阅读说明：本技术 一种有机硅基无醛阻燃整理剂的制备方法 (Preparation method of organic silicon-based formaldehyde-free flame-retardant finishing agent ) 是由 廖褚华 于 2020-07-07 设计创作，主要内容包括：本发明涉及一种有机硅基无醛阻燃整理剂的制备方法,属于阻燃剂技术领域。本发明以聚磷酸铵为阻燃芯材、以碳酸钙为壁材,制备碳酸钙包覆聚磷酸铵微胶囊,制备一种有机硅基无醛阻燃整理剂,聚磷酸铵无毒无味,不产生腐蚀气体,热稳定性高,是一种性能优良的非卤阻燃剂,聚磷酸铵受热时会产生磷酸、偏磷酸等物质,可以促进成炭,并且聚磷酸铵往往会产生难燃性气体,因此可以获得到较好的阻燃效果,采用碳酸钙壁材对聚磷酸铵进行微胶囊包覆处理能够使得聚磷酸铵本身具有的特殊性气味能够被碳酸钙壁材屏蔽,同时可以有效防止聚磷酸铵与织物接触,当织物受到高温时,碳酸钙因受热破裂,释放出内部的聚磷酸铵,达到良好的阻燃的效果。(The invention relates to a preparation method of an organic silicon-based formaldehyde-free flame retardant finishing agent, belonging to the technical field of flame retardants. The invention takes ammonium polyphosphate as a flame-retardant core material and calcium carbonate as a wall material to prepare calcium carbonate-coated ammonium polyphosphate microcapsules to prepare an organic silicon-based formaldehyde-free flame-retardant finishing agent, the ammonium polyphosphate is nontoxic and tasteless, does not generate corrosive gas, has high thermal stability, is a non-halogen flame retardant with excellent performance, can generate substances such as phosphoric acid, metaphosphoric acid and the like when being heated, can promote carbon formation, ammonium polyphosphate can generate flame-retardant gas, so that a better flame-retardant effect can be obtained, the ammonium polyphosphate is subjected to microcapsule coating treatment by adopting the calcium carbonate wall material, so that the peculiar smell of the ammonium polyphosphate can be shielded by the calcium carbonate wall material, meanwhile, the contact between ammonium polyphosphate and the fabric can be effectively prevented, and when the fabric is heated to high temperature, calcium carbonate is broken due to heating, so that the internal ammonium polyphosphate is released, and a good flame-retardant effect is achieved.)

1. A preparation method of an organic silicon-based formaldehyde-free flame retardant finishing agent is characterized by comprising the following specific preparation steps:

(1) adding alkylphenol polyoxyethylene ether and ethylene diamine tetraacetic acid into deionized water, and stirring at the rotating speed of 160-180 r/min for 10-15 min at normal temperature to obtain an emulsifier solution;

(2) adding silicone oil and paraffin oil into an emulsifier solution, placing the mixture into a high-shear emulsifying machine, and stirring the mixture for 1 to 2 hours at a rotating speed of 12000 to 16000r/min under a water bath condition of 30 to 40 ℃ to obtain an organic silicon emulsion;

(3) adding polyvinyl alcohol and citric acid into the organic silicon emulsion, and stirring at the rotating speed of 400-500 r/min for 20-30 min at normal temperature to obtain organic silicon mixed emulsion;

(4) adding melamine, sodium metaborate and calcium carbonate coated ammonium polyphosphate microcapsules into the organic silicon mixed emulsion, stirring at the rotating speed of 500-600 r/min for 40-60 min at normal temperature, then placing the mixture into an ultrasonic dispersion machine, and performing ultrasonic treatment for 1-2 h at normal temperature to obtain the organic silicon-based formaldehyde-free flame retardant finishing agent.

2. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 1, wherein the silicone oil, paraffin oil, alkylphenol ethoxylates, ethylene diamine tetraacetic acid, polyvinyl alcohol, citric acid, melamine, sodium metaborate, calcium carbonate-coated ammonium polyphosphate microcapsules, 30-40 parts by weight of deionized water, 15-20 parts by weight of paraffin oil, 3-4 parts by weight of alkylphenol ethoxylates, 3-4 parts by weight of ethylene diamine tetraacetic acid, 12-16 parts by weight of polyvinyl alcohol, 6-8 parts by weight of citric acid, 6-8 parts by weight of melamine, 18-24 parts by weight of sodium metaborate, 15-20 parts by weight of calcium carbonate-coated ammonium polyphosphate microcapsules, and 60-80 parts by weight of deionized water.

3. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 1, wherein the power of the ultrasonic treatment in the step (4) is 500-600W.

4. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 1, wherein the calcium carbonate coated ammonium polyphosphate microcapsule prepared in the step (4) is prepared by the following specific steps:

(1) adding anhydrous sodium carbonate into 1/2 deionized water, and stirring at the rotation speed of 120-140 r/min for 20-30 min at normal temperature to obtain a sodium carbonate solution;

(2) adding anhydrous calcium chloride into the residual 1/2 deionized water, and stirring at the rotating speed of 140-160 r/min for 15-20 min at normal temperature to obtain a calcium chloride solution;

(3) adding ammonium polyphosphate into absolute ethyl alcohol, and stirring at the rotating speed of 300-350 r/min for 20-30 min at normal temperature to obtain an ammonium polyphosphate ethyl alcohol suspension;

(4) slowly dropwise adding a calcium chloride solution into an ammonium polyphosphate ethanol suspension, and stirring at the rotating speed of 400-500 r/min for 10-15 min at normal temperature to obtain a mixed suspension;

(5) slowly dropwise adding a sodium carbonate solution into the mixed suspension, and stirring and reacting for 1-2 hours at a rotating speed of 350-400 r/min under a water bath condition of 50-60 ℃ to obtain a reaction mixed solution;

(6) and placing the reaction mixed solution into a reduced pressure suction filter for suction filtration, taking a filter cake, washing the filter cake with deionized water for 3-5 times, placing the filter cake into a drying oven at the temperature of 60-80 ℃ for drying for 1-2 hours, and cooling at normal temperature to obtain the calcium carbonate coated ammonium polyphosphate microcapsule.

5. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 4, wherein the weight parts of ammonium polyphosphate, anhydrous sodium carbonate, anhydrous calcium chloride, anhydrous ethanol and deionized water are 10-20 parts of ammonium polyphosphate, 16-32 parts of anhydrous sodium carbonate, 20-40 parts of anhydrous calcium chloride, 40-80 parts of anhydrous ethanol and 80-160 parts of deionized water.

6. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 4, wherein the dropping rate of the calcium chloride solution in the step (4) is 40-60 mL/min.

7. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 4, wherein the dropping rate of the sodium carbonate solution in the step (5) is 60-80 mL/min.

8. The preparation method of the organic silicon-based aldehyde-free flame retardant finishing agent according to claim 4, wherein the pressure of the suction filtration in the step (6) is 60-80 Pa.

9. The preparation method of the organic silicon-based formaldehyde-free flame retardant finishing agent according to claim 4, wherein the average particle size of the calcium carbonate-coated ammonium polyphosphate microcapsule in the step (6) is 20-40 μm.

Technical Field

The invention relates to a preparation method of an organic silicon-based formaldehyde-free flame retardant finishing agent, belonging to the technical field of flame retardants.

Background

Flame retardance refers to the reduction of flammability of the textile in a flame, slowing the rate of flame spread, and allowing the textile to self-extinguish quickly and without smoldering when the flame is removed. The combustion characteristics of various fibers are different due to different chemical structures and different combustion performances. Non-flame retardant fibers can be classified as combustible fibers and combustible fibers; the flame retardant fiber may be classified into a noncombustible fiber and a nonflammable fiber. The limiting oxygen index LOI refers to the minimum oxygen volume ratio required by the fabric to maintain combustion in the combustion process, and is one of important indexes for measuring the flame retardant effect of the fabric. The greater the limiting oxygen index value, the less flammable the fabric will be.

Cotton fiber is a combustible fiber, and the combustion process is complicated. Three elements of matter combustion are: combustible materials, oxygen and fire sources, and flame retardance is an element for eliminating the combustion of substances. According to the main factors influencing combustion, the flame retardant mechanism is divided into condensed phase flame retardant and gas phase flame retardant, wherein the condensed phase flame retardant is beneficial to carbonization, and the gas phase flame retardant can slow down chain oxidation reaction in flame. Coacervate and gas phase flame retardancy has long been recognized as two major modes of flame retardancy. In the process of flame retardation, condensed phase flame retardation and gas phase flame retardation are inseparable, and the condensed phase flame retardant changes the combustion balance by reducing the amount of volatile thermal degradation products on one hand and forms a carbon layer with low thermal conductivity on the other hand; the gas-phase flame retardant can inhibit the burning of the flame-retardant fabric and increase the generation amount of the carbon layer so as to reduce the heat release and increase the heat loss of heat radiation.

The amount of heat released during combustion in a short time is limited, and if the amount of heat released from the ignition source can be absorbed in a short time, the amount of heat radiated to the combustion surface and acting on the radicals can be reduced, and combustion can be suppressed to some extent. Therefore, the flame retardant with high heat capacity can perform endothermic reactions such as phase change, dehydration and the like to reduce the temperature of the fiber surface and a flame zone, slow down the speed of thermal cracking reaction, reduce the generation of combustible gas and achieve the purpose of flame retardance. Therefore, the heat absorption effect is mainly flame retardant through physical effects of cooling, heat insulation, dilution and the like.

After the flame retardant is heated, a glass-shaped or stable foam covering layer which is used for insulating heat, oxygen, combustible gas and heat and thermal radiation can be formed on the surface of the fiber material, so that the energy fed back to the flame-retardant fabric is reduced, and the spread of combustion is prevented. The covering layer can prevent the pyrolysis of the fabric and prevent combustible products generated by thermal decomposition from entering a gas phase to continuously participate in a combustion process, for example, an organic phosphorus flame retardant can generate a charring layer with stable structure when being heated. In the gas phase combustion zone, the flame retardant may trap free radicals in the combustion reaction, interrupting the combustion reaction. Chain reaction theory of combustion suggests that free radicals are a necessary condition for maintaining combustion, but gas phase flame retardance is insensitive to the chemical structure of the fiber material as compared to condensed phase flame retardance. For example, when the decomposition temperature of the halogen-containing flame retardant is close to that of the flame-retardant fabric, the flame retardant is thermally decomposed in a gas-phase combustion zone to generate free radicals capable of capturing combustion reaction, reducing the concentration of pyrolysis products of the flame retardant, and inhibiting or breaking chain reaction.

Flame retardant finishes can be classified according to the degree of durability of the flame retardant fabric as non-durable, semi-durable, and durable; the flame retardant can be divided into an additive type and a reactive type according to the relationship between the flame retardant and the material to be flame-retarded; the flame retardant elements may be classified into organic phosphorus, phosphorus-nitrogen, halogen-phosphorus, halogen, nitrogen, antimony, aluminum-magnesium, inorganic phosphorus, and the like. Flame retardants used for durable flame retardant treatment of cotton fabrics are generally phosphorus containing flame retardants, the most common of which are phosphate based flame retardants. In recent years, the synergistic flame retardant system has become a hot spot of flame retardant research with the advantages of improving flame retardant efficiency and reducing the content of expensive components in the flame retardant system.

The efficient cotton flame retardant can influence one or more stages of combustion of cotton fabrics in a physical or chemical mode so as to achieve the purpose of flame retardance. Suitable flame retardants may also vary for different stages of burning of cotton fabric. In the heating stage of the cotton fabric, the flame retardant which is easy to form a non-combustible gaseous coating layer and an expansion coating layer or can reduce the melting point of a flame retardant is effective and is suitable for the flame retardance of the first stage; in the degradation stage of the cotton fabric, the concentration of combustible gas can be reduced through chemical approaches such as carbonization, dehydrogenation and dehydration, namely the mode of thermal oxidation degradation is changed to achieve the purpose of flame retardance in the second stage. Any flame retardant which produces non-combustible gas, reduces the concentration of combustible gas or generates a gaseous free radical scavenger can reduce the combustion speed to produce the flame retardant effect at the stage when the cotton fabric decomposition product is ignited. Therefore, after the cotton fabric is ignited, the heat transfer speed of the surface of the combustible is reduced, and the free radicals of the combustion chain reaction are reduced, so that the combustion process can be slowed down.

The novel flame retardant applied to the textile industry needs to consider the following conditions: (1) high efficiency, low toxicity and durability, and the finished fabric reaches the legal flame retardant standard of related textiles; (2) the smoke quantity is small, and the toxicity is low; (3) the fiber can meet the requirements of fiber manufacturing and textile processing technologies, and has good stability; (4) the wearability of the fiber or textile is kept; (5) can endow the fabric with other composite properties, such as antifouling, mildew resistance, water repellency, crease resistance, antistatic property and the like; (6) the cost is economical.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the problem that the existing flame-retardant finished fabric can release formaldehyde in use, the preparation method of the organic silicon-based formaldehyde-free flame-retardant finishing agent is provided.

In order to solve the technical problems, the invention adopts the technical scheme that:

(1) adding alkylphenol polyoxyethylene ether and ethylene diamine tetraacetic acid into deionized water, and stirring at the rotating speed of 160-180 r/min for 10-15 min at normal temperature to obtain an emulsifier solution;

(2) adding silicone oil and paraffin oil into an emulsifier solution, placing the mixture into a high-shear emulsifying machine, and stirring the mixture for 1 to 2 hours at a rotating speed of 12000 to 16000r/min under a water bath condition of 30 to 40 ℃ to obtain an organic silicon emulsion;

(3) adding polyvinyl alcohol and citric acid into the organic silicon emulsion, and stirring at the rotating speed of 400-500 r/min for 20-30 min at normal temperature to obtain organic silicon mixed emulsion;

(4) adding melamine, sodium metaborate and calcium carbonate coated ammonium polyphosphate microcapsules into the organic silicon mixed emulsion, stirring at the rotating speed of 500-600 r/min for 40-60 min at normal temperature, then placing the mixture into an ultrasonic dispersion machine, and performing ultrasonic treatment for 1-2 h at normal temperature to obtain the organic silicon-based formaldehyde-free flame retardant finishing agent.

The coating comprises, by weight, 30-40 parts of silicone oil, 15-20 parts of paraffin oil, 3-4 parts of alkylphenol polyvinyl ether, 3-4 parts of ethylenediamine tetraacetic acid, 12-16 parts of polyvinyl alcohol, 6-8 parts of citric acid, 6-8 parts of melamine, 18-24 parts of sodium metaborate, 15-20 parts of calcium carbonate coated ammonium polyphosphate microcapsules and 60-80 parts of deionized water.

And (4) the power of ultrasonic treatment in the step (4) is 500-600W.

The calcium carbonate coated ammonium polyphosphate microcapsule prepared in the step (4) comprises the following specific preparation steps:

(1) adding anhydrous sodium carbonate into 1/2 deionized water, and stirring at the rotation speed of 120-140 r/min for 20-30 min at normal temperature to obtain a sodium carbonate solution;

(2) adding anhydrous calcium chloride into the residual 1/2 deionized water, and stirring at the rotating speed of 140-160 r/min for 15-20 min at normal temperature to obtain a calcium chloride solution;

(3) adding ammonium polyphosphate into absolute ethyl alcohol, and stirring at the rotating speed of 300-350 r/min for 20-30 min at normal temperature to obtain an ammonium polyphosphate ethyl alcohol suspension;

(4) slowly dropwise adding a calcium chloride solution into an ammonium polyphosphate ethanol suspension, and stirring at the rotating speed of 400-500 r/min for 10-15 min at normal temperature to obtain a mixed suspension;

(5) slowly dropwise adding a sodium carbonate solution into the mixed suspension, and stirring and reacting for 1-2 hours at a rotating speed of 350-400 r/min under a water bath condition of 50-60 ℃ to obtain a reaction mixed solution;

(6) and placing the reaction mixed solution into a reduced pressure suction filter for suction filtration, taking a filter cake, washing the filter cake with deionized water for 3-5 times, placing the filter cake into a drying oven at the temperature of 60-80 ℃ for drying for 1-2 hours, and cooling at normal temperature to obtain the calcium carbonate coated ammonium polyphosphate microcapsule.

The weight parts of the ammonium polyphosphate, the anhydrous sodium carbonate, the anhydrous calcium chloride, the anhydrous ethanol and the deionized water are 10-20 parts of the ammonium polyphosphate, 16-32 parts of the anhydrous sodium carbonate, 20-40 parts of the anhydrous calcium chloride, 40-80 parts of the anhydrous ethanol and 80-160 parts of the deionized water.

And (4) the dropping rate of the calcium chloride solution in the step (4) is 40-60 mL/min.

And (3) the dropping rate of the sodium carbonate solution in the step (5) is 60-80 mL/min.

And (4) performing suction filtration in the step (6) under the pressure of 60-80 Pa.

The calcium carbonate coated ammonium polyphosphate microcapsule in the step (6) has an average particle size of 20-40 μm.

Compared with other methods, the method has the beneficial technical effects that:

(1) the invention takes ammonium polyphosphate as a flame-retardant core material and calcium carbonate as a wall material to prepare calcium carbonate coated ammonium polyphosphate microcapsules and prepare an organic silicon-based formaldehyde-free flame-retardant finishing agent, the ammonium polyphosphate is nontoxic and tasteless, does not generate corrosive gas, has high thermal stability and is a non-halogen flame retardant with excellent performance, the ammonium polyphosphate can generate substances such as phosphoric acid, metaphosphoric acid and the like when being heated and can promote to form carbon, and the ammonium polyphosphate can generate flame-retardant gas frequently, so that better flame-retardant effect can be obtained, when the use environment is humid and the humidity in the air is high or a fabric is contacted with water, the ammonium polyphosphate can generate moisture absorption oxidation deterioration phenomenon, in order to prevent the occurrence of the phenomenon, the service life is prolonged, the ammonium polyphosphate is coated and modified by the calcium carbonate, and the flame-retardant effect of the ammonium polyphosphate on the fabric substrate is mainly reflected in the initial decomposition temperature, therefore, ammonium polyphosphate is subjected to microcapsule coating so as to have better thermal stability and have better flame retardant effect at a specific temperature, the ammonium polyphosphate is subjected to microcapsule coating treatment by adopting a calcium carbonate wall material, so that the peculiar smell of the ammonium polyphosphate can be shielded by the calcium carbonate wall material, meanwhile, the release of toxic substances can be reduced, the ammonium polyphosphate is coated by calcium carbonate, the microcapsule is adhered to the surface of a fabric through an organic silicon emulsion, the ammonium polyphosphate can be effectively prevented from contacting the fabric, when the fabric is subjected to high temperature, the calcium carbonate is broken by heating to release the ammonium polyphosphate inside, and a good flame retardant effect is achieved;

(2) the invention takes the organic silicon emulsion as the base material, and adds the melamine and the sodium metaborate, an organic silicon base aldehyde-free flame retardant finishing agent, the organic silicon contains silicon-oxygen bond, and at least one organic group compound directly connected with the silicon atom, the invention has the advantages of safety and innocuity, the organic silicon emulsion is a textile auxiliary agent with excellent performance, can endow the fabric with various excellent performances, and can also prevent the dripping of the flame retardant, the silicon polymer in the organic silicon emulsion can be combined into the polymer structure through a mechanism similar to the cross-linking mechanism of an interpenetrating network part, has little influence on the performance of the product, can also increase the impact strength of the polymer, reduce the permeability and the like, the organic silicon can improve the vitrification temperature of the fabric and the residual carbon quantity after combustion, thereby leading the fabric to obtain better flame retardant effect, the melamine can emit the flammable gas by heating, can dilute the flammable gas, the sodium metaborate can cultivate and seal the surface of a combustion object during combustion to form a vitreous covering layer to play an isolation role, and in addition, binding water is discharged at the combustion temperature to play cooling and heat absorption roles, the thermal decomposition path of certain combustibles is changed, and the generation of combustible gas is inhibited.

Detailed Description

Respectively weighing 10-20 parts by weight of ammonium polyphosphate, 16-32 parts by weight of anhydrous sodium carbonate, 20-40 parts by weight of anhydrous calcium chloride, 40-80 parts by weight of anhydrous ethanol and 80-160 parts by weight of deionized water, adding the anhydrous sodium carbonate into 1/2 parts by weight of deionized water, stirring at the rotating speed of 120-140 r/min for 20-30 min at normal temperature to obtain a sodium carbonate solution, adding the anhydrous calcium chloride into the rest 1/2 parts by weight of deionized water, stirring at the rotating speed of 140-160 r/min for 15-20 min at normal temperature to obtain a calcium chloride solution, adding the ammonium polyphosphate into the anhydrous ethanol, stirring at the rotating speed of 300-350 r/min for 20-30 min at normal temperature to obtain an ammonium polyphosphate ethanol suspension, slowly dropwise adding the calcium chloride solution into the ammonium polyphosphate ethanol suspension at the speed of 40-60 mL/min, stirring at the rotating speed of 400-500 r/min at normal temperature for 10-15 min to obtain a mixed suspension, dropwise adding a sodium carbonate solution into the mixed suspension at a speed of 60-80 mL/min, stirring and reacting for 1-2 h at a rotating speed of 350-400 r/min under a water bath condition of 50-60 ℃ to obtain a reaction mixed solution, placing the reaction mixed solution into a reduced pressure suction filter, carrying out suction filtration under a condition of 60-80 Pa, taking a filter cake, washing with deionized water for 3-5 times, drying in an oven at a temperature of 60-80 ℃ for 1-2 h, and cooling at normal temperature to obtain calcium carbonate coated ammonium polyphosphate microcapsules with an average particle size of 20-40 mu m; respectively weighing 30-40 parts by weight of silicone oil, 15-20 parts by weight of paraffin oil, 3-4 parts by weight of alkylphenol polyoxyethylene, 3-4 parts by weight of ethylenediamine tetraacetic acid, 12-16 parts by weight of polyvinyl alcohol, 6-8 parts by weight of citric acid, 6-8 parts by weight of melamine, 18-24 parts by weight of sodium metaborate, 15-20 parts by weight of calcium carbonate coated ammonium polyphosphate microcapsule and 60-80 parts by weight of deionized water, adding alkylphenol polyoxyethylene and ethylenediamine tetraacetic acid into the deionized water, stirring at the rotating speed of 160-180 r/min for 10-15 min at normal temperature to obtain an emulsifier solution, adding the silicone oil and the paraffin oil into the emulsifier solution, placing the emulsifier solution into a high shear emulsifying machine, stirring at the rotating speed of 12000-16000 r/min for 1-2 h under the water bath condition of 30-40 ℃ to obtain an organosilicon emulsion, adding the polyvinyl alcohol and the citric acid into the organosilicon emulsion, stirring at the rotating speed of 400-500 r/min at normal temperature for 20-30 min, and (3) obtaining an organic silicon mixed emulsion, adding melamine, sodium metaborate and calcium carbonate coated ammonium polyphosphate microcapsules into the organic silicon mixed emulsion, stirring at the rotating speed of 500-600 r/min for 40-60 min at normal temperature, then placing the mixture into an ultrasonic dispersion machine, and carrying out ultrasonic treatment at the power of 500-600W for 1-2 h at normal temperature to obtain the organic silicon-based formaldehyde-free flame retardant finishing agent.