WO2016202233A1

WO2016202233A1 - Flame retardant of red phosphorus micro powder in aqueous suspension and manufacturing method and application thereof

Info

Publication number: WO2016202233A1
Application number: PCT/CN2016/085663
Authority: WO
Inventors: 郭岳; 李谦
Original assignee: 中蓝晨光化工研究设计院有限公司
Priority date: 2015-06-17
Filing date: 2016-06-14
Publication date: 2016-12-22
Also published as: CN104861203B; CN104861203A

Abstract

Disclosed are a flame retardant of red phosphorus micro powder in aqueous suspension and manufacturing method thereof. The manufacturing method comprises the steps of: adding a wetting and dispersing agent and an appropriate amount of water into red phosphorus micro powder and performing a grinding operation; adding water into the wet ground red phosphorus micro powder to perform a dispersing operation; and adding an anti-settling agent into the dispersion of red phosphorus micro powder and dispersing the same continuously until uniform to obtain a flame retardant of red phosphorus micro powder in aqueous suspension, wherein the red phosphorus content is 20-60%, and the viscosity is 10-500 cp, usually 10-100 cp. The aqueous suspension has good flowability and thixotropy, and the flame-retardant effect thereof on a material treated thereby is good and uniform; meanwhile, the suspension has good stability, low odor, and a wide variety of applications in polymers, paints, coatings and fabrics requiring flame retardance.

Description

Red phosphorus micro powder aqueous suspension flame retardant and preparation method and application thereof

Technical field

The invention relates to a red phosphorus flame retardant, and more particularly to a red phosphorus micro powder aqueous suspension flame retardant and a preparation method thereof, and belongs to the technical field of flame retardant preparations and preparation.

Background technique

Red phosphorus is a highly effective flame retardant. Red phosphorus is easily oxidized to phosphorus oxide by heat. In the case of water, it is rapidly converted into phosphoric acid, metaphosphoric acid, polyphosphoric acid, etc. to cover the surface of the fuel and protect it. And shielding effect, mixed phosphoric acid has a strong dehydration and carbonization effect on the polymer at high temperature, and can form a stable glass carbonization layer on the surface of the fuel to further enhance the flame retardant effect. The addition of red phosphorus in the finishing of polymer foaming materials, epoxy and unsaturated polyester coatings, coatings and fabrics can effectively play a role in flame retardancy, but the red phosphorus micropowder is easy to agglomerate due to its small particle size. Uneven dispersion, it is difficult to play a good, uniform flame retardant effect; directly use water or other solvents to disperse and mix the red phosphorus micropowder, this addition also has great drawbacks. First, since the density of red phosphorus is about 2.34 g/cm3, which is much larger than the density of water or the organic solvent used, it is easy to settle and the solid-liquid phase is dispersed, and the dispersion is uneven at the time of addition; secondly, water and others are used. The solvent directly disperses red phosphorus. The content of red phosphorus in the solution is limited. When the content of red phosphorus in the solution exceeds 20%, the sedimentation rate is very fast. When the red phosphorus is just dispersed for about 10 minutes, it is almost complete. Settling, so that it can not be well added and a large amount of addition, especially when dealing with a large amount of polymer, paint, coating and fabric requiring high content of red phosphorus, it can not meet the required requirements, and achieve a very uniform The flame retardant effect; finally, because of its rapid settling speed, it cannot be prepared in large quantities in a certain period of time.

Summary of the invention

The invention aims to provide a red phosphorus micropowder aqueous suspension flame retardant and a preparation method thereof for the problem that the existing red phosphorus micropowder is difficult to disperse and difficult to be added in a large amount when used for coating, coating and fabric flame retardant. The red phosphorus micropowder aqueous suspension flame retardant prepared by the method has a red phosphorus content of 20% to 60%, and the active ingredient has high red phosphorus content, and the aqueous suspension has good fluidity, and is easy to be added, processed and dispersed during use. It is uniform and has a good uniform flame retardant effect on the treated material. At the same time, the aqueous suspension flame retardant has good stability, stable time of more than half a year, low odor, and can be prepared and used on a large scale.

The object of the present invention is achieved based on the following principles and the technical solutions implemented.

The preparation principle of the red phosphorus micro powder aqueous suspension flame retardant of the invention is:

First, by using a wetting dispersant and grinding the dispersant on the surface of the solid particles, the surface tension of the solidified particles is also easily wetted while reducing the interfacial tension between the liquid-liquid or solid-liquid. At the same time, an adsorption layer can be formed on the surface of the solid particles to increase the charge on the surface of the solid particles, and to increase the reaction force between the particles forming the steric hindrance, so that the surface of the solid particles forms a bilayer structure, and the outer layer of the dispersant is polar. The end has a strong affinity with water, which can increase the degree of wetness of solid particles by water, and the solid particles are separated by electrostatic repulsion; secondly, by adding anti-settling agent to the water dispersion system of red phosphorus fine powder, The anti-settling agent forms a three-dimensional network structure in the system and increases the uniformity and suspension performance of the system, thereby maintaining the relative stability of the dispersion system. In addition, in order to match the viscosity of the flame retardant material, the viscosity of the suspension can also be adjusted by adding a thickener to achieve a better operation effect.

According to the above principle, the technical solution adopted by the present invention is as follows:

The invention relates to a red phosphorus micro powder aqueous suspension flame retardant, characterized in that the red phosphorus micro powder aqueous suspension has a red phosphorus content of 20% to 50%, a viscosity of 10 to 500 cp, and usually 10 to 100 cp.

The preparation method of the red phosphorus micro powder aqueous suspension flame retardant is carried out as follows:

A. In the weighed red phosphorus micropowder, based on the red phosphorus micropowder, add 0.5 to 5% by weight. Grinding dispersing agent and 5-10% water, grinding, so that the surface of the red phosphorus powder is evenly covered with a wetting dispersing agent;

B. The red phosphorus micropowder coated with a layer of wet dispersing agent after being ground in step A is transferred into a plastic cup container, and 80-390% of water is added as red phosphorus powder according to the weight ratio, and then the high-speed shearing emulsifier is used. Disperse at 3000~5000rpm for 30min;

C. In the red phosphorus micropowder solution dispersed in step B, add anti-settling agent which is 1~10% of the mass of red phosphorus micropowder solution, and continue to disperse for 10-15 min at 3000-6000 rpm until the anti-settling agent is evenly dispersed. That is, a red phosphorus micropowder aqueous suspension flame retardant product is obtained.

According to the viscosity requirement of the flame retardant material, after adding the anti-precipitation agent for dispersion in step C, a thickener of 0.1 to 5% by mass of the red phosphorus micropowder solution may be added, and the dispersion is further continued to obtain the red phosphorus powder having an increased viscosity. Suspension flame retardant products.

The red phosphorus fine powder may be replaced by stabilized red phosphorus fine powder, and the particle diameter thereof is less than 100 μm.

The stabilized red phosphorus fine powder refers to a red phosphorus fine powder coated with an organic or inorganic material.

The wetting dispersing agent is an anionic polyfunctional polymer alkoxide solution, an acrylate copolymer ammonium salt solution, an acrylamide propyl trimethyl ammonium chloride solution, a butyl acrylate-acrylic acid copolymer ammonium salt solution, N- At least one of oleoyl sarcosine octadecyl salt solution, ammonium lauryl sulfate solution or ammonium lauryl sulfate solution.

The anti-settling agent is one or more of fumed silica, organic bentonite, modified urea solution, acrylic emulsion or hydrogenated castor oil.

The thickener is one or more of polyvinyl alcohol PVA, polyethylene glycol PEG, polyacrylamide PMA or soluble starch.

The thickener is polyvinyl alcohol PVA1788, polyethylene glycol PEG600 or polyacrylamide PMA having a molecular weight of 3 million.

The red phosphorus micropowder aqueous suspension flame retardant prepared by the invention can be used in the form of liquid addition for impregnation and coating flame retardancy of polymer aqueous foaming, carpet, non-woven fabric, etc., and can also be directly used for natural Flame retardant of rubber, elastomer, latex, adhesive, coating and polymer foaming, generally used in a weight ratio of 5 to 15%, and also with metal hydroxides, melamine and its derivatives, polyphosphates, etc. Used together to achieve better flame retardant effects.

The outstanding technical effects of the present invention are manifested in:

1. Adding a wetting dispersing agent and wet-grinding treatment, after the dispersing agent is uniformly adsorbed on the surface of the red phosphorus fine powder, not only can the solid particles be wetted by water, but also the electrostatic repulsion between the solid particles. Keep away from it, thus effectively preventing the agglomeration of red phosphorus powder.

2. Adding water to the red phosphorus micropowder after wetting and grinding, and then adding anti-settling agent to the red phosphorus micropowder water dispersion system can effectively increase the suspension performance of the dispersion system, thereby maintaining the relative dispersion of the dispersion system well. Stable, and stable for more than half a year, low odor.

3. By adjusting the viscosity of the suspension by adding a thickener, the viscosity requirements of different flame retardant materials can be met, thereby achieving better operation results.

4. The aqueous suspension flame retardant of the invention has a red phosphorus content of 20% to 60%, a viscosity of 10 to 500 cp, usually 10 to 100 cp, not only an active ingredient having a high red phosphorus content, but also an aqueous suspension having good fluidity. It is easy to add, handle and disperse even when used, and has a good uniform flame retardant effect on the treated material. At the same time, the aqueous suspension flame retardant has good stability, stable time of more than half a year, and low odor, which can be large. Scale preparation and use.

detailed description

Example 1

A. Add 20g of acrylate copolymer ammonium salt to 20g and 50μm red phosphorus powder. After grinding the liquid and 2g of water, the surface of the red phosphorus powder is uniformly covered with a layer of wet dispersing agent;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 78g water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 0.5 g of the modified urea solution to the red phosphorus micropowder solution dispersed in step B, and continue to disperse for 10 min at 3000 rpm to obtain a red phosphorus micropowder aqueous suspension flame retardant product.

The properties of the red phosphorus micropowder aqueous suspension flame retardant are as follows:

Viscosity: 10 cp, low odor, suspension, storage time of 6 months, long-term storage with thixotropic, slight agitation to become a flowable liquid.

Example 2

A, in 100g, 100μm red phosphorus powder, adding 3g anionic polyfunctional polymer alkoxide solution and 5g water, grinding, the surface of the red phosphorus powder is evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 95g of water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 2.5 g of the modified urea solution to the red phosphorus micropowder solution dispersed in the step B, and continue to disperse for 5 min at 5000 rpm to obtain a red phosphorus micropowder aqueous suspension flame retardant product.

Viscosity: 20 cp, low odor, suspension, storage time of 6 months, long-term preservation with thixotropic, slight agitation to become a flowable liquid.

Example 3

A, in 100g, particle size of 50μm red phosphorus micropowder, 2g of acrylate copolymer ammonium salt solution and 8 water were added after grinding, the surface of the red phosphorus powder was evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 90g of water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 2.5 g of modified urea solution to the red phosphorus micropowder solution dispersed in step B, and continue to disperse for 10 min at 3000 rpm, then add 0.2 g of polyacrylamide, and disperse for 2 min at 3000 rpm to obtain an aqueous suspension of red phosphorus micropowder. Flame retardant products.

Example 4

A, in 500g, particle size 50μm stabilized red phosphorus micropowder, 25g of ammonium lauryl sulfate solution and 25 water, after grinding, the surface of the red phosphorus powder is evenly covered with a layer of wet dispersant;

B. The red phosphorus micropowder coated with a layer of wet dispersing agent after being ground in step A is transferred into a plastic cup, and 425 g of water is added, and then dispersed at 5000 rpm for 30 min with a high speed shear emulsifier disperser;

C. Add 30 g of fumed silica and 20 g of acrylic emulsion to the red phosphorus micropowder solution dispersed in step B, and continue to disperse at 4000 rpm for 15 min, then add 50 g of soluble starch, and disperse for 5 min at 5000 rpm to obtain red phosphorus powder. Suspension flame retardant products.

Viscosity: 500cp, very low odor, thixotropic fluid, storage time of 6 months, long-term preservation with thixotropic, slight agitation to become a flowable liquid.

Example 5

A, in 200g, particle size of 100μm red phosphorus micropowder, 10g of butyl acrylate-acrylic acid copolymer ammonium salt solution and 10g of water were added to grind, the surface of the red phosphorus micropowder was evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 160 g of water is added, and then dispersed by a high-speed shear emulsifier at 3000 rpm for 30 min;

C. Add 10 g of hydrogenated castor oil and 5 g of organic solution to the red phosphorus micropowder solution dispersed in step B. Bentonite, and continued to disperse for 15 min at 6000 rpm, then add 2 g of polyvinyl alcohol, and disperse for 5 min at 5000 rpm to obtain a red phosphorus micropowder aqueous suspension flame retardant product.

Viscosity: 20cp, very low odor, thixotropic fluid, storage time of 6 months, long-term preservation with thixotropic, slight agitation to become a flowable liquid.

Example 6

A, in a 100g, 10μm stabilized red phosphorus micropowder, 4g of acrylate copolymer ammonium salt solution and 4g of water were added to grind, the surface of the red phosphorus micropowder was evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 86g of water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 2.5 g of modified urea solution and 5 g of fumed silica to the red phosphorus micropowder solution dispersed in step B, and continue to disperse at 3000 rpm for 10 min, then add 6 g of PEG 600, and disperse for 5 min at 4000 rpm to obtain red phosphorus. Micronized aqueous suspension flame retardant products.

Viscosity: 50 cp, very low odor, thixotropic fluid, storage time of 6 months, long-term preservation with thixotropic, slight agitation to become a flowable liquid.

Example 7

A, in 2000g, a particle size of 100μm red phosphorus micropowder, 10g of ammonium lauryl sulfate ammonium salt solution, and 200g of water after grinding, the surface of the red phosphorus micropowder is evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 1790g water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 100 g of acrylic acid emulsion and 100 g of hydrogenated castor oil to the red phosphorus micropowder solution dispersed in step B, and continue to disperse at 5000 rpm for 10 min to obtain a red phosphorus micropowder aqueous suspension flame retardant. product.

Viscosity: 150 cp, very low odor, thixotropic fluid, storage time of 6 months, long-term storage with thixotropic, slight agitation to become a flowable liquid.

Example 8

A, in 100g, 50μm red phosphorus powder, add 2g acrylate copolymer ammonium salt solution, and 2g acrylamidopropyltrimethylammonium chloride solution and 8g water, and then grind, the surface of red phosphorus powder is even Covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 150 g of water is added, and then dispersed at 4000 rpm for 30 min with a high-speed shear emulsifier disperser;

C. Add 5 g of modified urea solution to the red phosphorus micropowder solution dispersed in step B, and continue to disperse for 12 min at 5000 rpm, then add 0.2 g of polyvinyl alcohol, and continue to disperse for 2 min at 3000 rpm to obtain an aqueous suspension of red phosphorus micropowder. Flame retardant products.

Viscosity: 50 cp, very low odor, suspension, storage time of 6 months, long-term preservation with thixotropic, slight agitation to become a flowable liquid.

Example 9

A, in 200g, 30μm red phosphorus powder, adding 2g of ammonium lauryl ammonium salt solution and 14g of water and grinding, the surface of the red phosphorus powder is evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 200g of water is added, and then dispersed at 5000 rpm with a high-speed shear emulsifier disperser for 30 min;

C. Add 18g of fumed silica and 2g of acrylic emulsion to the red phosphorus micropowder solution dispersed in step B, and continue to disperse for 15min at 5000rpm to obtain a red phosphorus micropowder aqueous suspension flame retardant. Product.

Viscosity: 120 cp, very low odor, suspension, storage time of 6 months, long-term storage with thixotropic, slight agitation to become a flowable liquid.

Example 10

A, in 500g, 30μm red phosphorus powder, 10g anionic polyfunctional polymer alkoxide solution, 5g butyl acrylate-acrylic acid copolymer ammonium salt solution and 50g water, grinding, causing red phosphorus powder surface Evenly covering a layer of wet dispersant;

B. The red phosphorus micropowder coated with a layer of wet dispersing agent after being ground in step A is transferred into a plastic cup, and 1500 g of water is added, and then dispersed at 5000 rpm for 30 min with a high speed shear emulsifier disperser;

C. Add 10 g of hydrogenated castor oil to the red phosphorus micropowder solution dispersed in step B, and continue to disperse for 13 min at 4000 rpm, then add 25 g of polyethylene glycol, and disperse for 5 min at 3000 rpm to obtain a red phosphorus micropowder aqueous suspension. Fuel product.

Viscosity: 65 cp, low odor, suspension, storage time of 6 months, long-term storage with thixotropic, slight agitation to become a flowable liquid.

Example 11

A, in 50g, particle size of 10μm red phosphorus micropowder, 5g of ammonium lauryl sulfate solution and 5g of water were added to grind, the surface of the red phosphorus micropowder was evenly covered with a layer of wet dispersant;

B, the red phosphorus powder coated with a layer of wet dispersing agent after the step A is transferred into a plastic cup, 100g of water is added, and then dispersed by a high-speed shear emulsifier at 3000rpm for 30min;

C. Add 5 g of organic bentonite to the red phosphorus micropowder solution dispersed in step B, and continue to disperse at 5000 rpm for 10 min to obtain a red phosphorus micropowder aqueous suspension flame retardant product.

Viscosity: 30 cp, low odor, suspension, storage time of 6 months, long-term storage with thixotropic, slight agitation to become a flowable liquid.

Claims

The invention relates to a red phosphorus micro powder aqueous suspension flame retardant, characterized in that the red phosphorus micro powder aqueous suspension has a red phosphorus content of 20% to 60% and a viscosity of 10 to 500 cp.
The red phosphorus micropowder aqueous suspension flame retardant according to claim 1, wherein the red phosphorus micropowder aqueous suspension has a viscosity of 10 to 50 cp.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 1 or 2, wherein the process steps are as follows:

A. In the weighed red phosphorus micropowder, based on the red phosphorus micropowder, 0.5-5% wetting dispersing agent and 5-10% water are added respectively according to the weight ratio, and then ground to make the surface of the red phosphorus powder evenly Covered with a layer of wet dispersant;

B. The red phosphorus micropowder coated with a layer of wet dispersing agent after being ground in step A is transferred into a plastic cup container, and 80-390% of water is added as red phosphorus powder according to the weight ratio, and then the high-speed shearing emulsifier is used. Disperse at 3000~5000rpm for 30min;

C. In the red phosphorus micropowder solution dispersed in step B, add anti-settling agent which is 1~10% of the mass of red phosphorus micropowder solution, and continue to disperse for 10-15 min at 3000-6000 rpm until the anti-settling agent is evenly dispersed. That is, a red phosphorus micropowder aqueous suspension flame retardant product is obtained.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, characterized in that: after adding the anti-precipitant agent for dispersion in step C, the thickening of the red phosphorus micropowder solution is 0.1-5% by weight. Agent.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, wherein the red phosphorus micropowder is replaced by stabilized red phosphorus micropowder, and the particle diameter thereof is less than 100 μm.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, wherein the wetting dispersant is an anionic polyfunctional polymer alkoxide solution, an acrylate copolymer ammonium salt solution, and propylene. Amidopropyltrimethylammonium chloride solution, butyl acrylate-acrylic acid copolymer ammonium At least one of a salt solution, a solution of N-oleoyl sarcosine octadecyl salt, a solution of ammonium lauryl sulfate or a solution of ammonium lauryl sulfate.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, wherein the anti-settling agent is fumed silica, organic bentonite, modified urea solution, acrylic emulsion or hydrogenated castor oil. One or several.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, wherein the thickener is in polyvinyl alcohol PVA, polyethylene glycol PEG, polyacrylamide PMA or soluble starch. One or several.
The method for preparing a red phosphorus micropowder aqueous suspension flame retardant according to claim 3, wherein the thickener is polyvinyl alcohol PVA1788, polyethylene glycol PEG600 or polyacrylamide PMA having a molecular weight of 3 million. .
The red phosphorus micropowder aqueous suspension flame retardant according to claim 1 or 2, which is used in the form of liquid addition in the polymer aqueous foaming, carpet, non-woven fabric impregnation and coating flame retardant application, or directly It is used for flame retardant of natural rubber, artificial rubber, latex, adhesive, coating and polymer foaming. The dosage is 5-15% by weight.