CN112411184A - Finishing process of formaldehyde-free flame-retardant wool product - Google Patents
Finishing process of formaldehyde-free flame-retardant wool product Download PDFInfo
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/13—Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
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- D—TEXTILES; PAPER
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- 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
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention relates to a finishing process of formaldehyde-free flame-retardant wool products, which comprises the steps of immersing the wool products into a solution containing aromatic aldehyde, controlling Schiff base reaction between the wool products and the aromatic aldehyde to obtain an intermediate product, immersing the intermediate product into a solution containing phosphite ester, and controlling Pudovik addition reaction between the intermediate product and the phosphite ester to obtain the flame-retardant wool products. The invention utilizes the chemical reaction among aromatic aldehyde, phosphite ester and wool product to fix phosphite ester on wool fiber firmly through covalent bond. The aromatic aldehyde adopted by the invention is a natural product, the phosphite ester has high flame retardant efficiency, the process operation is simple, and the reaction condition is mild. The flame-retardant wool product prepared by the method has the advantages of excellent flame-retardant effect, good washing resistance, low toxicity of the used flame retardant, mild treatment conditions, guarantee of environmental protection and safety of the flame-retardant wool product in the use process, no formaldehyde release and important practical application value.
Description
Technical Field
The invention belongs to the technical field of textile flame-retardant function finishing, and particularly relates to a finishing process of a formaldehyde-free flame-retardant wool product.
Background
Wool is an important natural protein fiber, has the excellent characteristics of good wearability, comfortable wearing, ecological health care and the like, and is known as a high-grade textile material. Wool textile products have been widely used in various fields of life, but also bring fire hazards to people. Because of the high nitrogen content and the high moisture content, the wool fiber has certain flame retardant property, but the inherent flame retardant property of the wool fiber can not meet the requirement of the flame retardant textile, and the improvement of the flame retardant property of the wool textile to improve the fire safety of the wool textile and meet the international market demand has very realistic significance.
The traditional halogen flame retardant has high flame retardant efficiency, but many of the traditional halogen flame retardant are not environmentally-friendly and even toxic. Halogen compounds have been proven to produce a large amount of toxic gases during combustion and have a series of serious problems such as persistence, bioaccumulation and environmental toxicity, and thus have been limited or even prohibited in the textile industry. Inorganic salt flame retardants such as titanium salt and zirconium salt have good flame retardant effect, but also have the problem of environmental pollution. The organic phosphorus flame retardant is a very important flame retardant, has multiple varieties, low toxicity and high flame retardant efficiency, is widely used as a substitute of a halogen flame retardant, but most phosphorus flame retardants for textiles have the problem of formaldehyde release.
The existing phosphorus-containing commercial flame retardant N-hydroxymethyl-3- (dimethoxyphosphono) propionamide (Pyrovatex CP) generally reacts with cotton fabrics by adopting a cross-linking agent, and the N-hydroxymethyl cross-linking agent has good effect but has the problem of formaldehyde release. Pyrovatex CP can also be applied to wool fabrics in the same way to retard flame, but also has formaldehyde emission problems. The Chinese invention patent CN 109054694A discloses a preparation process of flame-retardant down feather textile, which adopts a two-step method of diethyl phosphite, N-hydroxymethyl acrylamide and epichlorohydrin to synthesize a flame retardant monomer, and then uses the synthesized silicone-acrylic emulsion as a flame-retardant adhesive to be simultaneously used with the flame retardant monomer and uniformly coated on the surface of textile fabric to prepare the flame-retardant down feather textile. In addition, research is carried out on synthesizing a phosphorus-containing flame retardant by using diethyl phosphite, acrylamide and glyoxal or epichlorohydrin or hexachlorocyclotriphosphazene, and then improving the flame retardant performance of cotton and linen fabric by using the synthesized phosphorus-containing flame retardant through a roll baking method (synthesis and application of formaldehyde-free flame retardant for linen [ J ]. proceedings of university of Dalian industries, 2009,28(002): 154-156; synthesis and application of formaldehyde-free phosphorus-nitrogen flame retardant finishing agent for natural fiber [ J ]. wool spinning technology, 2019,47(05): 58-62; preparation and application of formaldehyde-free flame retardant FRC-P for cotton [ J ]. printing and dyeing, 2006,32(24): 14-16; preparation and application of durable formaldehyde-free flame retardant for cotton [ J ]. printing and dyeing auxiliary agent, 2014,31(10):6-10), which mainly relates to the synthesis of flame retardant, and needs to prepare the flame retardant cotton and linen fabric through multi-step reactions, the method has the advantages of complex operation, long process flow, low practical application value and high toxicity of the adopted glyoxal and epichlorohydrin.
Therefore, a method which is simple and convenient to operate and short in process flow is urgently needed to be researched for realizing formaldehyde-free flame retardant finishing of wool products.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a finishing process of a formaldehyde-free flame-retardant wool product.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for finishing non-formaldehyde flame-retarding wool products includes immersing wool products in the solution containing aromatic aldehyde, controlling Schiff base reaction between wool products and aromatic aldehyde to obtain intermediate product, immersing the intermediate product in the solution containing phosphite ester, and controlling the Pudovik addition reaction between intermediate product and phosphite ester to obtain flame-retarding wool products.
Aldehyde group of aromatic aldehyde and amino of wool products can generate Schiff base reaction under certain conditions to form a Schiff base system, and active P-H bond in phosphite ester molecule can generate Pudovik addition reaction with C-N bond in the Schiff base system. The phosphite ester is firmly fixed on the wool fiber through a covalent bond by means of the chemical reaction among the aromatic aldehyde, the phosphite ester and the wool product, the flame-retardant wool product with excellent washing resistance is prepared through two-step reaction, the phosphite ester can promote the wool fiber to be decomposed into carbon in the thermal decomposition process, a protective layer is formed on the surface of the wool fiber, and heat and oxygen are isolated, so that the flame-retardant property of the wool product is improved. The flame-retardant wool product prepared by the method has the advantages of excellent flame-retardant effect, good washing resistance, low toxicity of the used flame retardant, mild treatment conditions, guarantee of environmental protection and safety of the flame-retardant wool product in the use process, no formaldehyde release and important practical application value.
According to the invention, N-hydroxymethyl cross-linking agents are not needed in the process of preparing the flame-retardant wool product with excellent durability, so that the problem of formaldehyde release does not exist in the using process; the invention does not need to use halogen flame retardant in the process of preparing the flame-retardant wool product with excellent durability, can obtain excellent flame-retardant performance only by using the ecological environment-friendly flame retardant, has no pollution in the using process and does not harm human bodies.
In the prior art, phosphite is often used for preparing flame-retardant fabrics, phosphite is used for synthesizing a flame retardant, and then the flame-retardant fabrics are applied to the fabrics to obtain the final flame-retardant fabrics, wherein the synthesis reaction needs 1-2 steps, the application needs 1 step, the synthesis and the application are carried out separately, the operation is complex, and the process flow is long. According to the invention, the wool product is directly used as one of reaction raw materials, namely the wool product, phosphite ester and aromatic aldehyde are subjected to chemical reaction together, the phosphite ester is combined with wool fibers through covalent bonds, the reaction only needs 2 steps, the operation is simple and convenient, the process is short, and the conditions are mild. It is difficult for the person skilled in the art to think of wool products as one of the starting materials for the reaction on the basis of the prior art, because: 1) the state of a reaction system has great influence on the reaction rate and the reaction degree, in the prior art, the Pudovik addition reaction is carried out in a solution system, all used reagents are easily dissolved in a solvent, the reaction reagents are fully contacted, the reaction rate is high, the reaction degree is high, if wool is used as a raw material of the Pudovik addition reaction, as wool fibers are difficult to dissolve and are solid substances, the reaction system is not a solution system any more, the reaction rate and the reaction degree are unknown, and a person skilled in the art cannot expect whether the Pudovik addition reaction can be carried out or not; 2) not all amines can be used as amines for the addition reaction of Pudovik, and the skilled person will not think of wool as amines for the addition reaction of Pudovik, provided that the prior art does not use wool as amines for the addition reaction of Pudovik and that wool is not reported to be used as amines for the addition reaction of Pudovik; 3) the preparation of durable flame-retardant fabric in the prior art is usually realized by reacting a synthetic flame retardant with hydroxyl groups on the fabric through a cross-linking agent, and inspired by the prior art, a person skilled in the art wants to prepare a durable flame-retardant wool product by placing the attention on the hydroxyl groups on wool instead of amine groups, so that the problem of preparing the durable flame-retardant wool product by reacting the amine groups on the wool with other substances is not considered; 4) the prior art has reacted phosphites with other substances with the aim of synthesizing readily water-soluble flame retardants which can be used for textile finishing, for example wool as one of the "other substances", the product obtained no longer having the readily water-soluble, textile-finishing properties.
As a preferred technical scheme:
the finishing process of the formaldehyde-free flame-retardant wool product is characterized in that the wool product is wool fiber or fabric.
The finishing process of the formaldehyde-free flame-retardant wool product comprises the following steps of (1) preparing aromatic aldehyde into a finished product, wherein the aromatic aldehyde is more than one of benzaldehyde, p-hydroxybenzaldehyde, vanillin and cinnamaldehyde; the phosphite ester is diethyl phosphite or dimethyl phosphite.
The finishing process of the formaldehyde-free flame-retardant wool product comprises the following specific steps:
(1) dissolving aromatic aldehyde in ethanol to obtain aromatic aldehyde alcohol solution;
(2) dissolving aromatic alditol solution in water, and uniformly mixing to obtain a first processing solution;
(3) immersing the wool product into the first processing liquid, heating to a certain temperature, and preserving heat for a certain time to obtain an intermediate product;
(4) dissolving phosphite ester in ethanol to obtain phosphite ester alcoholic solution;
(5) dissolving phosphite ester alcohol solution in water, and uniformly mixing to obtain second processing liquid;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to a certain temperature, and then preserving heat for a certain time to obtain the flame-retardant wool product.
The finishing process of the formaldehyde-free flame-retardant wool product comprises the following steps of (1), wherein in the step (1), the mass-to-volume ratio of aromatic aldehyde to ethanol is 1g: 1-3 mL; in the step (2), the concentration of the aromatic aldehyde in the first processing liquid is 0.05-1.5 mol/L.
According to the finishing process of the formaldehyde-free flame-retardant wool product, in the step (3), the mass ratio of the wool product to the first processing liquid is 1: 20-50, the wool product cannot be immersed due to too large mass ratio of the wool product to the first processing liquid, and waste is caused due to too small ratio; the certain temperature is 80-98 ℃, the temperature is increased to be beneficial to dissolving the aromatic aldehyde, opening the wool scale layer and promoting the reaction between the aromatic aldehyde and the wool fibers; the certain time is 40-90 min, the reaction time is too short, the reaction is incomplete, the reaction time is too long, the reaction degree is increased slightly, and energy is wasted.
According to the finishing process of the formaldehyde-free flame-retardant wool product, in the step (4), the mass-to-volume ratio of phosphite ester to ethanol is 1g: 1-3 mL; the concentration of phosphite ester in the second processing liquid in the step (5) is 0.1-1.5 mol/L, the concentration of phosphite ester is lower, the flame retardant effect is not obvious, the concentration is higher, the flame retardant effect promotion effect is not obvious, and waste is easily caused.
According to the finishing process of the formaldehyde-free flame-retardant wool product, in the step (6), the certain temperature is 80-98 ℃, the raising of the temperature is favorable for opening a wool scale layer, and the addition reaction of phosphite ester and the Schiff base system formed in the step (3) is promoted; the certain time is 30-80 min, the reaction time is too short, the reaction is incomplete, the reaction time is too long, the reaction degree is increased slightly, and energy is wasted.
According to the finishing process of the formaldehyde-free flame-retardant wool product, the molar ratio of the aromatic aldehyde in the first processing liquid in the step (2) to the phosphite ester in the second processing liquid in the step (5) is 1: 1-2, the usage amount of the phosphite ester is high, and the complete aldehyde reaction of the aromatic aldehyde can be ensured.
According to the finishing process of the formaldehyde-free flame-retardant wool product, the LOI of the flame-retardant wool product is 30.9-35.9%; after washing for 0 time, the carbon length measured according to the standard GB/T5455 plus 2014 'determination of smoldering and afterflame time of the combustion performance of the textile in the vertical direction is 7.3-9.2 cm, after washing for 10 times, the carbon length measured according to the standard GB/T5455 plus 2014' determination of smoldering and afterflame time of the combustion performance of the textile in the vertical direction is 9.8-11.5 cm, and the washing method is carried out according to AATCC 61-2006 'accelerated test of washing-resistant color fastness for household and commercial use'; the flame retardant grade is measured to reach B according to the standard of GB/T17591 and 2006 flame retardant textile1Grade; according to GB/T2912.1-2009 test for textile Formaldehyde part 1: free and hydrolyzed formaldehyde (water extraction) was not detected as a result of the standard test.
Has the advantages that:
(1) the aromatic aldehyde used in the invention is a natural product, the diethyl phosphite raw material has sufficient source and low toxicity, and the prepared flame-retardant wool product does not contain formaldehyde, thereby ensuring the safety and environmental protection of the flame-retardant wool in the using process;
(2) the phosphorus content of the diethyl phosphite is high, and the phosphorus-containing groups can effectively promote the carbonization reaction of the wool fibers in the combustion process, so that the flame-retardant effect of the wool fibers is achieved, and the flame-retardant wool product has excellent flame-retardant performance;
(3) according to the invention, the diethyl phosphite is combined with the Pudovik addition reaction of an aromatic aldehyde/wool fiber Schiff base system, so that the flame-retardant wool product has better flame-retardant durability;
(4) the method has the advantages of simple process, mild conditions, low economic cost, wide application prospect and important practical application value.
Drawings
FIG. 1 shows the carbon length of the flame-retardant wool fabric of example 1 of the present invention after washing with water for various 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 or modifications of the present invention may be made by those skilled in the art after reading the teaching 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 finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving p-hydroxybenzaldehyde in ethanol to obtain a p-hydroxybenzaldehyde alcoholic solution; the mass-volume ratio of the p-hydroxybenzaldehyde to the ethanol is 6.1g to 6 mL;
(2) dissolving a p-hydroxybenzaldehyde alcoholic solution in water, and uniformly mixing to obtain a first processing solution; the concentration of the p-hydroxybenzaldehyde in the first processing liquid is 0.5 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 90 ℃, keeping the temperature for 60min, and carrying out Schiff base reaction on the wool fabric and p-hydroxybenzaldehyde to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 20;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 10.4g:10 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 0.75 mol/L; the molar ratio of the p-hydroxybenzaldehyde in the first processing liquid to the diethyl phosphite in the second processing liquid in the step (2) is 2: 3;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 90 ℃, preserving the heat for 60min, and carrying out a Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fabric.
Comparative example 1
A finishing process of formaldehyde-free flame-retardant wool fabric, which is basically the same as that of example 1, except that p-hydroxybenzaldehyde is not used.
Example 2
A finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving p-hydroxybenzaldehyde in ethanol to obtain a p-hydroxybenzaldehyde alcoholic solution; the mass-volume ratio of the p-hydroxybenzaldehyde to the ethanol is 12.2g to 12 mL;
(2) dissolving a p-hydroxybenzaldehyde alcoholic solution in water, and uniformly mixing to obtain a first processing solution; the concentration of the p-hydroxybenzaldehyde in the first processing liquid is 1 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 85 ℃, keeping the temperature for 90min, and carrying out Schiff base reaction on the wool fabric and p-hydroxybenzaldehyde to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 20;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 17.3g:18 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 1.25 mol/L; in the step (2), the molar ratio of the p-hydroxybenzaldehyde in the first processing liquid to the diethyl phosphite in the second processing liquid is 4: 5;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 80 ℃, keeping the temperature for 60min, and carrying out a Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fabric.
Example 3
A finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving vanillin in ethanol to obtain vanillin solution; the mass-volume ratio of the vanillin to the ethanol is 4.6 g: 5 mL;
(2) dissolving vanillin alcohol solution in water, and uniformly mixing to obtain a first processing solution; the concentration of vanillin in the first processing liquid is 0.3 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 98 ℃, keeping the temperature for 60min, and carrying out Schiff base reaction on the wool fabric and vanillin to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 20;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 6.9g:7 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 0.5 mol/L; in the step (2), the molar ratio of vanillin in the first processing liquid to diethyl phosphite in the second processing liquid is 3: 5;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 90 ℃, keeping the temperature for 50min, and carrying out Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fabric.
Example 4
A finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving cinnamaldehyde in ethanol to obtain a cinnamaldehyde alcohol solution; the mass-volume ratio of the cinnamaldehyde to the ethanol is 9.3 g:10 mL;
(2) dissolving the cinnamaldehyde alcohol solution in water, and uniformly mixing to obtain a first processing solution; the concentration of the cinnamaldehyde in the first processing liquid is 0.7 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 95 ℃, preserving the heat for 70min, and carrying out Schiff base reaction on the wool fabric and cinnamaldehyde to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 20;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 13.8g:14 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 1 mol/L; in the step (2), the molar ratio of the cinnamaldehyde in the first processing liquid to the diethyl phosphite in the second processing liquid is 7: 10;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 90 ℃, preserving the heat for 60min, and carrying out a Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fabric.
Example 5
A finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving cinnamaldehyde in ethanol to obtain a cinnamaldehyde alcohol solution; the mass-volume ratio of the cinnamaldehyde to the ethanol is 1g:3 mL;
(2) dissolving the cinnamaldehyde alcohol solution in water, and uniformly mixing to obtain a first processing solution; the concentration of the cinnamaldehyde in the first processing liquid is 1 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 90 ℃, preserving the heat for 60min, and carrying out Schiff base reaction on the wool fabric and cinnamaldehyde to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 50;
(4) dissolving dimethyl phosphite in ethanol to obtain dimethyl phosphite alcoholic solution; the mass volume ratio of the dimethyl phosphite to the ethanol is 1g to 3 mL;
(5) dissolving dimethyl phosphite alcohol solution in water, and uniformly mixing to obtain second processing liquid; the concentration of the dimethyl phosphite in the second processing liquid is 1.2 mol/L; in the step (2), the molar ratio of the cinnamaldehyde in the first processing liquid to the dimethyl phosphite in the second processing liquid is 5: 6;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 90 ℃, keeping the temperature for 65min, and carrying out Pudovik addition reaction between the intermediate product and dimethyl phosphite to obtain the flame-retardant wool fabric.
Comparative example 2
A finishing process of flame-retardant wool fabric comprises the following specific steps:
(1) synthesizing a commercial flame retardant Pyrovatex CP;
the raw materials are as follows: dimethyl phosphite, acrylamide, sodium methoxide (catalyst) and formaldehyde, and the specific synthetic process can refer to the prior art;
(2) after a commercial flame retardant Pyrovatex CP (1.2mol/L), an etherified trimethylol melamine crosslinking agent (50g/L) and a fiber protective agent (50g/L) are prepared into finishing liquid, wool fabric (same as in example 5) is finished by adopting a rolling and baking process (the pre-baking temperature is 80 ℃, the time is 3min, the baking temperature is 150 ℃, the time is 2min), and the flame-retardant wool fabric is obtained.
The proportional relationship between the amount of dimethyl phosphite used in step (1) and the amount of wool fabric used in step (2) was the same as in example 5.
Example 6
A finishing process of formaldehyde-free flame-retardant wool fabric comprises the following specific steps:
(1) dissolving benzaldehyde in ethanol to obtain a benzaldehyde alcoholic solution; the mass volume ratio of the benzaldehyde to the ethanol is 2g:3 mL;
(2) dissolving a benzaldehyde alcohol solution in water, and uniformly mixing to obtain a first processing solution; the concentration of benzaldehyde in the first processing liquid is 1.2 mol/L;
(3) immersing the wool fabric into the first processing liquid, heating to 95 ℃, preserving the heat for 65min, and carrying out Schiff base reaction on the wool fabric and benzaldehyde to obtain an intermediate product; the mass ratio of the wool fabric to the first processing liquid is 1: 50;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 1g:2.5 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 1.4 mol/L; in the step (2), the molar ratio of benzaldehyde in the first processing liquid to diethyl phosphite in the second processing liquid is 6: 7;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 86 ℃, keeping the temperature for 70min, and carrying out a Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fabric.
Example 7
A finishing process of formaldehyde-free flame-retardant wool fibers comprises the following specific steps:
(1) dissolving benzaldehyde and cinnamaldehyde in ethanol to obtain an aldehyde mixture alcohol solution; the mass-volume ratio of the aldehyde mixture to the ethanol is 3g:3 mL; the molar ratio of benzaldehyde to cinnamaldehyde is 1: 1;
(2) dissolving the aldehyde mixture alcohol solution in water, and uniformly mixing to obtain a first processing solution; the concentration of the aldehyde mixture in the first processing liquid is 1.5 mol/L;
(3) immersing wool fibers into the first processing liquid, heating to 98 ℃, preserving heat for 75min, and carrying out Schiff base reaction on the wool fibers and the aldehyde mixture to obtain an intermediate product; the mass ratio of the wool fibers to the first processing liquid is 1: 50;
(4) dissolving diethyl phosphite in ethanol to obtain a diethyl phosphite alcoholic solution; the mass-volume ratio of diethyl phosphite to ethanol is 1g:2.8 mL;
(5) dissolving a diethyl phosphite alcohol solution in water, and uniformly mixing to obtain a second processing solution; the concentration of the diethyl phosphite in the second processing liquid is 1.5 mol/L; in the step (2), the molar ratio of the aldehyde mixture in the first processing liquid to the diethyl phosphite in the second processing liquid is 1: 1;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to 93 ℃, preserving the heat for 75min, and carrying out a Pudovik addition reaction between the intermediate product and diethyl phosphite to obtain the flame-retardant wool fiber.
The flame retardant wool products prepared in examples 1 to 7, the flame retardant wool fabric prepared in comparative example 1, and the flame retardant wool fabric prepared in comparative example 2 were tested for flame retardant performance and water washing resistance.
The Limiting Oxygen Index (LOI) of the fabric is determined according to GB/T5454-1997 textile Combustion Performance test oxygen index method.
The carbon length of the fabric is measured according to the standard GB/T5455-2014 'determination of smoldering and afterflame time of the damage length of the textile in the vertical direction of the burning performance'.
The combustion performance of the fabric is evaluated according to the GB/T17591 and 2006 flame-retardant fabric standard.
The content of free and hydrolysed formaldehyde on the fabric is referred to GB/T2912.1-2009 test for textile formaldehyde part 1: free and hydrolyzed formaldehyde (water extraction method) were tested.
The washing method of the flame-retardant wool fabric is referred to AATCC 61-2006 accelerated test of wash fastness for household and commercial use.
The flame retardant properties of the flame retardant wool fabric were finally measured as follows:
as can be seen from the table, the unfinished wool fabric is completely combusted in the vertical combustion process, the carbon length is 30cm, which shows that the flame retardant property is poor, the LOI of the wool fabric finished by phosphite ester is increased from 24.3% of unfinished wool fabric to more than 30.9%, the carbon length is obviously reduced, and the carbon length is less than 15cm after 0 time and 10 times of water washing, which reaches B in GB/T17591 plus 2006 flame retardant Fabric1The requirement of grade flame retardant property shows that the flame retardant property of the flame retardant wool product is excellent.
As shown in figure 1, the flame-retardant wool fabric prepared in example 1 has increased carbon length with the increase of the number of washing times, and can still be self-extinguished in a vertical burning test after 20 times of washing, and the carbon length is less than 15.0cm and reaches B1Requirements for grade flame retardant properties. In addition, the formaldehyde content results of the flame-retardant wool products prepared by the above embodiments are all 'undetected', which indicates that the finished wool products do not have the problem of formaldehyde release, because the flame-retardant process does not need to adopt an N-hydroxymethyl crosslinking agent in the using process and does not generate formaldehyde in the using process.
The results show that the wool product finished by the method has good flame retardant property and washing resistance.
Comparing example 1 with comparative example 1, it can be seen that the water washing resistance of the product prepared in example 1 is significantly better than that of comparative example 1, because the flame retardant processing liquid in comparative example 1 does not contain p-hydroxybenzaldehyde, does not undergo schiff base reaction, and further does not undergo podovik addition reaction, and the diethyl phosphite and wool fiber can only be bonded by non-covalent bonds such as van der waals force, and the like, and are easy to fall off in the water washing process, so that the phosphorus content on the wool fabric is reduced, the flame retardant performance is lost, and the wool fabric is not resistant to water washing.
Comparing example 5 with comparative example 2, it can be seen that the water washing resistance of the flame-retardant wool fabric prepared in example 5 is better than that of comparative example 2, which is probably caused by the indirect crosslinking method adopted in comparative example 2. In addition, the hand feeling and formaldehyde content of the flame-retardant wool fabrics prepared in the example 5 and the comparative example 2 are tested, and the flame-retardant wool fabric prepared in the example 5 is softer in hand feeling and free from formaldehyde release, while the flame-retardant wool fabric prepared in the comparative example 2 is poorer in hand feeling and has the problem of formaldehyde release because the formaldehyde is used in the process of synthesizing the flame retardant in the comparative example 2, the cross-linking agent is used in the process of finishing the fabric, and the formaldehyde is slowly released in the using process.
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 finishing process of formaldehyde-free flame-retardant wool products is characterized in that the wool products are immersed in a solution containing aromatic aldehyde, Schiff base reaction is controlled to occur between the wool products and the aromatic aldehyde to obtain an intermediate product, then the intermediate product is immersed in a solution containing phosphite ester, and Pudovik addition reaction is controlled to occur between the intermediate product and the phosphite ester to obtain the flame-retardant wool products.
2. The finishing process of formaldehyde-free flame-retardant wool product according to claim 1, wherein the wool product is wool fiber or fabric.
3. The finishing process of formaldehyde-free flame-retardant wool product according to claim 1, wherein the aromatic aldehyde is one or more of benzaldehyde, p-hydroxybenzaldehyde, vanillin and cinnamaldehyde; the phosphite ester is diethyl phosphite or dimethyl phosphite.
4. The finishing process of the formaldehyde-free flame-retardant wool product according to any one of claims 1 to 3, which is characterized by comprising the following specific steps:
(1) dissolving aromatic aldehyde in ethanol to obtain aromatic aldehyde alcohol solution;
(2) dissolving aromatic alditol solution in water, and uniformly mixing to obtain a first processing solution;
(3) immersing the wool product into the first processing liquid, heating to a certain temperature, and preserving heat for a certain time to obtain an intermediate product;
(4) dissolving phosphite ester in ethanol to obtain phosphite ester alcoholic solution;
(5) dissolving phosphite ester alcohol solution in water, and uniformly mixing to obtain second processing liquid;
(6) and (4) completely immersing the intermediate product obtained in the step (3) into a second processing liquid, heating to a certain temperature, and then preserving heat for a certain time to obtain the flame-retardant wool product.
5. The finishing process of the formaldehyde-free flame-retardant wool product according to claim 4, wherein in the step (1), the mass-to-volume ratio of the aromatic aldehyde to the ethanol is 1g: 1-3 mL; in the step (2), the concentration of the aromatic aldehyde in the first processing liquid is 0.05-1.5 mol/L.
6. The finishing process of the formaldehyde-free flame-retardant wool product according to claim 4, wherein in the step (3), the mass ratio of the wool product to the first processing liquid is 1: 20-50; the certain temperature is 80-98 ℃; the certain time is 40-90 min.
7. The finishing process of the formaldehyde-free flame-retardant wool product according to claim 4, wherein in the step (4), the mass-to-volume ratio of the phosphite ester to the ethanol is 1g: 1-3 mL; and (5) the concentration of the phosphite ester in the second processing liquid is 0.1-1.5 mol/L.
8. The finishing process of the formaldehyde-free flame-retardant wool product according to claim 4, wherein in the step (6), the certain temperature is 80-98 ℃; the certain time is 30-80 min.
9. The finishing process of formaldehyde-free flame-retardant wool products according to claim 4, wherein the molar ratio of the aromatic aldehyde in the first processing liquid in the step (2) to the phosphite ester in the second processing liquid in the step (5) is 1: 1-2.
10. The finishing process of formaldehyde-free flame-retardant wool products according to claim 4, wherein the LOI of the flame-retardant wool products is 30.9-35.9%; after washing for 0 time, the carbon length measured according to the standard GB/T5455 plus 2014 'determination of smoldering and afterflame time of the combustion performance of the textile in the vertical direction is 7.3-9.2 cm, after washing for 10 times, the carbon length measured according to the standard GB/T5455 plus 2014' determination of smoldering and afterflame time of the combustion performance of the textile in the vertical direction is 9.8-11.5 cm, and the washing method is carried out according to AATCC 61-2006 'accelerated test of washing-resistant color fastness for household and commercial use'; the flame retardant grade reaches the grade B1 according to the standard of GB/T17591 and 2006 flame retardant textile; according to GB/T2912.1-2009 test for textile Formaldehyde part 1: free and hydrolyzed formaldehyde (water extraction) was not detected as a result of the standard test.
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| CN113089319A (en) * | 2021-04-09 | 2021-07-09 | 苏州大学 | Phosphorus/nitrogen/sulfur synergistic flame retardant and application thereof in flame retardant finishing of protein fiber products |
| CN114645453A (en) * | 2022-04-06 | 2022-06-21 | 苏州大学 | Durable flame-retardant protein fiber product and preparation method thereof |
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| CN113024815B (en) * | 2021-04-09 | 2022-04-01 | 苏州大学 | Phosphorus/nitrogen/silica sol flame-retardant liquid and application thereof in flame-retardant finishing of protein fiber products |
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| CN114908565A (en) * | 2022-05-24 | 2022-08-16 | 苏州大学 | Preparation method of durable flame-retardant polyester fabric |
| CN115073686A (en) * | 2022-06-28 | 2022-09-20 | 河北大学 | Preparation method of bio-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin |
| CN115073686B (en) * | 2022-06-28 | 2023-07-21 | 河北大学 | Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin |
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