CN110982121A - Triazinyl phosphorus-nitrogen flame retardant, and preparation method and application thereof - Google Patents
Triazinyl phosphorus-nitrogen flame retardant, and preparation method and application thereof Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention discloses a triazine-based phosphorus-nitrogen flame retardant, a preparation method and application thereof. The raw materials used in the invention are easy to obtain, and the obtained novel triazine-based phosphorus-nitrogen flame retardant product has white color, high yield and good thermal stability. The flame retardant has the advantages that the initial decomposition temperature is 250 ℃, and the flame retardant has better thermal stability; the oxygen index of the cotton cloth finished by the flame retardant is 29 percent; and the flame retardant performance is good through horizontal and vertical combustion tests.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of flame retardants, and more particularly relates to a triazine-based phosphorus-nitrogen flame retardant containing DOPO groups, and a preparation method and application thereof.
Background
The continuous progress of society, people's environmental protection consciousness is gradually improved, and fire retardant also gradually gets on the road of environmental protection. Halogen-free, non-toxic and smokeless fire retardants will become the focus of research. Polymers as a class of materials are generally flammable. Thermoplastic and thermosetting polymers (e.g., polyamides, polyesters, epoxies, and polyurethanes) require the use of flame retardants in many applications for reasons of flammability. Generally, halogenated compounds (more specifically, aromatic polybrominated compounds) have been used as flame retardant additives in polymers. It is generally believed that these products inhibit the radical gas phase reaction in the flame when they are ignited.
The flame retardant of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) containing only phosphorus is mostly not ideal. Nitrogen and phosphorus flame retardants represented by nitrogen and phosphorus are widely used in various fields because of their halogen-free, low toxicity and good flame retardant effect. In recent years, researches show that phosphorus and nitrogen synergistic flame retardance is an effective method for improving flame retardance efficiency, so that a nitrogen-phosphorus flame retardant has wide application prospect and gradually becomes the central importance of the flame retardant, and therefore, how to improve the flame retardance of the flame retardant containing the DOPO group needs to be further researched.
Disclosure of Invention
In view of the above, the invention aims to provide a triazine-based phosphorus-nitrogen flame retardant having good flame retardant performance and thermal stability.
The invention also aims to provide a preparation method of the triazine-based nitrogen-phosphorus flame retardant, the method has the advantages of easily available raw materials, simple process, short production time, high efficiency and high purity of the prepared flame retardant.
In order to achieve the purpose, the invention adopts the following technical scheme:
a triazine-based phosphorus-nitrogen flame retardant has a structure shown in a formula I:
the invention also provides a preparation method of the triazine-based phosphorus-nitrogen flame retardant, which comprises the following steps:
s1, preparation of flame retardant intermediate:
reaction route of DOPO hydroxymethyl intermediate with cyanuric chloride:
under the condition of continuous stirring, dissolving DOPO hydroxymethyl intermediate and cyanuric chloride in an organic solvent A, placing in an ice water bath, reacting for 4-6h, and after the reaction is finished, carrying out post-treatment to obtain a flame retardant intermediate with a formula I-2;
s2, preparation of triazine-based phosphorus-nitrogen flame retardant:
the synthesis route of the triazine phosphorus-nitrogen flame retardant comprises the following steps:
under the condition of continuous stirring, dissolving the flame retardant intermediate in an organic solvent B, stirring to form a turbid liquid, slowly adding triethyl phosphite, heating to 90-100 ℃ for reaction for 6-9h, and after the reaction is finished, carrying out post-treatment to obtain the triazinyl phosphorus nitrogen flame retardant with the formula I;
preferably, in the step of S1, the reaction molar ratio of the cyanuric chloride to the DOPO intermediate is 1 (1-1.1).
Preferably, in the step S1, the organic solvent a is one of acetone and tetrahydrofuran.
Preferably, in step S1, the post-processing procedure is: the reaction solution was cooled to room temperature, and after a white precipitate was precipitated, the precipitate was filtered under reduced pressure and washed with acetone.
Preferably, in the step S2, the reaction molar ratio of the flame retardant intermediate to the triethyl phosphite is 1 (2-2.1).
Preferably, in the step S2, the organic solvent B is one of benzene and toluene.
Preferably, in the step S2, the triethyl phosphite is controlled to be dripped off within 0.5-1h at the temperature of 90 ℃.
Preferably, in step S2, the post-processing procedure is: the reaction solution was cooled to room temperature, and after a white precipitate was precipitated, the reaction solution was filtered under reduced pressure.
Preferably, the preparation method of the DOPO hydroxymethyl intermediate comprises the following steps:
dissolving DOPO in tetrahydrofuran or ethanol under the condition of continuous stirring, slowly adding a formaldehyde aqueous solution, heating to 60-70 ℃ for reaction for 5-7h, filtering the reaction solution after the reaction is finished, cooling the filtrate to room temperature, separating out white crystals, and recrystallizing with methanol or ethanol to obtain a DOPO hydroxymethyl intermediate with a formula I-1;
the synthesis route of the DOPO hydroxymethyl intermediate is as follows:
preferably, the reaction molar ratio of the DOPO and the formaldehyde in the aqueous formaldehyde solution is 1: 1.1.
Preferably, the mass fraction of the aqueous formaldehyde solution is 37%.
Preferably, the formaldehyde aqueous solution is controlled to be dripped off within 0.5h at the temperature of 60 ℃.
The invention further provides application of the triazine-based phosphorus-nitrogen flame retardant in flame retardant processes of high polymer materials and functional molecular materials.
Preferably, the triazine phosphorus nitrogen flame retardant is used in the flame retardant process of polyamide, epoxy resin, polyurethane, textile and plastics for electronic equipment.
The reaction temperature in step S1 is the necessary condition for controlling the reaction, and when the first chlorine atom in cyanuric chloride is replaced, the reaction temperature is controlled below 0 ℃; when the last third chlorine atom is to be replaced, the reaction temperature is generally controlled to be above 90 ℃. In step S2, the reaction yield is decreased if the reaction temperature is less than 90 ℃, or greater than 100 ℃.
The triazine-based phosphorus-nitrogen flame retardant disclosed by the invention has good flame retardant performance based on the facts that the triazine-based phosphorus-nitrogen flame retardant has good flame retardant and heat resistant performances because of containing a triazine structure, nitrogen-containing elements in the structure show good chemical stability because of containing nitrogen heterocycles, the triazine-based flame retardant has a special structure of tertiary nitrogen, can serve as a gas source and also can serve as a carbon source, the special structure enables the triazine-based phosphorus-nitrogen flame retardant to easily construct a double-source or triple-source halogen-free intumescent flame retardant system, and the phosphorus element and the nitrogen element have good synergistic effects. Therefore, the triazine structure rich in nitrogen is introduced into the phosphorus flame retardant, the novel nitrogen-phosphorus flame retardant is constructed through the cyanuric chloride and the DOPO group, and the cyanuric chloride with the triazine structure and the DOPO group can jointly construct the nitrogen-phosphorus flame retardant with good flame retardant effect.
According to the technical scheme, compared with the prior art, the triazine-based phosphorus-nitrogen flame retardant provided by the invention has the following technical effects:
(1) the triazine-based phosphorus-nitrogen flame retardant containing the DOPO group has good flame retardant performance, and is finished into cotton cloth to be subjected to horizontal and vertical combustion tests, and the test result shows that the combustion speed of the cotton cloth finished by the flame retardant is slower than that of the cotton cloth and blank cotton cloth finished by the raw material DOPO, and the damage length during horizontal combustion is short.
(2) The triazine-based phosphorus-nitrogen flame retardant containing the DOPO group has good thermal stability, the initial decomposition temperature of the flame retardant is 250 ℃, the flame retardant is completely decomposed after 500 ℃, and the char forming rate is 12.4%.
(3) The triazine phosphorus nitrogen flame retardant containing the DOPO group belongs to a flame retardant material, the flame retardant is finished in cotton cloth for measuring the oxygen index, the oxygen index of blank cotton cloth is only 18 percent, the oxygen index of the DOPO finished cotton cloth is 27 percent, and the oxygen index of the flame retardant finished cotton cloth is 29 percent and is higher than the standard flame retardant of 26 percent.
(4) The preparation method of the triazine phosphorus nitrogen flame retardant containing the DOPO group is simple, mild in reaction condition, easy to operate, low in cost and high in yield.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of the triazinyl phosphazene flame retardant of example 1.
FIG. 2 is the thermogravimetric plot of the triazinyl phosphorus-nitrogen based flame retardant of example 1.
FIG. 3 is a diagram showing a sample of the triazinyl phosphazene flame retardant of example 1.
FIG. 4 is a graph of horizontal burn damage length of blank cotton, DOPO-finished cotton, and triazine-based phosphazene flame retardant-finished cotton of example 1.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a triazine-based phosphorus-nitrogen flame retardant, which has a structure shown in a formula I:
the preparation method of the triazine-based phosphorus-nitrogen flame retardant comprises the following steps:
preparation of DOPO hydroxymethyl intermediate:
weighing DOPO (6.0221g, 0.028mol) and placing the DOPO in a 250mL three-neck flask with a thermometer, measuring 100mL tetrahydrofuran as a solvent and adding the solvent into the three-neck flask, stirring to completely dissolve the DOPO, measuring (2.50mL, 0.0308mol) formaldehyde aqueous solution and slowly adding the formaldehyde aqueous solution into the three-neck flask, continuing stirring, heating to 60 ℃, and carrying out reflux reaction for 6 hours. After the reaction was completed, the reaction solution was filtered to obtain a filtrate, the filtrate was cooled to room temperature, a white solid was precipitated, and recrystallized from methanol to obtain a white solid intermediate, which was dried and ground to obtain 4.7736g in mass and 70% in yield.
S1, preparation of flame retardant intermediate:
respectively weighing a DOPO intermediate (3.7002g, 0.015mol) and cyanuric chloride (2.7625g, 0.015mol) and sequentially placing the DOPO intermediate and the cyanuric chloride into a 250mL three-neck flask, weighing 100mL of acetone as a solvent, adding the acetone into the three-neck flask, stirring until the acetone is fully dissolved, placing the mixture into an ice water bath, continuously stirring for reaction for 4 hours, separating out a white precipitate, filtering under reduced pressure, washing a filter cake with an acetone solvent to obtain white solid powder, wherein the mass of the white solid powder is 3.6396g, and the yield is 61%.
S2, preparation of triazine-based phosphorus-nitrogen flame retardant:
the intermediate (2.0093g, 0.005mol) was weighed and charged into a 250mL three-necked flask equipped with a thermometer, 70mL of a benzene solvent was further charged into the flask, and stirred for 10min to form a turbid solution, triethyl phosphite (1.8mL, 0.01mol) was added dropwise over 1 hour, and after completion of the addition, stirring was continued, the temperature was raised to 90 ℃ and the reaction was carried out for 6 hours. The solution turns from turbid to clear in the reaction process, and after the reaction is finished, the reaction solution is cooled to room temperature to separate out white precipitate. And (3) carrying out vacuum filtration to obtain the triazine nitrogen phosphorus flame retardant containing the DOPO group, wherein the mass is 1.6105g, and the yield is 55%.
The embodiment also provides application of the triazine-based phosphorus-nitrogen flame retardant in flame retardant processes of polyamide, epoxy resin, polyurethane, textile and plastics for electronic equipment.
The invention also collects the data of infrared spectrum and thermogravimetry on the obtained triazine-based phosphorus-nitrogen flame retardant, and the specific analysis is as follows:
(1) and (3) infrared test analysis of the triazine-based phosphorus-nitrogen flame retardant.
The test adopts a WQF-510A Fourier transform infrared spectrometer, and the selected method is a potassium bromide tabletting method. Respectively weighing about 2mg of flame retardant sample and about 100mg of dried potassium bromide, fully grinding the flame retardant sample and the dried potassium bromide in an agate mortar, tabletting the mixture by using a tabletting machine, placing the pressed sheet sample in a light beam of an instrument, and measuring the thickness in the range of 500-4000 cm--1Scanning to obtain the infrared spectrum attached figure 1 of the flame retardant.
From the attached FIG. 1, it can be taken: 3421cm-1The peak is the stretching vibration peak of O-H in the compound crystal water, 1594cm-1、1355cm-1、800cm-The absorption peak appearing at the 1 position is the vibration peak of the triazine ring skeleton, 1432cm-1The absorption peak is the stretching vibration peak of P-Ph, 1213cm-1、935cm-1The absorption peak at (B) is the stretching vibration peak of P-O-Ph.
(2) Thermogravimetric test analysis of the triazine-based phosphorus-nitrogen flame retardant.
The test adopts a TGA-Q500 type thermogravimetric analyzer of the company ta in America, the used atmosphere is a nitrogen atmosphere, the test temperature range is 25-600 ℃, the temperature rise rate is 20 ℃/min, the flow rate of the nitrogen gas is controlled to be 40mL/min, and the sample mass is about 6 mg.
As can be seen from fig. 2: the triazine nitrogen phosphorus flame retardant has no serious mass loss before 250 ℃, which shows that the flame retardant has good thermal stability. The initial decomposition temperature is 250 ℃, the weight loss process is divided into a stage, the flame retardant is decomposed by heating at the temperature of 250-500 ℃, the P-containing compound is dehydrated to generate phosphate, and the quality is rapidly lost. The curve hardly changes after 500 ℃, the residual carbon content is 12.4 percent, and the carbon forming rate is higher.
Example 2
The embodiment provides a triazine-based phosphorus-nitrogen flame retardant, which has a structure shown in a formula I:
the preparation method of the triazine-based phosphorus-nitrogen flame retardant comprises the following steps:
preparation of DOPO hydroxymethyl intermediate:
weighing DOPO (10.8002g, 0.05mol) and placing in a 250mL three-neck flask with a thermometer, measuring 150mL ethanol as a solvent and adding into the three-neck flask, stirring to completely dissolve the DOPO, measuring (4.40mL, 0.055mol) formaldehyde aqueous solution and slowly dripping into the three-neck flask, continuing stirring, heating the reaction solution to 70 ℃, and carrying out reflux reaction for 6 hours. After the reaction was completed, the reaction solution was filtered to obtain a filtrate, the filtrate was cooled to room temperature to precipitate a white solid, which was recrystallized from ethanol to obtain a white solid intermediate, which was dried and ground to obtain 9.8560g in mass and 80% in yield.
S1, preparation of flame retardant intermediate:
respectively weighing DOPO intermediate (6.7605g, 0.0275mol) and cyanuric chloride (4.6010g, 0.025mol) and sequentially placing the DOPO intermediate and the cyanuric chloride into a 250mL three-neck flask, weighing 100mL of acetone as a solvent, adding the acetone into the three-neck flask, placing the three-neck flask into an ice water bath, reacting for 5 hours under the condition of continuous stirring, separating out white precipitate, filtering under reduced pressure, washing a filter cake with the acetone solvent to obtain white solid powder, weighing 5.7680g of the powder, and obtaining the yield of 60%.
S2, preparation of triazine-based phosphorus-nitrogen flame retardant:
the intermediate (3.9820g, 0.01mol) was weighed into a 250mL three-necked flask equipped with a thermometer, 70mL of a toluene solvent was further added to the flask, and stirred for 10min to form a turbid solution, and triethyl phosphite (3.6mL, 0.02mol) was added dropwise over 1 hour, and after completion of the addition, stirring was continued, and the temperature was raised to 100 ℃ to react for 7 hours. The solution turns from turbid to clear in the reaction process, and after the reaction is finished, the reaction solution is cooled to room temperature to separate out white precipitate. And (3) carrying out vacuum filtration to obtain the triazine-based nitrogen-phosphorus flame retardant containing the DOPO groups, wherein the mass is 3.5806g, and the yield is 60%.
The embodiment also provides application of the triazine-based phosphorus-nitrogen flame retardant in flame retardant processes of polyamide, epoxy resin, polyurethane, textile and plastics for electronic equipment.
Example 3
The embodiment provides a triazine-based phosphorus-nitrogen flame retardant, which has a structure shown in a formula I:
the preparation method of the triazine-based phosphorus-nitrogen flame retardant comprises the following steps:
preparation of DOPO hydroxymethyl intermediate:
weighing DOPO (10.800g, 0.05mol) and placing in a 250mL three-neck flask with a thermometer, measuring 100mL tetrahydrofuran as a solvent and adding into the three-neck flask, stirring to completely dissolve the DOPO, measuring (4.40mL, 0.055mol) formaldehyde aqueous solution and slowly dropping into the three-neck flask, continuing stirring, heating the reaction solution to 65 ℃, and carrying out reflux reaction for 6 hours. After the reaction was completed, the reaction solution was filtered to obtain a filtrate, the filtrate was cooled to room temperature, a white solid was precipitated, and recrystallized from methanol to obtain a white solid intermediate, which was dried and ground to obtain 8.4506g in mass and 68% in yield.
S1, preparation of flame retardant intermediate:
respectively weighing a DOPO intermediate (6.1505g, 0.025mol) and cyanuric chloride (4.6250g, 0.025mol), sequentially placing the DOPO intermediate and the cyanuric chloride in a 250mL three-neck flask, weighing 80mL of LTHF as a solvent, adding the solvent into the three-neck flask, stirring until the DOPO intermediate and the cyanuric chloride are fully dissolved, placing the three-neck flask in an ice water bath, continuously stirring for reaction for 5 hours, separating out a white precipitate, filtering under reduced pressure, washing a filter cake with a THF solvent to obtain white solid powder, weighing 5.5200g of the white solid powder, and obtaining the yield of 56%.
S2, preparation of triazine-based phosphorus-nitrogen flame retardant:
the intermediate (3.9910g, 0.01mol) was weighed into a 250mL three-necked flask equipped with a thermometer, 70mL of benzene solvent was further added to the flask, and stirred for 15min to form a turbid solution, triethyl phosphite (3.80mL, 0.021mol) was added dropwise over 1 hour, and after completion of the addition, stirring was continued, the temperature was raised to 95 ℃ and the reaction was carried out for 7 hours. The solution turns from turbid to clear in the reaction process, and after the reaction is finished, the reaction solution is cooled to room temperature to separate out white precipitate. And (3) carrying out vacuum filtration to obtain the triazine nitrogen phosphorus flame retardant containing the DOPO group, wherein the mass is 3.1600g, and the yield is 53%.
The embodiment also provides application of the triazine-based phosphorus-nitrogen flame retardant in flame retardant processes of polyamide, epoxy resin, polyurethane, textile and plastics for electronic equipment.
In order to further illustrate the technical effects of the triazine-based phosphorus-nitrogen flame retardant provided by the invention, the invention performs horizontal and vertical combustion and oxygen index (LOI) tests on blank cotton cloth, DOPO cotton cloth and flame retardant cotton cloth, and the following specific description is given:
preparing flame retardant cotton cloth:
the triazinyl phosphorus-nitrogen flame retardant of example 1 was sufficiently ground in an agate mortar, 4g of the ground flame retardant was taken out, ethanol was used as a solvent, and a flame retardant finishing liquid with a concentration of 40g/L was prepared by volume metering in a 100mL volumetric flask.
The preparation method comprises the following steps of taking 150mm × 80mm cotton cloth (produced by Jiangsu Jinling textile Co., Ltd.), immersing the cotton cloth into a 500mL beaker filled with a flame retardant finishing liquid, immersing for 20 minutes at 50 ℃, putting the beaker into an oven, setting the temperature of the oven at 100 ℃, drying for 30 minutes, and taking out to obtain the flame retardant-cotton cloth.
The novel triazine-based phosphorus-nitrogen flame retardant is replaced by a raw material DOPO to prepare DOPO-cotton cloth for comparison. According to GB/T5455-1997 textile combustion performance test vertical combustion method, an CZF-5 type horizontal vertical combustion tester is used for testing.
(1) And analyzing the horizontal burning test result.
The blank cotton cloth and the cotton cloth finished by the raw materials DOPO and the triazine-based phosphorus-nitrogen flame retardant respectively are subjected to a horizontal combustion test, and the results are shown in Table 1:
TABLE 1 horizontal Combustion data sheet
As can be seen from the data in Table 1, the combustion speeds of the blank and DOPO-finished cotton cloth and the cotton cloth finished by the phosphorus-nitrogen flame retardant are 219.5mm/min, 100.2mm/min and 80.2mm/min respectively when the cotton cloth is horizontally combusted, and the damage lengths of the test samples are 75mm, 70mm and 35mm respectively, so that the phosphorus-nitrogen flame retardant has a good flame retardant effect, and the flame retardant effect is superior to that of DOPO.
FIG. 4 is a horizontal post-combustion comparison of blank cotton, DOPO-finished cotton, and triazine-based phosphazene flame retardant-finished cotton, wherein: the damage lengths of the blank cotton cloth, the raw material DOPO and the cotton cloth finished by the flame retardant after horizontal combustion are respectively 75mm, 70mm and 35mm, the damage length of the flame retardant is the shortest, and the flame retardant effect of the flame retardant is superior to that of the DOPO.
(2) And analyzing the test result of the vertical combustion of the water.
The blank cotton cloth and the cotton cloth finished by the raw materials DOPO and the triazine phosphorus-nitrogen flame retardant respectively are subjected to a vertical combustion test, and the results are shown in Table 2:
TABLE 2 vertical Combustion data sheet
As can be seen from the data in the table, the damage length of the blank and DOPO-finished cotton cloth and the triazine-based phosphorus-nitrogen flame retardant-finished cotton cloth is 75mm when the cotton cloth is vertically combusted, but the combustion speed is 257.1mm/min, 150.5mm/min and 139.3mm/min respectively, so that although the damage length of the triazine-based phosphorus-nitrogen flame retardant-finished cotton cloth is the same as that of the blank cotton cloth and the DOPO-finished cotton cloth, the combustion speed is obviously lower than that of the blank cotton cloth and the DOPO-finished cotton cloth.
(3) Oxygen Index (LOI) determination analysis.
According to GB/T5455-1997 textile combustion performance test oxygen index method, an oxygen index tester is adopted for measurement. A cotton cloth sample of 70mm by 30mm in size was folded in three layers to have a width of 10mm, and the minimum oxygen concentration required for smooth combustion of the sample was expressed in percentage in a mixed gas flow of nitrogen and oxygen, and the results of measurement of the oxygen index of the sample are shown in Table 3. Wherein, the national reference standard is as follows: LOI <20 belongs to flammable materials, 20< LOI <26 belongs to flammable materials, and LOI >26 belongs to nonflammable materials.
TABLE 3 oxygen index data sheet
As can be seen from the data in the table, the blank cotton cloth has the Lowest Oxygen Index (LOI) of 18%, i.e., it burns rapidly in air. The LOI of the cotton cloth finished by the DOPO is 27 percent, and the LOI of the cotton cloth finished by the triazine phosphorus nitrogen flame retardant is respectively 29 percent, reaches the flame-retardant level and is higher than that of the blank cotton cloth and the DOPO finished cotton cloth.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A triazine-based phosphorus-nitrogen flame retardant is characterized in that the structure is shown as formula I:
2. the method for preparing the triazinyl phosphazene flame retardant according to claim 1, comprising the steps of:
s1, preparation of flame retardant intermediate:
under the condition of continuous stirring, dissolving DOPO hydroxymethyl intermediate of the following formula I-1 and cyanuric chloride in an organic solvent A, placing in an ice water bath, reacting for 4-6h, and after the reaction is finished, carrying out post-treatment to obtain a flame retardant intermediate of the following formula I-2;
s2, preparation of triazine-based phosphorus-nitrogen flame retardant:
under the condition of continuous stirring, dissolving the flame retardant intermediate in an organic solvent B, stirring to form a turbid liquid, slowly adding triethyl phosphite, heating to 90-100 ℃ for reaction for 6-9h, and after the reaction is finished, carrying out post-treatment to obtain the triazinyl phosphorus nitrogen flame retardant with the formula I;
3. the method for preparing triazine-based phosphorus-nitrogen based flame retardant according to claim 2, wherein in the step of S1, the reaction molar ratio of cyanuric chloride to DOPO hydroxymethyl intermediate is 1 (1-1.1).
4. The method of claim 2, wherein in step S1, the organic solvent a is one of acetone and tetrahydrofuran.
5. The method for preparing the triazine-based phosphorus-nitrogen based flame retardant according to claim 2, wherein in the step S1, the post-treatment process comprises the following steps: the reaction solution was cooled to room temperature, and after a white precipitate was precipitated, the precipitate was filtered under reduced pressure and washed with acetone.
6. The method for preparing the triazinyl phosphorus-nitrogen based flame retardant according to claim 2, wherein in the step S2, the reaction molar ratio of the flame retardant intermediate to the triethyl phosphite is 1 (2-2.1).
7. The method of claim 2, wherein in step S2, the organic solvent B is one of benzene and toluene.
8. The method for preparing the triazine-based phosphorus-nitrogen based flame retardant according to claim 2, wherein in the step S2, the post-treatment process comprises the following steps: the reaction solution was cooled to room temperature, and after a white precipitate was precipitated, the reaction solution was filtered under reduced pressure.
9. The application of the triazine-based phosphorus-nitrogen flame retardant according to claim 1, wherein the triazine-based phosphorus-nitrogen flame retardant is used in a flame retardant process of high polymer materials and functional molecular materials.
10. The use of the triazine-based phosphorus-nitrogen-based flame retardant according to claim 9, wherein the triazine-based phosphorus-nitrogen-based flame retardant is used in the flame retardant process of polyamide, epoxy resin, polyurethane, textile and plastics for electronic equipment.
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