CN112300369B - Reactive epoxy resin flame retardant and preparation method thereof - Google Patents
Reactive epoxy resin flame retardant and preparation method thereof Download PDFInfo
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- CN112300369B CN112300369B CN202011232032.6A CN202011232032A CN112300369B CN 112300369 B CN112300369 B CN 112300369B CN 202011232032 A CN202011232032 A CN 202011232032A CN 112300369 B CN112300369 B CN 112300369B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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)
Abstract
The invention provides a reactive epoxy resin flame retardant and a preparation method thereof, wherein the reactive epoxy resin flame retardant comprises the following components: a first synthetic product obtained by the reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and succinic anhydride and a second synthetic product obtained by the reaction of 2,4-diaminothiazole. The reactive flame retardant prepared by the invention keeps the P-H bond with stronger activity in the DOPO group, so that the flame retardant has good reaction activity, can further have good compatibility and bonding capability with epoxy resin, and can effectively solve the problem that the added and blended non-reactive flame retardant is easy to seep out from a polymer/resin system.
Description
Technical Field
The invention relates to a high-molecular flame retardant, in particular to a reactive epoxy resin flame retardant and a preparation method thereof.
Background
Resin materials are widely applied, for example, epoxy resins have the advantages of excellent adhesion, electrical insulation, chemical stability, mechanical properties and the like, and are widely applied to the fields of transportation, aerospace, integrated circuits and the like. However, the Limited Oxygen Index (LOI) of general-purpose epoxy resins is generally only about 20%, are easily burned, and are continuously burned after a fire with a large amount of smoke, and have a serious safety problem, so that the use thereof is limited by such drawbacks.
The flame retardant property of the epoxy resin can be improved to a certain extent by directly adding the additive flame retardant (comprising the organic flame retardant and the inorganic flame retardant) into the epoxy resin, however, the additive flame retardant is often added in a large amount and is difficult to disperse, so that the viscosity of the epoxy resin is increased rapidly, and the technological property of the epoxy resin is affected.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is an organic phosphorus heterocyclic compound, has a unique chemical structure, has high thermal stability, oxidation resistance and excellent water resistance, and is a common reactive flame retardant and an additive flame retardant. For example, chinese patent document CN102391545a discloses a nitrogen and phosphorus-containing flame retardant, a preparation method and an application thereof, wherein the flame retardant is obtained by an addition reaction of an imine product obtained by a condensation reaction of p-phenylenediamine and an aromatic aldehyde and DOPO. The DOPO-introduced flame retardant is an additive flame retardant, the addition amount of the DOPO-introduced flame retardant is large, and the flame retardance and other properties need to be further improved.
Compared with an additive flame retardant, the reactive flame retardant capable of directly introducing a flame-retardant group or element into an epoxy resin matrix chain segment has good dispersibility, can keep relatively low viscosity and good technological properties of the epoxy resin, has the advantages of relatively high-grade flame retardant performance of the epoxy resin and the like, and gradually becomes a research hotspot in the field. However, the conventional reactive flame retardants have been required to have further improved properties such as flame retardancy due to poor reactivity, and the like, and when they are applied to epoxy resins, the transparency, mechanical properties, and other qualities of the epoxy resins are not satisfactory.
Disclosure of Invention
The invention provides a reactive epoxy resin flame retardant, which is an efficient reactive flame retardant containing nitrogen, phosphorus and sulfur, and can effectively improve the flame retardant property of epoxy resin and keep better transparency and mechanical property of the resin. In one aspect of the present invention, there is provided a reactive epoxy resin flame retardant comprising: a first synthetic product obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (i.e., DOPO) with succinic anhydride, and a second synthetic product obtained by reacting 2,4-diaminothiazole.
The flame retardant provided by the invention adopts the specific second synthetic compound, has the characteristics of good flame retardance, flame retardance stability and the like, and the inventor considers through research and analysis that the second synthetic compound takes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), succinic anhydride (SAA for short) and 2,4-diaminothiazole as raw materials and is prepared through a two-step method (namely, a first synthetic product is prepared first, and then the first synthetic product and 2,4-diaminothiazole react to synthesize a second synthetic product), the molecular structure of the second synthetic product simultaneously contains three elements of nitrogen, phosphorus and sulfur for synergistic flame retardance, wherein the phosphorus element can play a role in gas phase and condensed phase flame retardance, quenches free radicals and catalyzes carbon during combustion, the nitrogen element can be converted into flammable gas during combustion, the sulfur element can enhance a carbon layer, and the synergistic effect of the three elements overcomes the defects of a single flame retardant element, so that the flame retardance of the material is effectively improved; in addition, in the second synthetic product, through reasonably assembling and modifying core structure segments of raw materials such as DOPO,2,4-diaminothiazole and the like, a P-H bond with stronger activity in a DOPO group can be reserved in the molecular structure of the second synthetic product, so that the flame retardant has good reactivity (such as the ring-opening reaction of an epoxy group of epoxy resin can be promoted), and further has good compatibility and bonding capability with the epoxy resin, the stability of the flame retardant resin formed by adopting the flame retardant is ensured, and the problem that the blended inactive flame retardant is easy to seep out from a polymer/resin system can be effectively solved; in addition, the second synthetic product contains-NH generated by the reaction of an acid anhydride group and an amino group on 2,4-diaminothiazole, and the-NH can participate in the curing of epoxy resin, so that the flame-retardant resin formed by the flame retardant can ensure good transparency, mechanical properties and other qualities.
Specifically, the first synthesis product is mainly obtained by condensing DOPO and succinic anhydride, the second synthesis product is obtained by condensing the first synthesis product and 2,4-diaminothiazole, and the chemical structural formula of the second synthesis product can be shown as follows:
in one embodiment of the present invention, the first synthesis product may be prepared according to a preparation process comprising the steps of: under the condition of ice-water bath, adding succinic anhydride into a first solution containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and heating the obtained first mixed system to 20-90 ℃ for reaction to obtain a first synthetic product; and/or, the second synthetic product may be prepared according to a preparation process comprising the steps of: under the condition of ice-water bath, adding organic alkali into a second solution system containing the first synthetic product and 2,4-diaminothiazole, and then heating the obtained second mixed system to 20-30 ℃ for reaction to obtain a second synthetic product.
Wherein, the organic base can comprise at least one of triethylamine, N-diisopropylethylamine, N-methylmorpholine and 4-dimethylaminopyridine.
Further, the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to succinic anhydride may be 1.0: (1.0-1.5); and/or, the molar ratio of the first synthesis product to 2,4-diaminothiazole may be 1.0: (1.2-2.0) is beneficial to the performances of flame retardance, stability and the like of the flame retardant.
In another aspect of the present invention, a preparation method of the reactive epoxy resin flame retardant is also provided, which includes:
under the condition of ice-water bath, adding succinic anhydride into a first solution containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and heating the obtained first mixed system to 20-90 ℃ for reaction to obtain a first synthetic product (DOPO-SAA for short);
under the condition of ice-water bath, adding organic alkali into a second solution containing the first synthetic product and 2,4-diaminothiazole, and then heating the obtained second mixed system to 20-30 ℃ for reaction to obtain a second synthetic product. Specifically, the reaction time of the first mixed system at 20-90 ℃ can be 2-5 hours; and/or the reaction time of the second mixed system at 20-30 ℃ can be 3-12 hours.
In one embodiment, the second mixed system may be heated to 20-25 ℃ to react to obtain the second synthetic product.
Generally, in specific implementation, the temperature of the first mixed system can be controlled to be 30-80 ℃ or 40-60 ℃ to carry out the reaction, so as to facilitate the reaction. In order to further improve the reaction efficiency, in an embodiment of the present invention, the first solution further contains a first catalyst, where the first catalyst includes at least one of aluminum trichloride, boron trichloride, ferric trichloride, zinc chloride, and tin tetrachloride; and/or the second solution also contains a second catalyst, and the second catalyst comprises 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCl) and/or 1-hydroxybenzotriazole (HOBt).
In one embodiment of the present invention, during the synthesis of the first synthesis product, the molar ratio of DOPO, succinic anhydride, and catalyst may be generally controlled to be 1.0: (1.0-1.5): (2.0-3.0); and/or, in the synthesis process of the second synthesis product, the molar ratio of 2,4-diaminothiazole, EDCl, HOBt, DOPO-SAA and the organic base can be controlled to be 1.0 to (1.2-2.0): (0.1-1.2): (1.2-2.0): (2.0-3.0).
The solvent in the first solution and the second solution may be a solvent conventional in the art, for example, in one embodiment of the present invention, the solvent of the first solution (referred to as the first solvent) may include at least one of dichloromethane, carbon tetrachloride, tetrachloroethane, nitrobenzene, nitromethane, and petroleum ether; and/or, the solvent of the second solution (denoted as second solvent) may include at least one of dichloromethane, N-dimethylformamide, N-dimethylacetamide, pyridine.
The reaction device used in the above reaction may be a reaction device commonly used in the art, such as a three-neck flask, etc., and the present invention is not particularly limited thereto and is not described in any greater detail.
In an embodiment of the present invention, the preparation method of the flame retardant may include the following steps:
1) Under the protection of nitrogen, uniformly mixing DOPO and a first catalyst in a first solvent to obtain a first solution; slowly dropwise adding an anhydrous ethanol solution of succinic anhydride (SAA) into the first solution under the stirring of an ice-water bath, and obtaining a first mixed system after the dropwise adding is finished; slowly heating the first mixed system to 20-90 ℃, and then continuously stirring for reaction for 2-5 hours; after the reaction, the reaction system was cooled to room temperature, and the DOPO derivative (i.e., the first synthesis product (DOPO-SAA)) was obtained after suction filtration, washing and drying. The reaction equation for this process is schematically shown below:
2) Under the protection of nitrogen, uniformly mixing a first synthetic product (DOPO-SAA), 2,4-diaminothiazole, EDCl and HOBt in a second solvent to obtain a second solution; slowly dropwise adding organic base into the second solution under the ice-water bath condition, and obtaining a second mixed system after dropwise adding; heating the second mixed system to 20-30 ℃ for reaction for 3-12 hours, and filtering the reaction system after TLC detection reaction is finished to obtain filtrate; and (3) after the filtrate is extracted, purifying and separating the filtrate by column chromatography (petroleum ether: ethyl acetate = 1: 2) to obtain a solid product, wherein the solid product is a second synthetic product. The reaction equation for this process is shown below:
in another aspect of the invention, the invention also provides an application of the reactive flame retardant in flame retardance of epoxy resin.
The implementation of the invention has at least the following beneficial effects:
according to the flame retardant provided by the invention, a second synthetic product synthesized by using DOPO, succinic anhydride and 2,4-diaminothiazole as main raw materials is adopted, so that the flame retardant has good flame retardance and other properties, and researches show that when the flame retardant is used for epoxy resin, when the addition amount of the reactive flame retardant is only 5.7wt% (the phosphorus content of an epoxy resin cured product is 0.49 wt%), the limit oxygen index of the epoxy resin cured product can be increased from 19.8% to 32.1%, and the vertical combustion grade reaches UL-94V-0 level; in addition, the flame retardant also has the advantages of good flame retardant stability and the like, and the flame retardant epoxy resin formed by adopting the flame retardant has good transparency, mechanical properties and other qualities, so that the flame retardant can be widely applied to the aspects of high-temperature structure flame retardant materials such as national defense materials, electronic and electrical materials, building materials and the like.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1:
the reactive epoxy resin flame retardant provided in this example is a second synthetic product prepared as follows:
under the protection of nitrogen, adding 21.60g (0.10 mol) of DOPO,26.67g (0.20 mol) of anhydrous aluminum trichloride and 300mL of dichloromethane into a three-neck flask, and uniformly mixing to obtain a first solution; slowly dropwise adding a mixed solution of 12.00g (0.12 mol) of succinic anhydride and absolute ethyl alcohol into the first solution under the stirring of an ice-water bath, and obtaining a first mixed system after dropwise adding; slowly heating the first mixed system to 50 ℃, continuously stirring for reacting for 3 hours, cooling to room temperature, carrying out suction filtration to collect filtrate, washing the filtrate with acetone, then carrying out rotary evaporation to remove the solvent, and carrying out vacuum drying to obtain a first synthetic product (DOPO-SAA), wherein the yield is 72.43%;
under the protection of nitrogen, 2.30g (0.02 mol) 2,4-diaminothiazole, 7.67g (0.04 mol) EDCI, 2.70g (0.02 mol) HOBt, 9.48g (0.03 mol) DOPO-SAA and 100mL dichloromethane are added into another three-neck flask provided with a magnetic stirrer, and stirred for 30min to uniformly mix the system to obtain a second solution; slowly dripping 4.05g (0.04 mol) of triethylamine into the second solution under the condition of ice-water bath to obtain a second mixed system after finishing dripping; and (3) reacting the second mixed system at 25 ℃ for 4 hours, filtering to obtain a filtrate after TLC detection reaction is finished, extracting the filtrate by acetone, and purifying and separating by column chromatography (petroleum ether: ethyl acetate = 1: 2) to obtain yellow solid powder (namely the second synthetic product) with the yield of 82.5%.
Example 2
The reactive epoxy resin flame retardant provided in this example is a second synthetic product prepared as follows:
under the protection of nitrogen, 21.60g (0.10 mol) of DOPO,33.33g (0.25 mol) of anhydrous aluminum trichloride and 200mL of nitrobenzene are added into a three-neck flask and uniformly mixed to obtain a first solution; slowly dropwise adding a mixed solution of 15.00g (0.15 mol) of succinic anhydride and absolute ethyl alcohol into the first solution under the stirring of an ice-water bath, and obtaining a first mixed system after dropwise adding; slowly heating the first mixed system to 40 ℃, continuously stirring for reacting for 5 hours, cooling to room temperature, carrying out suction filtration to collect filtrate, washing the filtrate with acetone, then carrying out rotary evaporation to remove the solvent, and carrying out vacuum drying to obtain a first synthetic product (DOPO-SAA) with the yield of 78.9%;
under the protection of nitrogen, 2.30g (0.02 mol) 2,4-diaminothiazole, 7.67g (0.04 mol) EDCI, 1.35g (0.01 mol) HOBt, 12.64g (0.04 mol) DOPO-SAA and 100mL N, N-dimethylformamide are added into another three-neck flask provided with a magnetic stirrer, and stirred for 30min to uniformly mix the system to obtain a second solution; slowly dripping 4.05g (0.04 mol) of triethylamine into the second solution under the condition of ice-water bath to obtain a second mixed system after finishing dripping; and (3) reacting the second mixed system at 25 ℃ for 6 hours, filtering to obtain a filtrate after TLC detection reaction is finished, extracting the filtrate by acetone, and purifying and separating by column chromatography (petroleum ether: ethyl acetate = 1: 2) to obtain yellow solid powder (namely a second synthetic product) with the yield of 83.21%.
Example 3
The reactive epoxy resin flame retardant provided in this example is a second synthetic product prepared as follows:
under the protection of nitrogen, adding 21.60g (0.10 mol) DOPO,35.16g (0.30 mol) anhydrous boron trichloride and 300mL dichloromethane into a three-neck flask, and uniformly mixing to obtain a first solution; slowly dropwise adding a mixed solution of 10.00g (0.10 mol) of succinic anhydride and absolute ethyl alcohol into the first solution under the stirring of an ice-water bath, and obtaining a first mixed system after dropwise adding; slowly heating the first mixed system to 60 ℃, continuously stirring for reacting for 2 hours, cooling to room temperature, carrying out suction filtration to collect filtrate, washing the filtrate with acetone, carrying out rotary evaporation to remove the solvent, and carrying out vacuum drying to obtain a first synthetic product (DOPO-SAA), wherein the yield is 74.82%;
2.30g (0.02 mol) 2,4-diaminothiazole, 5.75g (0.03 mol) EDCl, 2.70g (0.02 mol) HOBt, 7.58g (0.024 mol) DOPO-SAA and 100mL N, N-dimethylacetamide were added to another three-necked flask equipped with a magnetic stirrer under nitrogen protection, and stirred for 30min to mix the system uniformly to obtain a second solution; slowly dropwise adding 6.07g (0.06 mol) of N-methylmorpholine into the second solution under the condition of ice-water bath, and obtaining a second mixed system after dropwise adding; and (3) reacting the second mixed system at 22 ℃ for 6 hours, filtering to obtain a filtrate after TLC detection reaction is finished, extracting the filtrate by acetone, and purifying and separating by column chromatography (petroleum ether: ethyl acetate = 1: 2) to obtain yellow solid powder (namely a second synthetic product) with the yield of 85.13%.
Example 4
The reactive epoxy resin flame retardant provided in this example is a second synthetic product prepared as follows:
under the protection of nitrogen, 21.60g (0.10 mol) of DOPO,33.33g (0.25 mol) of anhydrous aluminum trichloride and 200mL of nitrobenzene are added into a three-neck flask and uniformly mixed to obtain a first solution; slowly dripping 10.00g (0.10 mol) of mixed solution of succinic anhydride and absolute ethyl alcohol into the first solution under the stirring of ice-water bath, and obtaining a first mixed system after finishing dripping; slowly heating the first mixed system to 60 ℃, continuously stirring for reacting for 2 hours, cooling to room temperature, carrying out suction filtration to collect filtrate, washing the filtrate with acetone, then carrying out rotary evaporation to remove the solvent, and carrying out vacuum drying to obtain a first synthetic product (DOPO-SAA), wherein the yield is 75.06%;
under the protection of nitrogen, 2.30g (0.02 mol) of 2,4-diaminothiazole, 5.75g (0.03 mol) of EDCl, 1.62g (0.012 mol) of HOBt, 12.64g (0.04 mol) of DOPO-SAA and 100mL of dichloromethane are added into another three-neck flask provided with a magnetic stirrer, and stirred for 30min to uniformly mix the system to obtain a second solution; slowly dropwise adding 5.06g (0.05 mol) of triethylamine into the second solution under the condition of ice-water bath, and obtaining a second mixed system after dropwise adding; and (3) reacting the second mixed system at 25 ℃ for 12 hours, filtering to obtain a filtrate after TLC detection reaction is finished, extracting the filtrate by acetone, and purifying and separating by column chromatography (petroleum ether: ethyl acetate = 1: 2) to obtain yellow solid powder (namely a second synthetic product) with the yield of 84.54%.
Application examples
The reactive epoxy resin flame retardant prepared in the example 1 is adopted, and is stirred and mixed with epoxy resin at 110 ℃ for uniform mixing, after half an hour, the temperature is reduced to 90 ℃, diaminodiphenylmethane (DDM) is added for continuous stirring, after a uniform solution is obtained, the solution is transferred to a preheated mold, thermosetting is carried out according to the conditions of two hours at 120 ℃, three hours at 150 ℃ and one hour at 180 ℃, and after the completion of curing, the solution is naturally cooled to room temperature, so that the flame-retardant epoxy cured material is obtained. Through tests, when the addition amount of the reactive flame retardant in the flame-retardant epoxy cured product sample is 5.7wt% (the phosphorus content of the epoxy resin cured product is 0.49 wt%), the vertical burning grade can pass UL-94V-0 grade, and the limiting oxygen index reaches 32.1%.
The reactive epoxy resin flame retardants prepared in examples 2 to 4 were tested according to the above procedures, and the results were similar to those described above and thus will not be described again.
Claims (9)
1. A reactive epoxy resin flame retardant, comprising: a first synthetic product obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with succinic anhydride and a second synthetic product obtained by reacting 2,4-diaminothiazole;
the first synthetic product is prepared according to a preparation process comprising the following steps: under the protection of nitrogen, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a first catalyst are uniformly mixed in a first solvent to obtain a first solution; under the stirring of ice-water bath, dropwise adding anhydrous ethanol solution of succinic anhydride into the first solution to obtain a first mixed system after the dropwise adding is finished; slowly heating the first mixed system to 20-90 ℃, and then continuously stirring for reaction for 2-5 hours; after the reaction is finished, cooling the reaction system to room temperature, and obtaining a first synthetic product (DOPO-SAA) through suction filtration, washing and drying; the reaction equation for this process is schematically shown below:
wherein, the first catalyst comprises at least one of aluminum trichloride, boron trichloride, ferric trichloride, zinc chloride and stannic chloride.
2. The flame retardant of claim 1,
the second synthetic product is prepared according to a preparation process comprising the following steps: under the condition of ice-water bath, adding organic alkali into a second solution system containing the first synthetic product and 2,4-diaminothiazole, and then heating the obtained second mixed system to 20-30 ℃ for reaction to obtain a second synthetic product.
3. The flame retardant of claim 2, wherein the organic base comprises at least one of triethylamine, N-diisopropylethylamine, N-methylmorpholine, 4-dimethylaminopyridine.
4. The flame retardant of claim 1, wherein the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to succinic anhydride is 1.0: (1.0-1.5).
5. The flame retardant of claim 2, wherein the molar ratio of the first synthesis product to 2,4-diaminothiazole is 1.0: (1.2-2.0).
6. The method of preparing a reactive epoxy resin flame retardant according to any one of claims 1 to 5, comprising:
under the protection of nitrogen, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a first catalyst are uniformly mixed in a first solvent to obtain a first solution; under the stirring of ice-water bath, dropwise adding anhydrous ethanol solution of succinic anhydride into the first solution to obtain a first mixed system after the dropwise adding is finished; slowly heating the first mixed system to 20-90 ℃, and then continuously stirring for reaction for 2-5 hours; after the reaction is finished, cooling the reaction system to room temperature, and obtaining a first synthetic product (DOPO-SAA) after suction filtration, washing and drying; the reaction equation for this process is schematically shown below:
wherein the first catalyst comprises at least one of aluminum trichloride, boron trichloride, ferric trichloride, zinc chloride and stannic chloride; under the condition of ice-water bath, adding organic alkali into a second solution containing the first synthetic product and 2,4-diaminothiazole, and then heating the obtained second mixed system to 20-30 ℃ for reaction to obtain a second synthetic product.
7. The method according to claim 6, wherein the first mixed system is reacted at 20 to 90 ℃ for 2 to 5 hours; and/or the reaction time of the second mixed system at 20-30 ℃ is 3-12 hours.
8. The production method according to claim 6 or 7, characterized in that the second solution further contains a second catalyst comprising 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and/or 1-hydroxybenzotriazole.
9. The production method according to claim 6 or 7, wherein the first solvent comprises at least one of dichloromethane, carbon tetrachloride, tetrachloroethane, nitrobenzene, nitromethane, petroleum ether; and/or the solvent of the second solution comprises at least one of dichloromethane, N-dimethylformamide, N-dimethylacetamide and pyridine.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2090618A2 (en) * | 2008-02-15 | 2009-08-19 | Schill + Seilacher "Struktol" Aktiengesellschaft | Hardenable epoxy resin formulation with polyester flame retardant |
| WO2010076276A1 (en) * | 2008-12-29 | 2010-07-08 | Basf Se | Dopo-flame retardant in epoxy resins |
| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN104017172A (en) * | 2014-05-29 | 2014-09-03 | 华南理工大学 | Phosphaphenanthrene symtriazine anhydride epoxy hardener and preparation method thereof |
| CN106750183A (en) * | 2016-12-06 | 2017-05-31 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| CN108997714A (en) * | 2018-07-23 | 2018-12-14 | 深圳职业技术学院 | Reactive flame retardant and its fire retarding epoxide resin for epoxy resin |
-
2020
- 2020-11-06 CN CN202011232032.6A patent/CN112300369B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2090618A2 (en) * | 2008-02-15 | 2009-08-19 | Schill + Seilacher "Struktol" Aktiengesellschaft | Hardenable epoxy resin formulation with polyester flame retardant |
| WO2010076276A1 (en) * | 2008-12-29 | 2010-07-08 | Basf Se | Dopo-flame retardant in epoxy resins |
| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN104017172A (en) * | 2014-05-29 | 2014-09-03 | 华南理工大学 | Phosphaphenanthrene symtriazine anhydride epoxy hardener and preparation method thereof |
| CN106750183A (en) * | 2016-12-06 | 2017-05-31 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| CN108997714A (en) * | 2018-07-23 | 2018-12-14 | 深圳职业技术学院 | Reactive flame retardant and its fire retarding epoxide resin for epoxy resin |
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