CN108641559B - Intumescent flame retardant and preparation method and application thereof - Google Patents
Intumescent flame retardant and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses an intumescent flame retardant and a preparation method and application thereof. The intumescent flame retardant is prepared from the following raw materials in parts by weight: modified ammonium polyphosphate: 4-6 parts; hyperbranched polyester: 3-4 parts; polyvinyl alcohols: 0-1 part; anhydrous ethanol: 45-50 parts. The hyperbranched polyester can be used as a char forming agent and a film forming agent; the invention provides the application of the intumescent flame retardant in engineering plastics, wherein the surface of the engineering plastics is treated by magnetron sputtering during application, the surface energy of the engineering plastics can be improved without complex surface wetting agent or chemical deposition treatment, the intumescent flame retardant is easy to coat, and the adhesion reaches 5B level. The hyperbranched polyester in the flame retardant has excellent char formation property, and the excellent flame retardant effect is achieved while the adhesion firmness of the coating is improved; the limiting oxygen index LOI on polypropylene reaches 32 percent and reaches the level of V0 in UL-94 test, and the coating has excellent flexibility, can adapt to the deformation of a matrix without falling off, and has wide application environment.
Description
Technical Field
The invention discloses an intumescent flame retardant and a preparation method and application thereof, and belongs to the technical field of flame-retardant coatings.
Background
With the development of society, the consumption of various engineering plastic products is rapidly increased, and high polymer materials are seen everywhere in our lives. The engineering plastics are easy to burn, and are easy to cause fire and life and property loss. Therefore, the research significance of carrying out flame retardant treatment on engineering plastics to delay the fire spreading speed and reduce life and property losses is great. However, in the flame retardant manner of engineering plastics, the conventional method is to mix and add the flame retardant into the base material by adopting a blending manner, and in order to achieve the ideal flame retardant property, a large addition amount is needed, so that the mechanical property of the engineering plastics is seriously damaged, and the practical application of the flame retardant material is limited.
The flame-retardant coating layer can not cause the problems, and the flame-retardant coating layer can still keep the original mechanical properties of the engineering plastics. However, there is also a related bottleneck to applying flame retardant coatings to engineering plastic surfaces. The two main reasons are that the surface polarity of the engineering plastic is low, so that the binding force between the coating and the substrate is reduced, and the adhesion force is insufficient. Secondly, the flexibility of the coating is difficult to obtain, and the coating can keep good flexibility by adding a plurality of components. Therefore, the flame-retardant coating with flexibility and high adhesion is a precondition for ensuring that the coating does not fall off in the transportation and application processes of the engineering plastics.
Chinese patent CN105256572B discloses a halogen-free flame-retardant coating adhesive and a preparation method thereof, and the method comprises various components of water-based acrylate emulsion, a phosphorus-nitrogen flame retardant, a polyhydroxy compound, a flame-retardant synergist, a dispersing agent, a wetting agent, a thickening agent and distilled water. The flame retardant components are complex and not simple enough, and chemical deposition is adopted, so that the adhesive strength is not sufficient, and the flame retardant property is not mentioned. Chinese patent CN106833259A discloses a plastic surface flame-retardant coating and a preparation method thereof, wherein the flame-retardant coating is prepared from a film-forming agent, a flame retardant, a curing agent, a flatting agent, a coupling agent, a filler and an ethylene glycol monobutyl ether solvent. The composition is complex, the solvent used is not an environmentally friendly solvent, and the flame retardant rating of the coating only reaches the V1 rating, and there is no mention of how to treat the plastic surface so that the coating adheres thereto. Chinese patent CN106189566A discloses "an intumescent flame retardant coating for engineering plastic surface and its preparation method" the treatment of engineering plastic surface with wetting agent mentioned herein is not suitable for continuous and rapid surface treatment of large amount of samples. Chinese patent CN101597307 discloses 'a UV-curable phosphorus-nitrogen-containing halogen-free flame retardant and a preparation method thereof', the flame retardant needs to be applied to wood, plastic and circuit boards in a film-forming manner under UV curing, but the application to the plastic is limited because the flame retardant is cured in resin and has insufficient flexibility. Therefore, there is an urgent need to develop a flame retardant coating which is widely used and is easy to use.
Disclosure of Invention
The invention aims to provide an environment-friendly intumescent flame retardant and a preparation method thereof, wherein hyperbranched polyester is selected and can be used as a char forming agent and a film forming agent; the invention also provides application of the intumescent flame retardant in engineering plastics, and magnetron sputtering is adopted to treat the surface of the engineering plastics so as to improve the surface performance of the engineering plastics.
The invention selects a hyperbranched polyester which is usually used as a plasticizer to improve the rheological property of engineering plastics, and is used as a film forming agent and a char forming agent for a flame retardant coating. When the flame-retardant coating is used in engineering plastics, the surface of the engineering plastics is treated by magnetron sputtering, and compared with the prior chemical deposition or addition of a surface wetting agent, the flame-retardant coating has higher flexibility and simplicity and is easy for industrial application; and the adhesiveness of the coating is improved in the process of improving the flame retardance, and the coating has excellent flame retardance and good flexibility and adhesive force.
The invention provides an intumescent flame retardant which is prepared from the following raw materials in parts by weight:
modified ammonium polyphosphate: 4-6 parts;
hyperbranched polyester (char-forming agent, film-forming agent): 3-4 parts;
polyvinyl alcohol (film-forming agent): 0-1 part;
anhydrous ethanol: 45-50 parts of a solvent;
the polyvinyl alcohol is one of polyvinyl formal, polyvinyl formal acetaldehyde and polyvinyl alcohol; the structure of the hyperbranched polyester is as follows:
In the above scheme, the preparation method of the modified ammonium polyphosphate comprises:
(1) ultrasonically dispersing 40-45 parts of ammonium polyphosphate in 150 parts of anhydrous ethanol at the temperature of 70-80 ℃, and then pouring the solution into a single-neck flask for magnetic stirring;
(2) dripping 1-2 parts of silane coupling agent into 10-12 parts of absolute ethyl alcohol, dripping 4-5 parts of glacial acetic acid at the dripping speed of 5-10ml/min, adjusting the pH value to 3-5, and then adding into the single-neck flask containing ammonium polyphosphate at the dripping speed of 5-10 ml/min;
(3) fully stirring the mixture for 2 to 2.5 hours at the temperature of between 70 and 75 ℃ and at the rotating speed of 200-300r/min to obtain a silane coupling agent modified ammonium polyphosphate crude product;
(4) carrying out suction filtration on the crude product, washing the crude product for a plurality of times by using absolute ethyl alcohol, and drying the crude product overnight at the temperature of 80-100 ℃ to obtain silane coupling agent modified ammonium polyphosphate;
(5) dissolving 15-20 parts of hyperbranched polyester in a solvent, adding 0.1-0.2 part of a catalyst, pouring into a three-neck flask, reacting at room temperature for half an hour, adding 5-7 parts of ammonium polyphosphate modified by the silane coupling agent into the three-neck flask, heating to 45-50 ℃, and reacting for 6-8 hours to obtain a modified ammonium polyphosphate crude product;
(6) and (3) washing the crude product with absolute ethyl alcohol for two to three times, then carrying out suction filtration to obtain a product, and drying at 80 ℃ overnight to obtain the final modified ammonium polyphosphate.
Further, in the preparation method of the modified ammonium polyphosphate, the silane coupling agent is 3-aminopropyl triethoxysilane.
Further, in the preparation method of the modified ammonium polyphosphate, the solvent is ethanol.
The catalyst is the combination of dicyclohexylcarbodiimide and 4-dimethylaminopyridine or the combination of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine.
The invention provides a preparation method of the intumescent flame retardant, which comprises the following steps:
(1) adding ethanol into a beaker, controlling the stirring speed at 800r/min, then adding hyperbranched polyester (a charring agent and a film forming agent), and continuously stirring for 5-10min after dissolving;
(2) slowly adding polyvinyl alcohol for multiple times at the same rotating speed, and continuously stirring for 5-10 min;
(3) after the step (2) is finished, raising the temperature to 130-140 ℃, adding modified ammonium polyphosphate into the solution, and stirring at constant temperature for 5-10min to uniformly disperse the modified ammonium polyphosphate in the solution;
(4) under the conditions that the stirring speed is 500-600r/min and the temperature is 130-140 ℃, evaporating the anhydrous ethanol until the anhydrous ethanol is in a viscous state, and stopping heating; obtaining the viscous flame retardant.
In the method, the hyperbranched polyester plays the roles of a char-forming agent and a film-forming agent.
The invention provides application of the intumescent flame retardant in engineering plastics. In application, the engineering plastic adopts magnetron sputtering to treat the surface of the engineering plastic so as to improve the surface energy of the engineering plastic and improve the adhesion of a coating.
The application comprises the following steps:
(1) placing an engineering plastic sample strip in a magnetron sputtering device, wherein a power supply is a Kaufman power supply, starting a molecular pump when vacuumizing is carried out to 35-50Pa, and injecting argon or helium with the flow of 18-20 sccm; irradiating for 0.5-1h at the bias voltage of 400-420V;
(2) and (3) coating the viscous flame retardant prepared by the method on the engineering plastic sample strip treated in the step (1) by adopting a pulling method to obtain the intumescent flame retardant coating.
In the scheme, the magnetron sputtering equipment is an unbalanced magnetron sputtering instrument.
The invention has the beneficial effects that:
(1) the used solvent only needs absolute ethyl alcohol, so that the pollution to the environment can be greatly reduced, and the environment-friendly effect is achieved;
(2) under the action of only using hyperbranched polyester or hyperbranched polyester and a film forming agent, a coating with excellent compact adhesion can be formed, so that the coating can obtain excellent flame retardant effect and good adhesion under the condition of low thickness;
(3) the coating has novel components, and the charring agent hyperbranched polyester also has the effect of a film forming agent and can provide excellent flame retardant effect;
(4) the surface energy of the engineering plastic is improved by adopting magnetron sputtering treatment without complex surface wetting agent or chemical deposition treatment, so that the coating is easy to coat and the coating adhesion is improved;
(5) the flame-retardant coating has bright appearance luster and excellent flexibility, can deform along with a high-molecular base material without falling off, and is suitable for a wider environment;
(6) the flame-retardant coating is not only suitable for engineering plastics, but also can be used for flame retardance of wood, steel and fabrics.
Drawings
FIG. 1 is an infrared spectrum of a modified ammonium polyphosphate obtained in example 1.
FIG. 2 is a photograph showing the surface adhesion of the intumescent flame retardant coating obtained in example 1 to polypropylene after the test.
FIG. 3 is a macroscopic and microscopic image of char formed after cone calorimetry test of the polypropylene coated with the flame retardant coating obtained in example 1.
FIG. 4 is a graph showing the variation of limiting oxygen index of different samples coated with polypropylene with different coating thicknesses, when the flame retardant coatings obtained in examples 1 to 3 are coated on the polypropylene.
FIG. 5 is a graph showing the flame retardant rating of the polypropylene coated with the flame retardant coatings obtained in examples 1 to 3, in which different samples were vertically burned at different coating thicknesses.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
firstly, 40 parts of ammonium polyphosphate is ultrasonically dispersed in 150 parts of absolute ethyl alcohol at the temperature of 80 ℃, and then poured into a single-neck flask for magnetic stirring. Then, 1 part of silane coupling agent is dropwise added into 10 parts of absolute ethyl alcohol, 4 parts of glacial acetic acid is dropwise added, the pH value is adjusted to 3.5, and then the mixture is dropwise added into the single-neck flask containing the ammonium polyphosphate. And fully stirring the mixture for 2 hours at the temperature of 75 ℃ at the rotating speed of 300r/min to obtain a silane coupling agent modified ammonium polyphosphate crude product. And then, carrying out suction filtration on the crude product, washing the crude product for a plurality of times by using absolute ethyl alcohol, and drying the crude product at 80 ℃ overnight to obtain a pure product. And dissolving 15 parts of hyperbranched polyester (char forming agent) in a solvent, adding 1 part of catalyst, pouring into a three-neck flask, reacting at room temperature for half an hour, adding 7 parts of the pure product into the three-neck flask, heating to 45 ℃, and reacting for 6 hours to obtain a modified crude product of the ammonium polyphosphate. And finally, washing the crude product with absolute ethyl alcohol for two to three times, carrying out suction filtration to obtain a product, drying at 80 ℃ overnight to obtain finally modified ammonium polyphosphate, adding 50 parts of ethanol into a beaker, adding 2 parts of hyperbranched polyester (a charring agent and a film forming agent) under the condition of magnetic stirring and heating until the hyperbranched polyester is completely dissolved, slowly adding 1 part of polyvinyl formal acetaldehyde in a small amount for multiple times, and continuing to stir at a high speed for 10min until the solution is in a transparent state. Under the condition that the temperature is 130 ℃, 3 parts of modified ammonium polyphosphate is added in sequence. And fully stirring the mixture for 5min at the rotating speed of 500r/min to obtain the evenly dispersed emulsion. At this speed and 130 ℃, heating and stirring were stopped until the solution reached a viscous state. Then taking a polypropylene sample strip, placing the sample strip in magnetron sputtering equipment, starting a molecular pump when the vacuum pumping is carried out to 35Pa, and flushing argon gas with the flow of 18 sccm; at a bias of 400V, irradiation was performed for 0.5 h. And finally, coating the viscous coating on the polypropylene sample strip subjected to magnetron sputtering treatment. The product obtained in this example was designated as sample 1.
The product obtained in this example was subjected to performance testing:
in the experimental process, the modified ammonium polyphosphate infrared spectrum is shown in figure 1. Amide bonds and methylene groups appear in the modified ammonium polyphosphate, and the absorption peak of the corresponding carboxyl hydroxyl of the hyperbranched polyester disappears, which indicates that the ammonium polyphosphate has been successfully modified.
Then, an adhesion test is carried out, the adhesion between the coating and the substrate is tested by using a 3M adhesive tape adhesion test method and referring to the standard ASTM D3359-02, and the result is shown in figure 2, wherein the left graph is the macroscopic bending of a sample strip, and the right graph is the adhesion test result; the flame retardant coating can be firmly attached to the polypropylene surface.
FIG. 3 is a macroscopic and microscopic image of char after the flame retardant coating is coated on polypropylene and burned. The upper left part is a top view after cone amount test, and the upper right part is a main view. The lower left is a scanning electron microscope image at low magnification, and the lower right is a scanning electron microscope image at high magnification. It can be seen that the carbon layer after combustion has good expansibility, and the formed carbon layer is compact, so that good heat insulation and oxygen insulation effects can be achieved.
Example 2
The modified ammonium polyphosphate prepared in example 1 was used.
Firstly, 50 parts of ethanol is added into a beaker, 2.5 parts of hyperbranched polyester (a charring agent and a film forming agent) is added under the condition of magnetic stirring and heating until the hyperbranched polyester is completely dissolved, then 1 part of polyvinyl formal acetaldehyde is slowly added for a plurality of times, and after the hyperbranched polyester is added, the high-speed stirring is continuously kept for 10min until the solution is in a transparent state. Under the condition that the temperature is 130 ℃, 3.75 parts of modified ammonium polyphosphate is added in sequence. And fully stirring the mixture for 5min at the rotating speed of 500-600r/min to obtain the emulsion with uniform dispersion. At this speed and 130 ℃, heating and stirring were stopped until the solution reached a viscous state. Then taking a polypropylene sample strip, placing the sample strip in magnetron sputtering equipment, starting a molecular pump when the power supply is a Kaufman power supply and the vacuum is pumped to 40Pa, and flushing argon with the flow of 19 sccm; at a bias of 410V, irradiation was performed for 0.5 h. And finally, coating the viscous coating on the polypropylene sample strip subjected to magnetron sputtering treatment. This example is designated as sample 2.
Example 3
The modified ammonium polyphosphate prepared in example 1 was used.
Firstly, 50 parts of ethanol is added into a beaker, 3 parts of hyperbranched polyester (a charring agent and a film forming agent) is added under the condition of magnetic stirring and heating until the hyperbranched polyester is completely dissolved, 1 part of polyvinyl formal acetaldehyde is slowly added for a plurality of times in small amount, and the high-speed stirring is continuously kept for 10min after the hyperbranched polyester is added until the solution is in a transparent state. Under the condition that the temperature is 130 ℃, 3 parts of modified ammonium polyphosphate is added in sequence. And fully stirring the mixture for 5min at the rotating speed of 500-600r/min to obtain the emulsion with uniform dispersion. At this speed and 130 ℃, heating and stirring were stopped until the solution reached a viscous state. Then taking a polypropylene sample strip, placing the sample strip in magnetron sputtering equipment, starting a molecular pump when the vacuum pumping is carried out to 40Pa, and flushing argon gas with the flow of 20 sccm; at a bias of 420V, irradiation was performed for 0.5 h. And finally, coating the viscous coating on the polypropylene sample strip subjected to magnetron sputtering treatment. This example is designated as sample 3.
FIG. 4 is a LOI oxygen index test graph, in which flame retardant coatings of sample 1, sample 2, and sample 3 were tested at different coating thicknesses, and the abscissa is the thickness of the coating.
Fig. 5 is a UL94 vertical burn test chart, taking sample 1, sample 2, sample 3 flame retardant coatings for testing, respectively, at different coating thicknesses, with the abscissa being the thickness of the coating. As can be seen from FIGS. 4 and 5, sample 3 is a sample in which modified ammonium polyphosphate and hyperbranched polyester are added in a one-to-one manner, and the coating thickness is 180 μm, which reaches V-0 level, LOI reaches 32%, and the flame retardant effect is good.
Example 4
The modified ammonium polyphosphate prepared in example 1 was used.
Firstly, 50 parts of ethanol is added into a beaker, 2.5 parts of hyperbranched polyester (a charring agent and a film forming agent) is added under the condition of magnetic stirring and heating until the hyperbranched polyester is completely dissolved, then 0.5 part of polyvinyl formal acetal is slowly added for a plurality of times, and after the hyperbranched polyester is added, the high-speed stirring is continuously kept for 10min until the solution is in a transparent state. Under the condition that the temperature is 130 ℃, 5 parts of modified ammonium polyphosphate is added in sequence. And fully stirring the mixture for 5min at the rotating speed of 500-600r/min to obtain the emulsion with uniform dispersion. At this speed and 130 ℃, heating and stirring were stopped until the solution reached a viscous state. Then taking a polypropylene sample strip, placing the sample strip in magnetron sputtering equipment, starting a molecular pump when the vacuum degree is 42Pa, and flushing argon gas with the flow of 20 sccm; at a bias of 420V, irradiation was performed for 0.5 h. And finally, coating the viscous coating on the polypropylene sample strip subjected to magnetron sputtering treatment.
Example 5
Firstly, 50 parts of ethanol is added into a beaker, 2.5 parts of hyperbranched polyester (a charring agent and a film forming agent) is added under the condition of magnetic stirring and heating until the hyperbranched polyester is completely dissolved, and then the high-speed stirring is continuously kept for 10min until the solution is in a transparent state. Under the condition that the temperature is 130 ℃, 5 parts of modified ammonium polyphosphate is added in sequence. And fully stirring the mixture for 5min at the rotating speed of 500-600r/min to obtain the emulsion with uniform dispersion. At this speed and 130 ℃, heating and stirring were stopped until the solution reached a viscous state. Then taking a polystyrene sample strip, placing the polystyrene sample strip in magnetron sputtering equipment, starting a molecular pump when the power supply is a Kaufman power supply and the vacuum is pumped to 40Pa, and flushing argon with the flow of 20 sccm; at a bias of 420V, irradiation was performed for 0.5 h. And finally, coating the viscous coating on the polystyrene sample strip subjected to magnetron sputtering treatment.
Claims (9)
1. An intumescent flame retardant characterized by: the feed is prepared from the following raw materials in parts by weight:
modified ammonium polyphosphate: 4-6 parts;
hyperbranched polyester: 3-4 parts;
polyvinyl alcohols: 0-1 part;
anhydrous ethanol: 45-50 parts of a solvent;
the preparation method of the modified ammonium polyphosphate comprises the following steps:
(1) ultrasonically dispersing 40-45 parts of ammonium polyphosphate in 150 parts of anhydrous ethanol at the temperature of 70-80 ℃, and then pouring the solution into a single-neck flask for magnetic stirring;
(2) dripping 1-2 parts of silane coupling agent into 10-12 parts of absolute ethyl alcohol, dripping 4-5 parts of glacial acetic acid at the dripping speed of 5-10mL/min, adjusting the pH value to 3-5, and then adding into the single-neck flask containing ammonium polyphosphate at the dripping speed of 5-10 mL/min;
(3) fully stirring the mixture for 2 to 2.5 hours at the temperature of between 70 and 75 ℃ and at the rotating speed of 200-300r/min to obtain a silane coupling agent modified ammonium polyphosphate crude product;
(4) carrying out suction filtration on the crude product, washing the crude product for a plurality of times by using absolute ethyl alcohol, and drying the crude product overnight at the temperature of 80-100 ℃ to obtain silane coupling agent modified ammonium polyphosphate;
(5) dissolving 15-20 parts of hyperbranched polyester in a solvent, adding 0.1-0.2 part of a catalyst, pouring into a three-neck flask, reacting at room temperature for half an hour, adding 5-7 parts of ammonium polyphosphate modified by the silane coupling agent into the three-neck flask, heating to 45-50 ℃, and reacting for 6-8 hours to obtain a modified ammonium polyphosphate crude product;
(6) washing the crude product with absolute ethyl alcohol for two to three times, then carrying out suction filtration to obtain a product, and drying at 80 ℃ overnight to obtain finally modified ammonium polyphosphate;
the polyvinyl alcohol is one of polyvinyl formal, polyvinyl formal acetaldehyde and polyvinyl alcohol; the structure of the hyperbranched polyester is as follows:
or
。
2. The intumescent flame retardant of claim 1, wherein: in the preparation method of the modified ammonium polyphosphate, the silane coupling agent is 3-aminopropyl triethoxysilane.
3. The intumescent flame retardant of claim 1, wherein: in the preparation method of the modified ammonium polyphosphate, the solvent is ethanol.
4. The intumescent flame retardant of claim 1, wherein: the catalyst is the combination of dicyclohexylcarbodiimide and 4-dimethylaminopyridine or the combination of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine.
5. A method for preparing the intumescent flame retardant of any of claims 1 to 4, characterized by comprising the steps of:
(1) adding ethanol into a beaker, controlling the stirring speed at 800r/min, then adding the hyperbranched polyester, and continuously stirring for 5-10min after dissolving;
(2) slowly adding polyvinyl alcohol for multiple times at the same rotating speed, and continuously stirring for 5-10 min;
(3) after the step (2) is finished, raising the temperature to 130-140 ℃, adding modified ammonium polyphosphate into the solution, and stirring at constant temperature for 5-10min to uniformly disperse the modified ammonium polyphosphate in the solution;
(4) under the conditions that the stirring speed is 500-600r/min and the temperature is 130-140 ℃, evaporating the absolute ethyl alcohol until the viscous state, and stopping heating; obtaining the viscous flame retardant.
6. Use of the intumescent flame retardant of any of claims 1 to 4 in engineering plastics.
7. Use according to claim 6, characterized in that: the surface of the engineering plastic is treated by magnetron sputtering to improve the surface energy of the engineering plastic so as to improve the adhesion of the coating.
8. Use according to claim 6, characterized in that: the method comprises the following steps:
(1) placing an engineering plastic sample strip in a magnetron sputtering device, wherein a power supply is a Kaufman power supply, starting a molecular pump when vacuumizing is carried out to 35-50Pa, and injecting argon or helium with the flow of 18-20 sccm; irradiating for 0.5-1h at the bias voltage of 400-420V;
(2) and (3) coating the viscous flame retardant on the engineering plastic sample strip treated in the step (1) by adopting a pulling method to obtain the intumescent flame retardant coating.
9. Use according to claim 8, characterized in that: the magnetron sputtering equipment is an unbalanced magnetron sputtering instrument.
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| NO346733B1 (en) | 2019-06-28 | 2022-12-05 | Klingelberg Products As | Flame retardant, method for its preparation and article comprising same |
| CN112921657A (en) * | 2021-01-18 | 2021-06-08 | 平阳盛兴无纺布有限公司 | Flame-retardant easily-decomposed environment-friendly non-woven fabric and preparation process thereof |
| CN113444424A (en) * | 2021-07-23 | 2021-09-28 | 江苏航运职业技术学院 | Preparation method of flame-retardant furniture composite coating |
| CN114653563B (en) * | 2022-02-11 | 2023-04-14 | 北新国际木业有限公司 | Surface flame-retardant treatment method for OSB (oriented strand board) and flame-retardant OSB |
| CN115386167B (en) * | 2022-09-27 | 2023-08-22 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
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