阅读说明：本技术 一种硅磷协同煤炭阻燃抑尘剂及其制备方法 (Silicon-phosphorus synergistic coal flame-retardant dust suppressant and preparation method thereof ) 是由 来水利 陈功 杨欣 李晨辉 于 2020-07-29 设计创作，主要内容包括：本发明属于煤炭阻燃抑尘剂领域,具体公开了一种硅磷协同煤炭阻燃抑尘剂及其制备方法,以质量份数计,其原料包括以下组分：0.10-0.30份磷系阻燃剂,0.15-0.30份硅烷偶联剂,0.008-0.018份催化剂,80.0-160.0份溶剂,0.10-0.40份硅系阻燃剂,0.1-0.4份pH调节剂,83.0-125.0份去离子水,57.0-95.0份醇类化合物,1.0-2.0份天然高分子,10.0-20.0份单体,4.0-8.0份pH缓冲剂,0.1-0.4份引发剂,0.02-0.08份交联剂,0.2-0.4份表面活性剂,0.2-1.0份增塑剂。本阻燃抑尘剂中引入了硅、磷元素,是一种高效的硅磷协同阻燃体系,能克服单一阻燃剂阻燃级别较低、极限氧指数小的缺点,具有优良的阻燃性能。喷洒后形成的高分子薄膜不仅能防止煤粉吹散,减少煤尘污染；而且能起到隔绝氧气的效果,从而防止煤炭自燃。(The invention belongs to the field of coal flame-retardant dust suppressant, and particularly discloses a silicon-phosphorus synergistic coal flame-retardant dust suppressant and a preparation method thereof, wherein the silicon-phosphorus synergistic coal flame-retardant dust suppressant comprises the following raw materials in parts by mass: 0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent, 0.008-0.018 part of catalyst, 80.0-160.0 parts of solvent, 0.10-0.40 part of silicon flame retardant, 0.1-0.4 part of pH regulator, 83.0-125.0 parts of deionized water, 57.0-95.0 parts of alcohol compound, 1.0-2.0 parts of natural polymer, 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 0.1-0.4 part of initiator, 0.02-0.08 part of cross-linking agent, 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer. The flame-retardant dust suppressant introduces silicon and phosphorus elements, is an efficient silicon-phosphorus synergistic flame-retardant system, can overcome the defects of low flame-retardant level and small limiting oxygen index of a single flame retardant, and has excellent flame-retardant performance. The polymer film formed after spraying can not only prevent the coal dust from blowing away, reduce the coal dust pollution; but also has the effect of isolating oxygen, thereby preventing the spontaneous combustion of coal.)

1. The silicon-phosphorus synergistic coal flame-retardant dust suppressant is characterized by comprising the following raw materials in parts by mass:

0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent, 0.008-0.018 part of catalyst, 80.0-160.0 parts of solvent, 0.10-0.40 part of silicon flame retardant, 0.1-0.4 part of pH regulator, 83.0-125.0 parts of deionized water, 57.0-95.0 parts of alcohol compound, 1.0-2.0 parts of natural polymer, 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 0.1-0.4 part of initiator, 0.02-0.08 part of cross-linking agent, 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer.

2. The silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 1, wherein the phosphorus flame retardant is DOPO.

3. The silicon-phosphorus synergistic coal flame retardant and dust suppression agent as claimed in claim 1, wherein the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.

4. The silicon-phosphorus synergistic coal fire-retardant dust suppressant according to claim 1, wherein the catalyst is at least one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

5. The silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 1, wherein the silicon-based flame retardant is nano SiO₂At least one of kaolin, diatomaceous earth, montmorillonite and attapulgite.

6. The silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 1, wherein the natural polymer is at least one of sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof and chitosan.

7. The silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 1, wherein the solvent is at least one of absolute ethyl alcohol, benzene, toluene, chloroform, acetone, cyclohexane and tetrahydrofuran;

the pH regulator is at least one of acetic acid and hydrochloric acid;

the pH buffering agent is sodium hydroxide;

the alcohol compound is at least one of methanol and ethanol; the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;

the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite;

the cross-linking agent is at least one of N, N' -methylene-bisacrylamide and dimethyldiallylammonium chloride;

the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;

the plasticizer is glycerol.

8. A preparation method of a silicon-phosphorus synergistic coal flame-retardant dust suppressant is characterized by comprising the following steps:

(1) mixing 0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent and 20.0-50.0 parts of solvent to obtain solution A;

dissolving 0.008-0.018 parts of catalyst by 10.0 parts of solvent to obtain solution B;

dropwise adding the solution B into the solution A, reacting at 60-120 ℃ for 5-12h to obtain a crude product, removing the solvent by rotary evaporation, and drying for 8-24h to obtain a flame-retardant intermediate;

(2) adding 57.0-95.0 parts of alcohol compound and 3.0-5.0 parts of deionized water into the flame-retardant intermediate, then adding a pH regulator to adjust the pH to 3.0-4.0, and performing ultrasonic hydrolysis for 1-2 hours to obtain a solution C;

adding 50.0-100.0 parts of solvent and 0.10-0.40 part of silicon flame retardant into the solution C, reacting at 70-120 ℃ for 8-24h, washing, performing suction filtration, and drying at 60-80 ℃ for 8-12h to obtain the flame retardant;

(3) mixing 1-2 parts of natural polymer, 0.2-0.8 part of flame retardant and 40-80 parts of deionized water to obtain a solution D;

mixing 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 20.0-40.0 parts of deionized water and 0.02-0.08 part of cross-linking agent to obtain solution E;

mixing 0.1-0.4 part of initiator and 10.0-20.0 parts of deionized water to obtain a solution F;

introducing inert gas into the solution D, simultaneously dropwise adding the solution E and the solution F into the solution D, and preserving heat for 4-6h at the temperature of 50-60 ℃ to obtain a solution G;

(4) and then adding 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer into the solution G, and uniformly stirring to obtain light yellow transparent viscous liquid, namely the silicon-phosphorus synergistic coal flame-retardant dust suppressant.

9. The preparation method of the silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 8, wherein in the step (1), the solution A is prepared under the protection of inert gas;

in the step (3), the preparation of the solution E is carried out under the ice-water bath condition.

10. The preparation method of the silicon-phosphorus synergistic coal flame-retardant dust suppressant according to claim 8, wherein in the step (2), the mass ratio of the alcohol compound to the deionized water is 19: 1.

Technical Field

The invention belongs to the technical field of coal flame-retardant dust suppressant, and particularly relates to a silicon-phosphorus synergistic coal flame-retardant dust suppressant and a preparation method thereof.

Background

Along with the rapid development of economy in China, the energy demand is larger and larger, and the mining, transportation and storage capacity of coal serving as a main energy source is increased year by year. At present, coal in China is mainly transported by railways, dust is easily generated due to airflow disturbance in the transportation process, not only can coal resources be seriously wasted, but also the surrounding air can be greatly polluted, and the health of people is seriously harmed. Meanwhile, the spontaneous combustion of coal also threatens the life of operators and the safety of mining equipment in the mining and storage of coal, and causes a great deal of economic loss and resource waste.

The traditional dust suppression methods comprise a sprinkling wetting method, a tarpaulin covering method, a wind-shield wall isolating method and the like, and have the problems of large water consumption, complex operation, low dust suppression efficiency and the like. With the emergence of chemical dust depressors, the chemical dust suppression method has received extensive attention and research due to its good dust suppression effect. The traditional dust suppressant mainly comprises wetting type, bonding type, condensation type and composite type. In recent years, chemical dust depressors gradually develop towards environmental protection, low price, high efficiency, wide application, multifunction and the like.

The flame retardant may be classified into a halogen-containing flame retardant, a phosphorus-containing flame retardant, a nitrogen-containing flame retardant, a silicon-containing flame retardant, an aluminum-magnesium-containing flame retardant, a nitrogen-phosphorus-containing flame retardant, and the like, depending on the kind of the element added. However, the smoke toxicity and environmental problems caused by halogen flame retardants are prominent, and the halogen-free or low-halogen flame retardant products are limited by the use of multiple industries, and are becoming the development trend of the industries. The single flame retardant has the defects of low flame retardant grade, small limiting oxygen index and large addition amount.

At present, most of China uses a dust suppressant and a flame retardant in a compounding way, and most of the flame retardants rely on imports and are high in cost. In addition, the hard shell type dust suppressant in the market is applied more and has poor pressure resistance, a cured layer of the product after being sprayed is brittle and is easy to crack after being vibrated and wind power in transportation, so that the dust suppression effect is lost, and the cost is high due to the fact that a large amount of dust suppressant needs to be sprayed repeatedly.

Disclosure of Invention

The invention aims to provide a silicon-phosphorus synergistic coal flame-retardant dust suppressant and a preparation method thereof, and the flame-retardant dust suppressant has the characteristics of flame retardance and dust suppression, strong flame-retardant dust suppression capability, flexible film forming, low cost, greenness and environmental friendliness.

The invention is realized by the following technical scheme:

the silicon-phosphorus synergistic coal flame-retardant dust suppressant comprises the following raw materials in parts by mass:

0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent, 0.008-0.018 part of catalyst, 80.0-160.0 parts of solvent, 0.10-0.40 part of silicon flame retardant, 0.1-0.4 part of pH regulator, 83.0-125.0 parts of deionized water, 57.0-95.0 parts of alcohol compound, 1.0-2.0 parts of natural polymer, 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 0.1-0.4 part of initiator, 0.02-0.08 part of cross-linking agent, 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer.

Further, the phosphorus flame retardant is DOPO.

Further, the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.

Further, the catalyst is at least one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

Further, the silicon flame retardant is nano SiO₂At least one of kaolin, diatomaceous earth, montmorillonite and attapulgite.

Further, the natural polymer is at least one of sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof, and chitosan.

Further, the solvent is at least one of absolute ethyl alcohol, benzene, toluene, chloroform, acetone, cyclohexane and tetrahydrofuran;

the pH regulator is at least one of acetic acid and hydrochloric acid;

the pH buffering agent is sodium hydroxide;

the alcohol compound is at least one of methanol and ethanol; the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;

the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite;

the cross-linking agent is at least one of N, N' -methylene-bisacrylamide and dimethyldiallylammonium chloride;

the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;

the plasticizer is glycerol.

The invention also discloses a preparation method of the silicon-phosphorus synergistic coal flame-retardant dust suppressant, which comprises the following steps:

(1) mixing 0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent and 20.0-50.0 parts of solvent to obtain solution A;

dissolving 0.008-0.018 parts of catalyst by 10.0 parts of solvent to obtain solution B;

dropwise adding the solution B into the solution A, reacting at 60-120 ℃ for 5-12h to obtain a crude product, removing the solvent by rotary evaporation, and drying for 8-24h to obtain a flame-retardant intermediate;

(2) adding 57.0-95.0 parts of alcohol compound and 3.0-5.0 parts of deionized water into the flame-retardant intermediate, then adding a pH regulator to adjust the pH to 3.0-4.0, and performing ultrasonic hydrolysis for 1-2 hours to obtain a solution C;

adding 50.0-100.0 parts of solvent and 0.10-0.40 part of silicon flame retardant into the solution C, reacting at 70-120 ℃ for 8-24h, washing, performing suction filtration, and drying at 60-80 ℃ for 8-12h to obtain the flame retardant;

(3) mixing 1-2 parts of natural polymer, 0.2-0.8 part of flame retardant and 40-80 parts of deionized water to obtain a solution D;

mixing 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 20.0-40.0 parts of deionized water and 0.02-0.08 part of cross-linking agent to obtain solution E;

mixing 0.1-0.4 part of initiator and 10.0-20.0 parts of deionized water to obtain a solution F;

introducing inert gas into the solution D, simultaneously dropwise adding the solution E and the solution F into the solution D, and preserving heat for 4-6h at the temperature of 50-60 ℃ to obtain a solution G;

(4) and then adding 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer into the solution G, and uniformly stirring to obtain light yellow transparent viscous liquid, namely the silicon-phosphorus synergistic coal flame-retardant dust suppressant.

Further, in the step (1), preparing a solution A under the protection of inert gas;

in the step (3), the preparation of the solution E is carried out under the ice-water bath condition.

Further, in the step (2), the mass ratio of the alcohol compound to the deionized water is 19: 1.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention discloses a silicon-phosphorus synergistic coal flame-retardant dust suppressant, which comprises a phosphorus flame retardant, a silane coupling agent, a catalyst, a solvent, a silicon flame retardant, a pH regulator, deionized water, an alcohol compound, a natural polymer, a monomer, a pH buffering agent, an initiator, a cross-linking agent, a surfactant and a plasticizer. The phosphorus flame retardant and the silane coupling agent are combined through free radical addition reaction to obtain a flame retardant intermediate, then the flame retardant intermediate is hydrolyzed to obtain a silanol group, the silanol group is dehydrated and combined with hydroxyl on the silicon flame retardant to obtain a silicon-phosphorus synergistic flame retardant, and finally the silicon-phosphorus synergistic coal flame retardant dust suppressant is combined with natural polymers, monomers, surfactants, plasticizers and other dust suppression components through free radical polymerization reaction to obtain the silicon-phosphorus synergistic coal flame retardant dust suppressant with both flame retardant and dust suppression performances. The flame-retardant dust suppressant has the functions of wetting, bonding, condensing, retaining water and the like, can condense and bond coal dust particles quickly after being sprayed, enhances the capture capacity of water to the coal dust due to good wettability, and achieves the effect of quickly reducing dust. After spraying, a layer of soft and compact polymer film is formed on the surface of the pulverized coal, and the pulverized coal has excellent mechanical property, flexibility, anti-vibration property and anti-wind erosion property, and is not easy to break due to wind erosion and vibration. Not only can play the effect of preventing coal dust from floating, but also can effectively slow down the evaporation of water to achieve the purpose of locking water, thereby greatly prolonging the dust suppression period. The flame-retardant dust suppressant introduces silicon and phosphorus elements, is an efficient silicon-phosphorus synergistic flame-retardant system, can overcome the defects of low flame-retardant level and small limiting oxygen index of a single flame retardant, can fully exert respective performances by synergistic use of multiple flame retardants, reduces the cost, and simultaneously improves the flame-retardant performance of the material. And the macromolecular film formed after spraying can play the effect of isolating oxygen, thereby preventing the spontaneous combustion of coal. The flame-retardant dust suppressant is made of an environment-friendly degradable material, and does not generate toxic and harmful gases when coal is combusted. The coal dust can be effectively slowed down and the coal can be prevented from spontaneous combustion in the processes of coal mining, storage, transportation and combustion, so that the air pollution and the waste of coal resources are reduced, and the method has great practical significance and application prospect.

Furthermore, the materials adopted by the natural polymer and the silicon flame retardant are from nature, have rich resources, low price, no pollution to the environment and good biocompatibility.

The invention also discloses a preparation method of the silicon-phosphorus synergistic coal flame-retardant dust suppressant, active hydrogen on the phosphorus flame retardant can generate free radical addition reaction with double bonds on the silane coupling agent, a catalyst is added to accelerate the reaction, and a flame-retardant intermediate is obtained through the reaction; then hydrolyzing the flame-retardant intermediate to obtain a silanol group, and dehydrating and combining the silanol group with hydroxyl on the silicon flame retardant to obtain the silicon-phosphorus synergistic flame retardant; and finally, combining the flame retardant with natural high molecules, monomers, a surfactant, a plasticizer and other dust suppression components through free radical polymerization to obtain the silicon-phosphorus synergistic coal flame-retardant dust suppressant with flame retardance and dust suppression simultaneously. The flame retardant is prepared by reacting several flame retardant components to obtain a flame retardant intermediate and finally preparing the flame retardant, and has better compatibility with materials.

Further, when the solution A is prepared, the inert gas is introduced to exhaust air, so that the condition that the subsequent reaction is influenced by the oxidation of free radicals generated in the reaction process of double bonds on the silane coupling agent and the phosphorus flame retardant by oxygen is prevented;

the monomer is easy to volatilize due to a large amount of heat generated during neutralization, so that the monomer can be prevented from volatilizing during neutralization in an ice-water bath.

Further, when the solution C is prepared, the mass ratio of the alcohol compound to the deionized water is 19:1, and the hydrolysis reaction is faster at the ratio, so that the hydrolysis is facilitated.

Drawings

FIG. 1 is a reaction scheme of the flame retardant dust suppressant of the present invention;

FIG. 2 is an infrared spectrum of KH570-DOPO and DOPO as flame retardant intermediates;

FIG. 3 is an XRD pattern of the flame retardant intermediates KH570-DOPO and DOPO;

FIG. 4 is an infrared spectrum of the flame retardant dust suppressant;

FIG. 5 is an XRD pattern of the flame retardant dust suppressant;

FIG. 6 shows the surface morphology of the pulverized coal after spraying water (a) and the flame retardant and dust suppressant (b), respectively;

FIG. 7 shows the results of the flame retardant performance test of the flame retardant dust suppressant.

Detailed Description

The invention discloses a silicon-phosphorus synergistic coal flame-retardant dust suppressant, which comprises the following raw materials in parts by mass:

0.10-0.30 part of phosphorus flame retardant, 0.15-0.30 part of silane coupling agent, 0.008-0.018 part of catalyst, 80.0-160.0 parts of solvent, 0.10-0.40 part of silicon flame retardant, 0.1-0.4 part of pH regulator, 83.0-125.0 parts of deionized water, 57.0-95.0 parts of alcohol compound, 1.0-2.0 parts of natural polymer, 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 0.1-0.4 part of initiator, 0.02-0.08 part of cross-linking agent, 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer.

Specifically, the phosphorus flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).

Specifically, the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.

Specifically, the catalyst is at least one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, and dimethyl azobisisobutyrate.

Specifically, the silicon-based flame retardant is nano SiO₂At least one of kaolin, diatomaceous earth, montmorillonite and attapulgite.

Specifically, the solvent is at least one of absolute ethyl alcohol, benzene, toluene, chloroform, acetone, cyclohexane and tetrahydrofuran.

Specifically, the pH regulator is at least one of acetic acid and hydrochloric acid.

Specifically, the pH buffer is sodium hydroxide.

Specifically, the alcohol compound is at least one of methanol and ethanol.

Specifically, the natural polymer is at least one of sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof, and chitosan.

Specifically, the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid.

Specifically, the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite.

Specifically, the crosslinking agent is at least one of N, N' -methylene bisacrylamide and dimethyldiallylammonium chloride.

Specifically, the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.

Specifically, the plasticizer is glycerol.

The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.