CN113845699B - Organic metal complex modified ammonium polyphosphate intumescent flame retardant and preparation method thereof - Google Patents
Organic metal complex modified ammonium polyphosphate intumescent flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic metal complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof 2+ ，Cu 2+ ，Mg 2+ ，Mn 2+ ，Ni 2+ ，Co 2+ ，Al 3+ Or Fe 3+ The organic ligand is any one of phenols, schiff bases, nitrogen heterocycles, amino acids and carboxylic acid compounds. The organic metal complex modified ammonium polyphosphate integrates an acid source, a gas source and a carbon source, can be independently used as an intumescent flame retardant, and the transition metal ions are beneficial to catalyzing high polymers to form carbon, so the organic metal complex modified ammonium polyphosphate is suitable for flame-retardant smoke-suppression modification of various high polymer materials; in addition, the intumescent flame retardant has good compatibility with high polymer materials. The preparation process of the organic metal complex modified ammonium polyphosphate intumescent flame retardant has the advantages of simple steps, strong operability, low cost and simple and convenient post-treatment process.
Description
Technical Field
The invention belongs to the field of high-molecular flame-retardant materials, and particularly relates to an organic metal complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof.
Technical Field
The high polymer material has excellent chemical resistance, mechanical property, electric insulation property and good processing property, so that the high polymer material is applied to various industries such as insulating materials, house decoration, space flight and aviation, electronic devices and the like. Common high polymer materials all have the defect of inflammability, which greatly limits the application of the materials and causes the study of broad scholars on the high polymer flame retardant materials.
Ammonium polyphosphate is a common commercial flame retardant additive with no toxicity and smoke and good thermal stability, contains a large amount of phosphorus elements and nitrogen elements, and can serve as an intumescent flame retardant in the combustion process. However, ammonium polyphosphate is an inorganic polymer compound, and is easy to absorb moisture in air when stored in the air, so that moisture absorption and hydrolysis are easy to occur; the ammonium polyphosphate used alone as a flame retardant is not very ideal for the flame retardant effect of the high polymer material and can cause the reduction of the mechanical property of the high polymer material. In addition, since ammonium polyphosphate does not contain a carbon source, in order to enhance the flame retardant efficiency of ammonium polyphosphate, it is necessary to improve the flame retardant efficiency of ammonium polyphosphate in cooperation with other char-forming agents.
Disclosure of Invention
The invention aims to provide an organic metal complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof, and aims to solve the problems of flammability and large smoke release amount of a high polymer material.
The chemical structural general formula of the organic metal complex modified ammonium polyphosphate intumescent flame retardant is as follows:
wherein M is 2+ Is Zn 2+ 、Cu 2+ 、Mg 2+ 、Mn 2+ 、Ni 2+ 、Co 2+ Any one of the metal ions of (1), M 3+ Is Al 3+ And Fe 3+ Any one of the metal ions of (1); r is any one of phenols, schiff bases, nitrogen heterocycles, amino acids and carboxylic acid compounds.
Further, the preparation method of the organic metal complex modified ammonium polyphosphate intumescent flame retardant comprises the following steps:
sequentially adding ammonium polyphosphate and a solvent into a three-neck flask provided with a mechanical stirrer and a thermometer; after the raw materials are uniformly mixed, dropwise adding a metal ion-containing solution into the three-neck flask at normal temperature, and stirring while dropwise adding; after the dropwise addition is finished, reacting for a period of time at normal temperature, then dropwise adding an organic ligand solution into the three-neck flask, and reacting for a period of time at a certain temperature; after the reaction is finished, cooling to room temperature, carrying out suction filtration, taking a filter cake, washing the filter cake for a plurality of times by using a solvent, and drying to obtain the organic metal complex modified ammonium polyphosphate intumescent flame retardant.
Wherein the solvent is one or more of toluene, xylene, tetrahydrofuran, water, dioxane, methanol, ethanol, acetone and acetonitrile.
The metal ion is Zn 2+ ，Cu 2+ ，Mg 2+ ，Mn 2+ ，Ni 2+ ，Co 2+ ，Al 3+ Or Fe 3+ Any one of the above.
The ligand is any one of phenols, schiff base, nitrogen heterocycle, amino acid and carboxylic acid compound.
The mass ratio of the metal ions to the ligand of the ammonium polyphosphate is 1: 0.2-2.
The reaction time at normal temperature is 1-3 hours.
The reaction temperature after the organic ligand is dripped is 20-80 ℃, and the reaction time is 18-36 hours.
The invention adopts ammonium polyphosphate, metal ions and various organic ligands as raw materials to synthesize the organic metal complex modified ammonium polyphosphate intumescent flame retardant, thereby integrating an acid source, a gas source and a carbon source, and due to the existence of the metal ions, the flame retardant efficiency of the ammonium polyphosphate is expected to be further improved, the ammonium polyphosphate intumescent flame retardant is suitable for flame retardant and smoke suppression modification of various high polymer materials and is compatible with the high polymer materials.
Compared with the prior art, the invention has the following advantages:
(1) The organic metal complex modified ammonium polyphosphate intumescent flame retardant provided by the invention has the advantages of simple synthesis process, short period, simple post-treatment process of the obtained flame retardant, high yield, and easiness in control and industrial production.
(2) The organic metal complex modified ammonium polyphosphate intumescent flame retardant provided by the invention integrates an acid source, a gas source and a carbon source, contains metal ions, and is a novel intumescent flame retardant.
(3) The organic metal complex modified ammonium polyphosphate intumescent flame retardant provided by the invention has adjustability, can be combined by selecting different metal ions and organic ligands, and solves the problems of flammability and high smoke toxicity of various high polymer materials.
Drawings
FIG. 1 is an infrared spectrum of urushiol-iron complex modified ammonium polyphosphate.
FIG. 2 is an infrared spectrum of urushiol-copper complex modified ammonium polyphosphate.
FIG. 3 is an infrared spectrum of urushiol-cobalt complex modified ammonium polyphosphate.
FIG. 4 is an infrared spectrum of urushiol-nickel complex modified ammonium polyphosphate.
FIG. 5 is an infrared spectrum of urushiol-zinc complex modified ammonium polyphosphate.
FIG. 6 is an infrared spectrum of catechol-iron complex modified ammonium polyphosphate.
Fig. 7 is an infrared spectrum of ammonium polyphosphate modified by cardanol-iron complex.
FIG. 8 is an infrared spectrum of ammonium polyphosphate modified by salicylaldehyde-diethylenetriamine Schiff base-cobalt complex.
FIG. 9 is an infrared spectrum of ammonium polyphosphate modified by salicylaldehyde-aminobenzothiazole Schiff base-iron complex.
FIG. 10 is an infrared spectrum of triazole derivative-zinc complex modified ammonium polyphosphate.
Detailed Description
The following examples specifically describe an organic metal complex modified ammonium polyphosphate intumescent flame retardant and a preparation method thereof designed by the present invention, but the embodiments of the present invention are not limited thereto (compounds capable of coordinating with metal can be implemented by using the technology provided by the present invention), and the examples should not be construed as limiting the present invention.
Example 1
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Zn (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 1 hour after dropwise adding, dropwise adding 0.30g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 2
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 2 hours after dropwise adding, dropwise adding 0.30g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 3
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 0.30g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 4
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.30g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 O solution in 60ml ethanol is added with stirring, after the addition is finished, the reaction is carried out for 3 hours at normal temperature, and then 0.75g urushiol is added into a three-neck flask50ml of ethanol solution, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for a plurality of times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 5
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.30g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 6
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.30g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 3.00g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 7
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.75g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding dropwise 60ml ethanol solution of O while stirring, reacting at room temperature for 3 hours after dropwise addition, then adding dropwise 50ml ethanol solution of 0.30g urushiol into a three-neck flask, heating to 60 ℃, refluxing and reacting for 18 hours, cooling to room temperature after reaction, suction filtering, taking filter cake, soaking and washing with ethanol for several times, and drying to obtain urushiol-zincThe complex compound modifies the ammonium polyphosphate intumescent flame retardant.
Example 8
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.75g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 0.75g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 9
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.75g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 10
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 0.75g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 11
1.50g of ammonium polyphosphate and 40ml of ethanolAdding into a three-neck flask with a mechanical stirrer, and dripping 1.50g Zn (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 0.30g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 12
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 0.75g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 13
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 14
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 24 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 15
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 36 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 16
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 40 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 17
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after adding dropwise, then adding 1.50g of 50ml of ethanol solution of urushiol dropwise into a three-neck flask,and then heating to 80 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out soaking and washing for a plurality of times by using ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 18
1.50g of ammonium polyphosphate and 40ml of methanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing bubble washing on the filter cake for several times by using methanol and ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 19
1.50g of ammonium polyphosphate and 40ml of water are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 2.96g (0.01 mol) of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of O aqueous solution while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of urushiol 50ml of ethanol solution into a three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out soaking and washing with water and ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 20
1.50g of ammonium polyphosphate and 40ml of toluene are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dripped into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding O in 60ml ethanol solution while stirring, reacting at normal temperature for 3 hours after the adding is finished, then adding 1.50g urushiol in 50ml ethanol solution dropwise into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake for a plurality of times by toluene and ethanol, and drying to obtain the productThe urushiol-zinc complex modifies the ammonium polyphosphate intumescent flame retardant.
Example 21
1.50g of ammonium polyphosphate and 40ml of dimethylbenzene are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing soaking and washing on the filter cake for several times by xylene and ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 22
1.50g of ammonium polyphosphate and 40ml of tetrahydrofuran are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing bubble washing on the filter cake for several times through tetrahydrofuran and ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 23
Adding 1.50g of ammonium polyphosphate and 40ml of dioxane into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing bubble washing for several times through dioxane and ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 24
1.50g of ammonium polyphosphate and 40ml of acetone are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing soaking and washing for several times by acetone and ethanol, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 25
1.50g of ammonium polyphosphate and 40ml of acetonitrile are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, washing with acetonitrile for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 26
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Mg (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-magnesium complex modified ammonium polyphosphate intumescent flame retardant.
Example 27
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, adding the mixture at normal temperature1.50g of Cu (NO) was added dropwise to a three-necked flask 3 ) 2 ·3H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-copper complex modified ammonium polyphosphate intumescent flame retardant.
Example 28
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Mn (NO) into the three-neck flask at normal temperature 3 ) 2 ·4H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the urushiol-manganese complex modified ammonium polyphosphate intumescent flame retardant.
Example 29
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Ni (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-nickel complex modified ammonium polyphosphate intumescent flame retardant.
Example 30
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Co (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding 60ml of ethanol solution of O while stirring, reacting for 3 hours at normal temperature after the dropwise addition is finishedAnd then dropwise adding 1.50g of urushiol 50ml of ethanol solution into the three-neck flask, heating to 80 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the urushiol-cobalt complex modified ammonium polyphosphate intumescent flame retardant.
Example 31
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Al (NO) into the three-neck flask at normal temperature 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-aluminum complex modified ammonium polyphosphate intumescent flame retardant.
Example 32
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Fe (NO) is dripped into the three-neck flask at normal temperature 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 1.50g of 50ml of ethanol solution of urushiol into a three-neck flask, heating to 80 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after reaction, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the urushiol-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 33
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Fe (NO) is dripped into the three-neck flask at normal temperature 3 ) 3 ·9H 2 Adding O60 ml ethanol solution while stirring, reacting at room temperature for 3 hr, adding 1.50g catechol 50ml ethanol solution dropwise, heating to 80 deg.C, reflux reacting for 18 hr, cooling to room temperature, vacuum filtering, collecting filter cake, and filtering with ethyl acetateAnd (3) soaking and washing for several times by alcohol, and drying to obtain the catechol-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 34
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Fe (NO) is dripped into the three-neck flask at normal temperature 3 ) 3 ·9H 2 And (2) adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after the adding is finished, then adding 1.50g of 50ml of ethanol solution of cardanol dropwise into the three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the cardanol-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 35
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of gallic acid into the three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the gallic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 36
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding is finished, dropwise adding 50ml of ethanol solution of 3.00 tannic acid into the three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the tannic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 37
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after the adding is finished, then adding 50ml of ethanol solution of 3.00g of cardanol dropwise into the three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the cardanol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 38
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of eugenol into the three-neck flask, heating to 80 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the eugenol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 39
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after the adding is finished, then adding 50ml of ethanol solution of 3.00 catechol dropwise into the three-neck flask, heating to 68 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the catechol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 40
Step one, 2.44g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dripping 40ml ethanol solution of 0.6g ethylenediamine into a three-neck flask at normal temperature, stirring while dripping, heating to 60 ℃, carrying out reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-ethylenediamine Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding the Schiff base ethanol solution obtained in the step one into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the salicylaldehyde-ethylenediamine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
EXAMPLE 41
Step one, placing 2.44g of salicylaldehyde and 20ml of ethanol solution into a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dripping 40ml of ethanol solution of 1.46g of triethylene tetramine into a three-neck flask at normal temperature, stirring while dripping, heating to 60 ℃, performing reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-triethylene tetramine Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after the addition is finished, then adding the Schiff base ethanol solution obtained in the step one into a three-neck flask dropwise, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the salicylaldehyde-triethylene tetramine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 42
Step one, placing 2.44g of salicylaldehyde and 20ml of ethanol solution into a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, 1.89g of a 40ml ethanol solution of tetraethylenepentamine is dripped into a three-neck flask at normal temperature, the mixture is stirred while being dripped, the temperature is raised to 60 ℃, reflux reaction is carried out for 12 hours, and the mixture is cooled to room temperature, so as to obtain the salicylaldehyde-tetraethylenepentamine Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding the Schiff base ethanol solution obtained in the step one into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the salicylaldehyde-tetraene pentamine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 43
Step one, 1.22g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dripping 40ml of ethanol solution of 1.2g of polyethyleneimine into a three-neck flask at normal temperature, stirring while dripping, heating to 60 ℃, performing reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-polyethyleneimine Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, then dropwise adding the Schiff base ethanol solution in the step one into a three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the salicylaldehyde-polyethyleneimine Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 44
Step one, 1.22g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dripping 40ml of ethanol solution of 1.83g of aminodiphenylmethane into a three-neck flask at normal temperature, stirring while dripping, heating to 60 ℃, carrying out reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-aminodiphenylmethane Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, then dropwise adding the Schiff base ethanol solution in the step one into a three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the salicylaldehyde-aminodiphenylmethane Schiff base-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 45
Step one, 1.22g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dropwise adding 1.5g of 40ml ethanol solution of 2-aminobenzothiazole into a three-neck flask at normal temperature, stirring while dropwise adding, heating to 60 ℃, performing reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-2-aminobenzothiazole Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, then dropwise adding the Schiff base ethanol solution in the step one into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the salicylaldehyde-2-aminobenzothiazole-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 46
Step one, 1.22g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, 0.84g of 40ml of ethanol solution of 2-amino-triazole is dripped into a three-neck flask at normal temperature, the mixture is stirred while being dripped, the mixture is heated to 60 ℃ for reflux reaction for 12 hours, and the mixture is cooled to room temperature to obtain the salicylaldehyde-2-amino-triazole Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding the Schiff base ethanol solution obtained in the step one into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the salicylaldehyde-2-amino-triazole-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 47
Step one, 1.22g of salicylaldehyde and 20ml of ethanol solution are placed in a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, 0.85g of 40ml of ethanol solution of 5-amino-tetrazole is dripped into the three-neck flask at normal temperature, stirring is carried out while dripping, the temperature is raised to 60 ℃, reflux reaction is carried out for 12 hours, and the salicylic aldehyde-5-amino-tetrazole Schiff base is obtained after cooling to room temperature.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and dripping 1.50g of Fe (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 3 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding the Schiff base ethanol solution obtained in the step one into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the salicylal-5-amino-tetrazole-iron complex modified ammonium polyphosphate intumescent flame retardant.
Example 48
Step one, placing 2.44g of salicylaldehyde and 20ml of ethanol solution into a three-neck flask with a thermometer stirring device; after the raw materials are uniformly mixed, dripping 40ml of ethanol solution of 1.03g of diethylenetriamine into a three-neck flask at normal temperature, stirring while dripping, heating to 60 ℃, performing reflux reaction for 12 hours, and cooling to room temperature to obtain the salicylaldehyde-diethylenetriamine Schiff base.
Step two, adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask provided with a mechanical stirrer, and dripping 1.50g of Co (NO) into the three-neck flask at normal temperature after the raw materials are uniformly mixed 3 ) 2 ·9H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, then dropwise adding the Schiff base ethanol solution in the step one into a three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the salicylaldehyde-diethylenetriamine Schiff base-cobalt complex modified ammonium polyphosphate intumescent flame retardant.
Example 49
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of urushiol into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain the urushiol-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 50
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding O in 60ml of ethanol solution while stirring, reacting at normal temperature for 3 hours after the adding is finished, then adding 3.00-methylimidazole in 50ml of ethanol solution in a three-neck flask dropwise, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, soaking and washing with ethanol for several times, and drying to obtain 2-methylimidazole-zinc complex modified ammonium polyphosphateAn intumescent flame retardant.
Example 51
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00-amino-1, 2, 4-triazole into a three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the 3-amino-1, 2, 4-triazole-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 52
The 3-amino-1, 2, 4-triazole derivative (D-ATA) is synthesized by adding 4.45g DOPO and 20ml dichloromethane solution into a three-neck flask equipped with a mechanical stirrer, adding 3.15ml triethylamine, adding 1.73g 3-amino-1, 2, 4-triazole when the temperature of the three-neck flask is reduced to 5 ℃, after the raw materials are mixed uniformly, dripping 5ml acetonitrile solution mixed with 2.18ml CH2Cl2, reacting for 24 hours at normal temperature after the dripping is finished, filtering, taking filter cakes, soaking and washing for several times by deionized water solution, and drying to obtain the D-ATA.
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00D-ATA into the three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after reaction, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the D-ATA-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 53
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 3.00g of 50ml of ethanol solution of 5-amino-tetrazole, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the 5-amino-tetrazole-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 54
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of adenine into the three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after reaction, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the adenine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 55
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of aspartic acid into the three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the aspartic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 56
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after the dropwise addition is finished, and thenAnd dropwise adding 50ml of ethanol solution of 3.00g of lysine into the three-neck flask, heating to 60 ℃, carrying out reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, taking a filter cake, carrying out ethanol soaking and washing for several times, and drying to obtain the lysine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 57
Adding 1.50g of ammonium polyphosphate and 40ml of ethanol into a three-neck flask with a mechanical stirrer, and after the raw materials are uniformly mixed, dropwise adding 1.50g of Zn (NO) into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of glutamic acid into the three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, performing ethanol soaking and washing for several times, and drying to obtain the glutamic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 58
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding 50ml of ethanol solution of 3.00g of glycine into the three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the glycine-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 59
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 Adding dropwise 60ml ethanol solution of O while stirring, reacting at room temperature for 3 hr, adding dropwise 50ml ethanol solution of 3.00g salicylic acid into a three-neck flask, heating to 60 deg.C, reflux reacting for 18 hr, cooling to room temperature, vacuum filteringAnd taking the filter cake, soaking and washing the filter cake for a plurality of times by using ethanol, and drying to obtain the salicylic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 60
1.50g of ammonium polyphosphate and 40ml of ethanol are added into a three-neck flask provided with a mechanical stirrer, and after the raw materials are uniformly mixed, 1.50g of Zn (NO) is dropwise added into the three-neck flask at normal temperature 3 ) 2 ·6H 2 And (2) dropwise adding 60ml of an ethanol solution of O while stirring, reacting at normal temperature for 3 hours after dropwise adding, dropwise adding a 50ml ethanol solution of 3.00g of oxalic acid into the three-neck flask, heating to 60 ℃, performing reflux reaction for 18 hours, cooling to room temperature after the reaction is finished, performing suction filtration, taking a filter cake, soaking and washing the filter cake with ethanol for several times, and drying to obtain the oxalic acid-zinc complex modified ammonium polyphosphate intumescent flame retardant.
Example 32 Anacardial-iron complex modified ammonium polyphosphate test the assay results are as follows:
FTIR(KBr，cm -1 ):3200(N-H)，2979(＝C-H),2927(-CH 3 ),2856(-CH 2 ) 1635, 1557 benzene ring backbone, 1256 (P = O), 1340 (C-N), 1057 (P-O), 880 (C-N), 800 (P-O-P), 680 (Fe-O).
Example 48 assay results for salicylaldehyde-diethylenetriamine schiff base-cobalt complex modified ammonium polyphosphate test are as follows:
FTIR(KBr，cm -1 ):3200(N-H)，1635(C＝N)，1602(C＝N),1384(N-H),1256(P＝O)，1057(P-O)，880(C-N)，800(P-O-P)，443(Co-N),418(Co-O).
example 52D-ATA-Zinc complex modified ammonium polyphosphate test assay results are as follows:
FTIR(KBr，cm -1 ):3200(N-H)，1600(C＝N),1200(P＝O)，952(P-O)，880(C-N)，800(P-O-P)，500(Zn-N)。
Claims (8)
1. the organic metal complex modified ammonium polyphosphate intumescent flame retardant is characterized in that the chemical structure general formula is as follows:
wherein, M 2+ Is Zn 2+ 、Cu 2+ 、Mg 2+ 、Mn 2+ 、Ni 2+ 、Co 2+ Any one of the metal ions of (1), M 3+ Is Al 3+ 、Fe 3+ Any one of the metal ions of (1); r is any one of phenols, schiff bases, nitrogen heterocycles, amino acids and carboxylic acid compounds.
2. The method for preparing an organometallic complex modified ammonium polyphosphate intumescent flame retardant as claimed in claim 1, wherein the ammonium polyphosphate and the solvent are firstly added in sequence into a three-neck flask provided with a mechanical stirrer and a thermometer; after the raw materials are uniformly mixed, dropwise adding a metal ion-containing solution into the three-neck flask at normal temperature, and stirring while dropwise adding; after the dropwise addition is finished, reacting for a period of time at normal temperature, then dropwise adding an organic ligand solution into the three-neck flask, and reacting for a period of time at a certain temperature; after the reaction is finished, cooling to room temperature, carrying out suction filtration, taking a filter cake, washing the filter cake for a plurality of times by using a solvent, and drying to obtain the organic metal complex modified ammonium polyphosphate intumescent flame retardant.
3. The preparation method of the organic metal complex modified ammonium polyphosphate intumescent flame retardant of claim 2, wherein the solvent is one or more of toluene, xylene, tetrahydrofuran, water, dioxane, methanol, ethanol, acetone and acetonitrile.
4. The method for preparing the organometallic complex modified ammonium polyphosphate intumescent flame retardant of claim 2, wherein the metal ion is Zn 2+ 、Cu 2+ 、Mg 2+ 、Mn 2+ 、Ni 2+ 、Co 2+ 、Al 3+ 、Fe 3+ Any one of the above.
5. The preparation method of the organometallic complex modified ammonium polyphosphate intumescent flame retardant of claim 2, wherein the organic ligand is any one of phenols, schiff bases, nitrogen heterocycles, amino acids and carboxylic acid compounds.
6. The preparation method of the organic metal complex modified ammonium polyphosphate intumescent flame retardant as claimed in claim 2, wherein the mass ratio of the ammonium polyphosphate, the metal ions and the ligand is 1: 0.2-2.
7. The preparation method of the organic metal complex modified ammonium polyphosphate intumescent flame retardant as claimed in claim 2, characterized in that the reaction time at normal temperature is 1-3 hours.
8. The method for preparing the expanded ammonium polyphosphate flame retardant modified by the organic metal complex according to claim 2, wherein the reaction temperature after the organic ligand is dripped is 20-80 ℃, and the reaction time is 18-36 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111143397.6A CN113845699B (en) | 2021-09-28 | 2021-09-28 | Organic metal complex modified ammonium polyphosphate intumescent flame retardant and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN101058730A (en) * | 2007-06-06 | 2007-10-24 | 四川大学 | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same |
| JP2016089144A (en) * | 2014-10-30 | 2016-05-23 | アイカ工業株式会社 | Hydrophobic resin-ammonium polyphosphate composite |
| CN110467747A (en) * | 2019-08-26 | 2019-11-19 | 兰州理工大学 | The fire-retardant complex compound of metal ion and preparation method with schiff bases structure |
| CN111138713A (en) * | 2019-12-30 | 2020-05-12 | 上海普利特复合材料股份有限公司 | Stearylamine modified ammonium polyphosphate and preparation method and application thereof |
| CN112194833A (en) * | 2020-09-30 | 2021-01-08 | 淮安丹文化工科技有限公司 | Intumescent flame-retardant polyethylene containing organic metal complex and preparation method thereof |
| CN112280100A (en) * | 2020-10-13 | 2021-01-29 | 裕克施乐塑料制品（太仓）有限公司 | Composite intumescent flame retardant and preparation method thereof |
-
2021
- 2021-09-28 CN CN202111143397.6A patent/CN113845699B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN101058730A (en) * | 2007-06-06 | 2007-10-24 | 四川大学 | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same |
| JP2016089144A (en) * | 2014-10-30 | 2016-05-23 | アイカ工業株式会社 | Hydrophobic resin-ammonium polyphosphate composite |
| CN110467747A (en) * | 2019-08-26 | 2019-11-19 | 兰州理工大学 | The fire-retardant complex compound of metal ion and preparation method with schiff bases structure |
| CN111138713A (en) * | 2019-12-30 | 2020-05-12 | 上海普利特复合材料股份有限公司 | Stearylamine modified ammonium polyphosphate and preparation method and application thereof |
| CN112194833A (en) * | 2020-09-30 | 2021-01-08 | 淮安丹文化工科技有限公司 | Intumescent flame-retardant polyethylene containing organic metal complex and preparation method thereof |
| CN112280100A (en) * | 2020-10-13 | 2021-01-29 | 裕克施乐塑料制品（太仓）有限公司 | Composite intumescent flame retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Effect of a novel P/N/S-containing reactive flame retardant on curing behavior, thermal and flame-retardant properties of epoxy resin;Rongkun Jian，等;《Journal of Analytical and Applied Pyrolysis》;20170719;360-368 * |
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