for improving the flame retardant property of an epoxy resin and polylactic acid composite material, but the flame retardant effect of the system is mainly caused by phosphorus elements and sulfur elements; document 1 (preparation of a novel nitrogen-silicon Schiff base and application thereof in a cellulose membrane. Donghua university journal (Nature science edition), 2019,45(6): 820-; in the method, sodium alginate and sodium carboxymethylcellulose are oxidized by sodium periodate to generate multi-aldehyde oxides, the multi-aldehyde oxides are respectively crosslinked with camel wool and wool through Schiff base, and then metal salts such as calcium chloride, aluminum sulfate and the like are adopted for ion exchange to prepare the flame-retardant wool fabric, however, the method mainly adopts metal ion chelates to play a flame-retardant effect. The Schiff base system in the prior art has a flame retardant effect only by being used together with phosphorus element, sulfur element or other mainstream flame retardant elements, the Schiff base reaction is only a carrier and is not a key of flame retardance, and the Schiff base reaction is not adopted in the prior art to prepare the intumescent flame retardant without the mainstream flame retardant elements.
The chain-shaped macromolecules have flexible chain segments and have small influence on the hand feeling of the flame-retardant textile. The chain macromolecular end group reaction group can generate chemical crosslinking with textile fibers, so that the flame-retardant fabric has certain durability.
If an intumescent flame retardant which does not contain mainstream flame-retardant elements and is a chain-shaped macromolecule can be prepared by adopting Schiff base reaction and is used for improving the flame-retardant property of real silk or wool fiber products, the preparation method has great significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a chain macromolecular flame retardant.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of chain macromolecular fire retardant comprises the steps of carrying out Schiff base reaction on dialdehyde and diamine to prepare the chain macromolecular fire retardant with end groups containing aldehyde groups, wherein the dialdehyde is terephthalaldehyde or isophthalaldehyde, and the diamine is urea or dicyandiamide; because the aldehyde is the dialdehyde, the amine is the diamine, the reaction conditions are controlled, and the chain-shaped macromolecules can be formed after full reaction.
The terephthalaldehyde or isophthalaldehyde is mainly used in the industries of dye, fluorescent whitening agent, medicine, perfume and the like, is a nontoxic product, contains two active aldehyde groups on a benzene ring in a molecule, and can react with amino to generate Schiff base to synthesize a chain macromolecular flame retardant. The invention adopts terephthalaldehyde or m-phthalaldehyde and urea or dicyandiamide to synthesize the flame retardant through Schiff base reaction, wherein the terephthalaldehyde, the m-phthalaldehyde, the urea and the dicyandiamide have no flame retardant property, and Schiff base C ═ N structure, amino, aldehyde group and benzene ring in the synthesized flame retardant molecule act together to form the novel intumescent flame retardant, although the novel intumescent flame retardant does not contain main flame retardant elements such as halogen, phosphorus and the like, the intumescent flame retardant effect can be achieved.
The terephthalaldehyde or isophthalaldehyde and urea or dicyandiamide are nontoxic products, and the prepared chain macromolecular flame retardant is a novel halogen-free phosphorus-free environment-friendly intumescent flame retardant.
Compared with halogen flame retardants and phosphorus flame retardants, the chain macromolecular flame retardant prepared by the invention has easily available and nontoxic raw materials, belongs to an ecological and environment-friendly intumescent flame retardant, has no pollution in the using process, and does not harm human bodies.
As a preferred technical scheme:
the preparation method of the chain macromolecular flame retardant comprises the following steps:
(1) dissolving dialdehyde and diamine in a mixed system of water and ethanol to obtain a solution;
(2) and heating the solution to a certain temperature, preserving the temperature for a period of time, and removing water and ethanol to obtain the chain macromolecular fire retardant with the end group containing aldehyde group.
In the preparation method of the chain macromolecular flame retardant, in the step (1), the mass content of the dialdehyde in the solution is 2-14%, and the molar ratio of the dialdehyde to the diamine is 1-1.2: 1; the content of the dialdehyde and the diamine in the solution is too low, and the finally obtained flame retardant effect is poor; too high, resulting in waste and increased cost; the molar ratio of the dialdehyde to the diamine is too small, so that the diamine is easily wasted; too large, easily resulting in incomplete reaction.
According to the preparation method of the chain macromolecular flame retardant, in the step (1), the volume ratio of water to ethanol is 90: 10-80: 20, and proper ethanol is added into water to facilitate the dissolution of terephthalaldehyde or isophthalaldehyde, so that the aldehyde group and amino group in the system are fully ensured to react.
The preparation method of the chain macromolecular fire retardant comprises the following steps of (2) keeping a certain temperature of 70-90 ℃ for 50-100 min; on the premise of ensuring that the solution does not boil, the temperature is raised to be beneficial to the dissolution of the terephthalaldehyde or isophthalaldehyde and Schiff base reaction, so that the Schiff base reaction temperature is set to be 70-90 ℃; the Schiff base reaction time is determined according to the Schiff base reaction, the time is too short, the reaction is incomplete, the time is too long, the reaction degree is slightly increased, and energy is wasted.
The invention also provides application of the chain macromolecular flame retardant prepared by the preparation method of the chain macromolecular flame retardant, the chain macromolecular flame retardant is prepared into flame-retardant finishing liquid, then real silk or wool products are finished by an impregnation adsorption method (impregnation, squeezing out excessive moisture and drying), and the impregnation temperature is controlled to enable the chain macromolecular flame retardant and the real silk or wool products to be crosslinked, so that durable flame-retardant real silk or wool products are obtained.
As a preferred technical scheme:
the application is that the dipping temperature is 70-90 ℃, the dipping time is 30-80 min, and the dipping bath ratio is 1: 30-50; the dipping temperature is set to be 70-90 ℃, which is beneficial to dissolving the chain macromolecular fire retardant and the aldehyde-ammonia crosslinking reaction between the fire retardant and real silk or wool fibers, and the dipping temperature is not too high, otherwise, the solution is boiled; the dipping time is set to be 30-80 min, the dipping time is not suitable to be too short, otherwise, the adsorption is less, the absorption is not suitable to be too long, and otherwise, energy is wasted; the dipping bath ratio of the invention is set to be 1: 30-50, the dipping bath ratio is not too small, otherwise, the fabric cannot be immersed, the dipping bath ratio is not too high, and otherwise, the waste is avoided.
In the application, the solvent in the flame-retardant finishing liquid is water and ethanol with the volume ratio of 90: 10-80: 20, the flame-retardant finishing liquid is obtained by dissolving the chain macromolecular flame retardant in a mixed system of the water and the ethanol, the water and the ethanol can not be removed when the chain macromolecular flame retardant is prepared, and the finally obtained product is the flame-retardant finishing liquid.
For the above applications, the silk or wool product is a fiber or fabric.
The application of the durable flame-retardant real silk product has the carbon length of 7.5-12.5 cm and the flame-retardant grade of B1After 20 times of washing, the carbon length is still less than 15 cm; the carbon length of the durable flame-retardant wool product is 6.9-9.5 cm, and the flame-retardant grade is B1And the carbon length is still less than 15cm after 20 times of water washing. The invention mechanism is as follows:
and performing Schiff base addition reaction on terephthalaldehyde or m-phthalaldehyde and urea or dicyandiamide at a certain temperature to obtain the chain macromolecular flame retardant with end groups containing aldehyde groups. The chain macromolecular fire retardant enters the real silk or wool fibers under the action of temperature, and the end aldehyde groups and the amino groups of the real silk or wool fibers generate aldehyde-ammonia crosslinking reaction and are fixed on the protein fibers to provide durable flame retardant performance. The Schiff base C-N structure, the amino group, the aldehyde group, the benzene ring and the like in the chain macromolecular flame retardant jointly act to form the intumescent flame retardant, and the Schiff base C-N structure, the amino group, the aldehyde group, the benzene ring and the like in the molecule can participate in the carbonization reaction of real silk or wool fibers in the combustion process, so that the thermal decomposition path of the real silk or wool fibers is changed, the real silk or wool fibers are effectively promoted to expand into carbon, the fibers below the carbon layer are protected, and the flame retardant performance of the real silk or wool fibers is improved. The aldehyde group can be used as an acid source, the benzene ring and the C ═ N structure can be used as a carbon source, and the amino group can be used as a gas source. In the heating process, aldehyde group and C ═ N structure carry out esterification reaction, amino is as the catalyst of esterification reaction, the reaction is carried out with higher speed, reaction product melts in the heating process, and the gas source decomposition product makes the melting product expand and foam, at this moment, the carbon source further decomposes, forms complete expansion system, solidifies into the expanded carbon layer at last, plays better isolated flame retardant effect. The chain-shaped macromolecules have a flame-retardant effect by a cluster aggregation principle (when the compounds have larger molecular weights and are arranged according to a certain rule, the special structure enables the compounds to have higher flame-retardant property than similar micromolecules). And the single terephthalaldehyde, m-phthalaldehyde, urea and dicyandiamide cannot effectively promote the carbonization of wool and real silk fibers, so that the flame retardant effect cannot be achieved.
Common flame-retardant elements such as halogen, phosphorus, silicon, sulfur and the like are mainstream flame-retardant elements, nitrogen belongs to synergistic flame-retardant elements, and the single flame-retardant effect is poor.
Has the advantages that:
(1) in the invention, the terephthalaldehyde or m-phthalaldehyde and the urea or dicyandiamide are nontoxic products, and the prepared flame retardant is a halogen-free phosphorus-free environment-friendly flame retardant system;
(2) the Schiff base C-N structure, amino, aldehyde group, benzene ring and other groups in the chain macromolecular flame retardant prepared by the invention can promote and participate in the char formation reaction of real silk or wool fibers in the combustion process, so that the intumescent flame retardant effect is achieved, and the flame retardant property of the flame retardant real silk or wool fiber product is excellent;
(3) in the invention, the chain macromolecular fire retardant has better flame-retardant durability by means of aldehyde-ammonia crosslinking reaction with real silk or wool fibers;
(4) the method has the advantages of simple process, short flow, environmental protection, sustainability, low economic cost, wide application prospect and important practical application value.
Drawings
FIG. 1 is a scanning electron microscope image of carbon residue after vertical burning of a real silk sample (a) and a flame-retardant real silk fabric (b) in example 2;
FIG. 2 shows the carbon length of the flame-retardant real silk fabric in example 2 after washing with water for different times.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a flame-retardant real silk fabric comprises the following steps:
(1) preparation of chain macromolecular flame retardant: dissolving 0.2mol of terephthalaldehyde and 0.2mol of urea in a mixed system of 90mL of water and 10mL of ethanol to obtain a solution, heating the solution to 80 ℃, preserving the temperature for 70min, and removing the water and the ethanol to obtain the chain macromolecular flame retardant with the end group containing aldehyde group;
(2) preparing a flame-retardant real silk fabric: firstly, dissolving the chain macromolecular fire retardant into a mixed system of 90mL of water and 10mL of ethanol to obtain a flame-retardant finishing liquid, then soaking the real silk fabric into the flame-retardant finishing liquid at a soaking bath ratio of 1:40, heating to 75 ℃, and preserving heat for 70min to obtain the flame-retardant real silk fabric.
Comparative example 1
A preparation method of a modified real silk fabric comprises the following specific processes: dissolving 0.2mol of terephthalaldehyde in a mixed system of 90mL of water and 10mL of ethanol to obtain finishing liquid, soaking the real silk fabric in the finishing liquid at a soaking bath ratio of 1:40, heating to 75 ℃, and preserving heat for 70min to obtain the modified real silk fabric.
Comparative example 2
A preparation method of a modified real silk fabric comprises the following specific processes: dissolving 0.2mol of urea in a mixed system of 90mL of water and 10mL of ethanol to obtain finishing liquid, soaking the real silk fabric in the finishing liquid at a soaking bath ratio of 1:40, heating to 75 ℃, and preserving heat for 70min to obtain the modified real silk fabric.
Example 2
A preparation method of a flame-retardant real silk fabric comprises the following steps:
(1) preparation of chain macromolecular flame retardant: dissolving 0.75mol of isophthalaldehyde and 0.7mol of dicyandiamide in a mixed system of 85mL of water and 15mL of ethanol to obtain a solution, heating the solution to 90 ℃, preserving the temperature for 50min, and removing the water and the ethanol to obtain the chain macromolecular flame retardant with the end group containing aldehyde group;
(2) preparing a flame-retardant real silk fabric: firstly, dissolving the chain macromolecular fire retardant into a mixed system of 85mL of water and 15mL of ethanol to obtain a flame-retardant finishing liquid, then soaking the real silk fabric into the flame-retardant finishing liquid at a soaking bath ratio of 1:50, heating to 85 ℃, and preserving heat for 60min to obtain the flame-retardant real silk fabric.
Example 3
A preparation method of flame-retardant wool fabric comprises the following steps:
(1) preparation of chain macromolecular flame retardant: dissolving 0.5mol of terephthalaldehyde and 0.4mol of urea in a mixed system of 85mL of water and 15mL of ethanol to obtain a solution, heating the solution to 70 ℃, preserving the temperature for 90min, and removing the water and the ethanol to obtain the chain macromolecular flame retardant with the end group containing aldehyde group;
(2) preparing a flame-retardant wool fabric: firstly, dissolving a chain macromolecular fire retardant into a mixed system of 85mL of water and 15mL of ethanol to obtain a fire-retardant finishing liquid, then soaking the wool fabric into the fire-retardant finishing liquid at a soaking bath ratio of 1:30, heating to 85 ℃, and preserving heat for 60min to obtain the fire-retardant wool fabric.
Example 4
A preparation method of flame-retardant wool fabric comprises the following steps:
(1) preparation of chain macromolecular flame retardant: dissolving 1.0mol of isophthalaldehyde and 0.8mol of dicyandiamide in a mixed system of 80mL of water and 20mL of ethanol to obtain a solution, heating the solution to 75 ℃, preserving the temperature for 80min, and removing the water and the ethanol to obtain the chain macromolecular flame retardant with the end group containing aldehyde group;
(2) preparing a flame-retardant wool fabric: firstly, dissolving a chain macromolecular fire retardant into a mixed system of 80mL of water and 20mL of ethanol to obtain a fire-retardant finishing liquid, then soaking the wool fabric into the fire-retardant finishing liquid at a soaking bath ratio of 1:50, heating to 90 ℃, and preserving heat for 60min to obtain the fire-retardant wool fabric.
Comparative example 3
A preparation method of a modified wool fabric comprises the following specific processes: dissolving 1.0mol of m-phthalaldehyde in a mixed system of 80mL of water and 20mL of ethanol to obtain finishing liquid, soaking the wool fabric in the finishing liquid at a soaking bath ratio of 1:50, heating to 90 ℃, and preserving heat for 60min to obtain the modified wool fabric.
Comparative example 4
A preparation method of a modified wool fabric comprises the following specific processes: firstly, dissolving 0.8mol of dicyandiamide in a mixed system of 80mL of water and 20mL of ethanol to obtain finishing liquid, then soaking the wool fabric in the finishing liquid at a soaking bath ratio of 1:50, heating to 90 ℃, and preserving heat for 60min to obtain the modified wool fabric.
The flame retardant performance of the fabrics prepared in examples 1-4 and comparative examples 1-4 was tested.
The carbon length is measured according to the standard GB/T5455-2014 "measurement of smoldering and afterflame time of the damage length of the textile in the vertical direction of the combustion performance". The combustion performance is evaluated according to the GB/T17591 and 2006 flame-retardant textile standard.
The washing method is carried out according to the standard of AATCC 61-2013 accelerated test on washing fastness for household and business, and the washing is repeated until the required washing times.
Table 1 shows the carbon length and flame retardant rating of the fabrics prepared in examples 1-4 and comparative examples 1-4.
TABLE 1
Figure BDA0003329739760000061
Figure BDA0003329739760000071
As can be seen from the table, the unfinished real silk fabric and the unfinished wool fabric are completely burned in the vertical burning process, and the carbon length is 30cm, which shows that the flame retardant property is poor. Real silk fabrics finished by terephthalaldehyde, real silk fabrics finished by urea, wool fabrics finished by m-phthalaldehyde and wool fabrics finished by dicyandiamide burn completely in a vertical burning test, and the carbon length is 30cm, which shows that the terephthalaldehyde, the urea, the m-phthalaldehyde and the dicyandiamide have no flame retardant function when used independently or only physically mixed. The carbon length of real silk and wool fabrics finished by the chain macromolecular fire retardant is lower than 15cm, and reaches B in GB/T17591 and 2006 flame-retardant fabrics1The requirement of the chain macromolecular flame retardant is to show that the chain macromolecular flame retardant has better flame retardant performance, and the main reason is that the Schiff base C-N structure, amino, aldehyde group, benzene ring and the like in the chain macromolecular flame retardant are matched with each other to form an intumescent flame retardant system, the flame retardant effect is achieved through the cluster aggregation principle, and the flame retardant is independently carried out on the chain macromolecular flame retardantPhthalaldehyde and urea alone do not constitute an effective intumescent flame retardant system (as shown in figure 1). As shown in figure 2, the carbon length of the finished real silk fabric is still less than 15cm after 20 times of water washing, and reaches B in GB/T17591-1The requirement of grade flame retardant performance indicates that the finished fabric has a durable flame retardant function.
The above embodiment illustrates that the real silk or wool fiber product modified by the chain macromolecular fire retardant has better flame retardant performance and washing resistance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a chain macromolecular fire retardant is characterized by comprising the following steps: the chain macromolecular fire retardant with the end group containing aldehyde group is prepared by Schiff base reaction of dialdehyde and diamine, wherein the dialdehyde is terephthalaldehyde or isophthalaldehyde, and the diamine is urea or dicyandiamide.
2. The method for preparing a chain macromolecular flame retardant according to claim 1, characterized by comprising the steps of:
(1) dissolving dialdehyde and diamine in a mixed system of water and ethanol to obtain a solution;
(2) and heating the solution to a certain temperature, preserving the temperature for a period of time, and removing water and ethanol to obtain the chain macromolecular fire retardant with the end group containing aldehyde group.
3. The preparation method of the chain macromolecular flame retardant according to claim 2, wherein in the step (1), the mass content of the dialdehyde in the solution is 2-14%, and the molar ratio of the dialdehyde to the diamine is 1-1.2: 1.
4. The preparation method of the chain macromolecular flame retardant according to claim 2, wherein in the step (1), the volume ratio of water to ethanol is 90: 10-80: 20.
5. The preparation method of the chain macromolecular flame retardant according to claim 2, wherein in the step (2), the certain temperature is 70-90 ℃ and the period of time is 50-100 min.
6. The application of the chain macromolecular flame retardant prepared by the preparation method of any one of claims 1 to 5 is characterized in that: preparing the chain macromolecular flame retardant into flame-retardant finishing liquid, finishing the real silk or wool product by an impregnation adsorption method, and controlling the impregnation temperature to enable the chain macromolecular flame retardant to be crosslinked with the real silk or wool product to obtain the durable flame-retardant real silk or wool product.
7. The use according to claim 6, wherein the dipping temperature is 70-90 ℃, the dipping time is 30-80 min, and the dipping bath ratio is 1: 30-50.
8. The application of the flame-retardant finishing liquid as claimed in claim 6, wherein the solvent in the flame-retardant finishing liquid is water and ethanol in a volume ratio of 90: 10-80: 20.
9. Use according to claim 6, wherein the real silk or wool product is a fiber or fabric.
10. The use according to claim 6, wherein the durable flame-retardant real silk product has a carbon length of 7.5-12.5 cm and a flame-retardant rating of B1After 20 times of washing, the carbon length is still less than 15 cm; the carbon length of the durable flame-retardant wool product is 6.9-9.5 cm, and the flame-retardant grade is B1And the carbon length is still less than 15cm after 20 times of water washing.
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