CN115678103B - Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof - Google Patents
Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115678103B CN115678103B CN202211449676.XA CN202211449676A CN115678103B CN 115678103 B CN115678103 B CN 115678103B CN 202211449676 A CN202211449676 A CN 202211449676A CN 115678103 B CN115678103 B CN 115678103B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- long
- chain alkane
- cyclotriphosphazene
- hexachlorocyclotriphosphazene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a long-chain alkane cyclotriphosphazene flame retardant, a preparation method and application thereof, wherein the chemical structure of the flame retardant is as follows:
the invention synthesizes and prepares the novel cyclotriphosphazene by monoglyceride and hexachlorocyclotriphosphazene, which is used as a flame retardant additive of a high polymer material, and has the characteristics of good heat resistance, good synergistic effect, rich flame retardant element content and high flame retardant efficiency.
Description
Technical Field
The invention relates to the technical field of flame retardant manufacturing, in particular to a long-chain alkane cyclotriphosphazene flame retardant, a preparation method and application thereof.
Background
With the development of society, the industry level is improved, and the combustion safety of building materials and products is emphasized by various industries, so that the variety of flame retardants on the market is increasing.
Phosphazene compounds have been studied and developed for hundreds of years since being synthesized, and are applied to wide fields such as military materials in the United states, and are also applied to various fields in China, particularly in the flame retardant field, but the market variety of the phosphazene flame retardant which is marketed in China is limited.
Phosphazenes are compounds which are formed by alternately arranging phosphorus and nitrogen elements and have stable phosphorus-nitrogen skeleton structures, and have good heat stability and flame retardance due to unique phosphorus-nitrogen hybridization structures and high phosphorus-nitrogen contents. The phosphazene has the advantages of no halogen, less smoke during combustion, high flame retardant efficiency, no generation of toxic and corrosive gas, and the like, and is regarded as a second-generation phosphorus-nitrogen intumescent flame retardant. Hexachlorocyclotriphosphazene (HCCP) is an efficient organic phosphorus flame retardant, but chlorine atoms in the HCCP are easily replaced, and the HCCP has poor stability, so that the HCCP can not be independently applied under high temperature condition as a flame retardant, and the problems of low flame retardant efficiency, poor element synergistic effect and the like of nitrogen-phosphorus flame retardants exist in the prior art.
Therefore, it is a problem that a person skilled in the art needs to solve to be able to provide a flame retardant which is stable, has a low addition amount, has good compatibility with polymer materials, and is safe and efficient.
Disclosure of Invention
In view of the above, the invention synthesizes and prepares the novel cyclotriphosphazene by monoglyceride and hexachlorocyclotriphosphazene, which is used as a flame retardant additive of a high polymer material and has the characteristics of good heat resistance, good synergistic effect, rich flame retardant element content and high flame retardant efficiency.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a long-chain alkane cyclotriphosphazene flame retardant has the chemical structure shown as follows:
the invention also provides a preparation method of the long-chain alkane cyclotriphosphazene flame retardant, which comprises the following steps:
(1) Tetrahydrofuran is added into hexachlorocyclotriphosphazene, and stirring is carried out to fully dissolve the hexachlorocyclotriphosphazene, thus obtaining solution A;
(2) Adding tetrahydrofuran into monoglyceride, stirring to dissolve monoglyceride completely to obtain solution B;
(4) Adding the solution B obtained in the step (2) into the solution A obtained in the step (1), continuously stirring, simultaneously introducing nitrogen for protection, and heating to 50-80 ℃; then slowly dripping an acid binding agent, and reacting for 5-48h; the mole ratio of hexachlorocyclotriphosphazene to monoglyceride is 1:1-6; the mol volume ratio of the hexachlorocyclotriphosphazene to the acid binding agent is 1mol:1-20ml;
(4) And (3) cooling the product obtained in the step (3), then decompressing and filtering, rotationally steaming the filtrate to obtain brown yellow viscous liquid, washing with deionized water to obtain white precipitate, recrystallizing with absolute ethyl alcohol, and drying at the temperature of 30-70 ℃ in vacuum to obtain the long-chain alkane cyclotriphosphazene flame retardant.
Preferably, adding the solution B obtained in the step (2) into the solution A obtained in the step (1), continuously stirring and simultaneously introducing nitrogen for protection, and slowly heating to 67 ℃; then triethylamine is slowly dripped into the mixture to react for 12 hours; the mole ratio of hexachlorocyclotriphosphazene to monoglyceride is 1:3.
the reaction mechanism is as follows:
preferably, in the step (1), the mass volume ratio of the hexachlorocyclotriphosphazene to the tetrahydrofuran is 1g:30ml-20g:100ml.
More preferably, in the step (1), the mass-volume ratio of the hexachlorocyclotriphosphazene to the tetrahydrofuran is 3.476g:30ml.
The tetrahydrofuran is refined tetrahydrofuran which is anhydrous and oxygen-free, the addition of the tetrahydrofuran is too small, the reaction is not facilitated, and unnecessary waste is caused by too much tetrahydrofuran.
Preferably, in the step (2), the mass-volume ratio of the monoglyceride to the tetrahydrofuran is 2g:100ml-20g:500ml.
More preferably, in the step (2), the mass-volume ratio of the monoglyceride to the tetrahydrofuran is 11.8325g:100ml.
Preferably, in the step (2), the acid binding agent is triethylamine or anhydrous potassium carbonate.
The beneficial effect of adopting above-mentioned technical scheme: triethylamine or anhydrous potassium carbonate can be used as an acid binding agent, and meanwhile, the reaction can be effectively promoted. And is easy to separate in the post-treatment, and has better compatibility with solvents.
The invention also discloses application of the long-chain alkane cyclotriphosphazene flame retardant in a polymer composite material.
Compared with the prior art, the invention discloses a preparation method for synthesizing the long-chain alkane cyclotriphosphazene flame retardant by using monoglyceride and hexachlorocyclotriphosphazene, the flame retardant prepared by the method has higher carbon element content, the content of the carbon element is improved to help to improve the flame retardant efficiency of the cyclotriphosphazene, a carbon layer with higher thickness is easy to form after combustion, the improvement of flame retardant performance is facilitated, and long-chain molecules in monoglyceride are beneficial to the compatibility of the flame retardant and a high polymer base material and the processing toughness of hard plastics are increased, so that the flame retardant is better dispersed in a high polymer, and the excellent flame retardant property of the flame retardant is better exerted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of trioctadecyl-2, 3-propyldioxy cyclotriphosphazene prepared in example 1 of the present invention;
FIG. 2 is a schematic illustration of a trioctadecyl-2, 3-propyldioxy-cyclotriphosphazene prepared in example 1 of the present invention 1 H-NMR spectrum;
FIG. 3 is a schematic representation of a tris (octadecyl ester-based 2, 3-propyldioxy) cyclotriphosphazene prepared in example 1 of the present invention 31 P-NMR characterization of the spectra.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
EXAMPLE 1 preparation of Tri (octadecyl ester) 2, 3-propyldioxy) cyclotriphosphazene
(1) 3.476g of hexachlorocyclotriphosphazene and 30ml of purified tetrahydrofuran are put into a 250ml dry four-neck flask provided with a stirrer and a condensation reflux device, so that the hexachlorocyclotriphosphazene is fully dissolved to obtain a solution A;
(2) 11.8325g of monoglyceride is dissolved in 100ml of refined tetrahydrofuran, and the mixture can be fully dissolved by slightly heating to obtain solution B;
(3) Adding the solution B obtained in the step (2) into the solution A obtained in the step (1), continuously stirring, simultaneously introducing nitrogen for protection, and slowly heating to 67 ℃; slowly dripping 8.5ml of triethylamine, reacting for 12 hours, and generating a large amount of white sediment at the bottom of the bottle;
(4) Cooling, filtering under reduced pressure, steaming the filtrate to obtain brown yellow viscous liquid, washing with deionized water to obtain white precipitate, recrystallizing with absolute ethanol, and oven drying at 40deg.C under vacuum with yield of about 61.9%.
FIG. 1 is an infrared spectrum of trioctadecyl-2, 3-propyldioxy cyclotriphosphazene, 3444.87cm -1 The absorption peak of-OH, possibly of water, is 1737.86cm -1 Is carbonyl peak in monoglyceride, 989.48cm- 1 Is characteristic absorption peak of P-O-C, 1219.01cm -1 、1197.79cm -1 Vibration absorption peak of p=n, 1101.36cm -1 、1051.20cm -1 Indicating the presence of phosphazene heterocycle, P-Cl at 628.80cm -1 、549.72cm -1 The vibration absorption peak of (c) disappeared, proving that Cl has been completely replaced.
FIG. 2 is a diagram of tris (octadecyl ester-2, 3-propyldioxy) cyclotriphosphazene 1 H-NMR spectrum shows that the proton peaks of two-OH groups in monoglyceride at chemical shifts of 3.63ppm and 3.71ppm disappeared, indicating that two hydroxyl groups in monoglyceride have been reacted, and that the proton peak of deuterated chloroform solvent is at chemical shift of 7.28 ppm.
FIG. 3 is a diagram of tris (octadecyl ester-2, 3-propyldioxy) cyclotriphosphazene 31 In the P-NMR characterization spectrogram, the chemical shift is 28×10 -2 A single peak at ppm indicates that there is only one chemical phosphorus atom in the product, which further demonstrates the product's singleness and higher purity. In summary, two hydroxyl groups in monoglycerides have been successfully incorporated into hexachlorocyclotriphosphazene to form trioctadecyl-2, 3-propyldioxy-cyclotriphosphazene.
Test example 1
Preparing an epoxy resin composite material:
the flame retardant synthesized in example 1 was added to an epoxy resin at a ratio of 5%, wherein 30g of the epoxy resin, 2.1g of the flame retardant and 12g of the curing agent DDM were uniformly mixed, poured into a mold and placed in an oven, cured at 100℃for 3 hours, cured at 160℃for 1 hour, after the curing was completed, all samples were cooled to room temperature, and demolded to obtain an epoxy composite material, and then a combustion test was performed, with the results shown in Table 1.
The experimental method comprises the following steps: the flammability of an epoxy composite material having a size of 100 x 150 x 3mm was tested according to ASTM D3801-2006 on a vertical burn tester; limiting Oxygen Index (LOI) testing of epoxy composites was performed on an oxygen index analyzer according to ASTM D2863, with a sample test size of 100 x 150 x 3mm.
The UL-94 standard is an experimental method standard regarding the burning properties of materials, established by underwriters' laboratories, for evaluating the ability of a material to extinguish after being ignited. Wherein, the flame retardant grade of the plastic is gradually increased from HB, V-2 and V-1 to V-0, and specifically comprises the following steps:
HB: the burning speed of a sample with the thickness of 3-13mm is required to be less than 40mm/min; samples less than 3mm thick, burn at a rate of less than 70mm/min, or extinguish before 100mm marking.
V-2: after the sample is subjected to the combustion test for 10 seconds for two times, the flame is extinguished within 30 seconds, and the burnt objects can fall off;
v-1: after the sample is subjected to the combustion test for 10 seconds for two times, the flame is extinguished within 30 seconds, and no combustion objects can fall off;
v-0: after the sample was subjected to the combustion test twice for 10 seconds, the flame was extinguished within 10 seconds, and no combustion object was allowed to fall.
Table 1: vertical burning test result of epoxy composite material
In conclusion, the flame retardant performance of the flame retardant/epoxy composite material does not reach V-2 level, but no molten drops of the combustibles drop, and the oxygen index of the epoxy composite material is 29.6%, so that the flame retardant/epoxy composite material belongs to flame retardant materials.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
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 (6)
1. A long-chain alkane cyclotriphosphazene flame retardant is characterized by comprising the following chemical structures:
2. the method for preparing the long-chain alkane cyclotriphosphazene flame retardant according to claim 1, which is characterized by comprising the following steps:
(1) Tetrahydrofuran is added into hexachlorocyclotriphosphazene, and stirring is carried out to fully dissolve the hexachlorocyclotriphosphazene, thus obtaining solution A;
(2) Adding tetrahydrofuran into monoglyceride, stirring to dissolve monoglyceride completely to obtain solution B;
(3) Adding the solution B obtained in the step (2) into the solution A obtained in the step (1), continuously stirring, simultaneously introducing nitrogen for protection, and heating to 50-80 ℃; then slowly dripping an acid binding agent, and reacting for 5-48h; the mole ratio of hexachlorocyclotriphosphazene to monoglyceride is 1:1-6; the mol volume ratio of the hexachlorocyclotriphosphazene to the acid binding agent is 1mol:1-20ml;
(4) And (3) cooling the product obtained in the step (3), then decompressing and filtering, rotationally steaming the filtrate to obtain brown yellow viscous liquid, washing with deionized water to obtain white precipitate, recrystallizing with absolute ethyl alcohol, and drying at the temperature of 30-70 ℃ in vacuum to obtain the long-chain alkane cyclotriphosphazene flame retardant.
3. The method for preparing a long-chain alkane cyclotriphosphazene flame retardant according to claim 2, wherein in the step (1), the mass volume ratio of the hexachlorocyclotriphosphazene to the tetrahydrofuran is 1g:30ml-20g:100ml.
4. The method for preparing a long-chain alkane cyclotriphosphazene flame retardant according to claim 2, wherein in the step (2), the mass volume ratio of the monoglyceride to the tetrahydrofuran is 2g:100ml-20g:500ml.
5. The method for preparing a long-chain alkane cyclotriphosphazene flame retardant according to claim 2, wherein in the step (2), the acid binding agent is triethylamine or anhydrous potassium carbonate.
6. The use of a long-chain alkane cyclotriphosphazene flame retardant according to claim 1 in high molecular composite materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211449676.XA CN115678103B (en) | 2022-11-18 | 2022-11-18 | Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211449676.XA CN115678103B (en) | 2022-11-18 | 2022-11-18 | Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115678103A CN115678103A (en) | 2023-02-03 |
| CN115678103B true CN115678103B (en) | 2023-07-07 |
Family
ID=85053781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211449676.XA Active CN115678103B (en) | 2022-11-18 | 2022-11-18 | Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678103B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4321217A (en) * | 1980-06-05 | 1982-03-23 | The United States Of America As Represented By The Secretary Of The Navy | Dialkylated phosphazene oligomers and method of preparation thereof |
| CN107337692A (en) * | 2017-07-04 | 2017-11-10 | 西北工业大学 | The preparation method of the phosphonitrile type epoxy resin of ring three |
| CN112979708A (en) * | 2021-04-08 | 2021-06-18 | 衡阳师范学院 | Preparation method and application of flame retardant containing bromocyclophosphazene |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5344742B2 (en) * | 2008-08-01 | 2013-11-20 | 株式会社Ａｄｅｋａ | Flame retardant thermoplastic resin composition |
-
2022
- 2022-11-18 CN CN202211449676.XA patent/CN115678103B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4321217A (en) * | 1980-06-05 | 1982-03-23 | The United States Of America As Represented By The Secretary Of The Navy | Dialkylated phosphazene oligomers and method of preparation thereof |
| CN107337692A (en) * | 2017-07-04 | 2017-11-10 | 西北工业大学 | The preparation method of the phosphonitrile type epoxy resin of ring three |
| CN112979708A (en) * | 2021-04-08 | 2021-06-18 | 衡阳师范学院 | Preparation method and application of flame retardant containing bromocyclophosphazene |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 一种新型环膦腈类化合物———三（邻氨基苯氧基） 环磷腈的制备;黄耿，等;《衡阳师范学院学报》;第37卷(第6期);60-63 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115678103A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Bisphenol-S bridged penta (anilino) cyclotriphosphazene and its application in epoxy resins: synthesis, thermal degradation, and flame retardancy | |
| CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
| Luo et al. | An efficient organic/inorganic phosphorus–nitrogen–silicon flame retardant towards low-flammability epoxy resin | |
| Gao et al. | Effect of a novel phosphorous–nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly (butylene terephthalate) | |
| Xu et al. | Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance | |
| Liu et al. | Novel cyclotriphosphazene-based epoxy compound and its application in halogen-free epoxy thermosetting systems: Synthesis, curing behaviors, and flame retardancy | |
| Wang et al. | A effective flame retardant for epoxy resins based on poly (DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) | |
| El Gouri et al. | Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin | |
| Fang et al. | An effective flame retardant for poly (ethylene terephthalate) synthesized by phosphaphenanthrene and cyclotriphosphazene | |
| CN112979708B (en) | Preparation method and application of low-halogen cyclophosphazene flame retardant | |
| CN105669760B (en) | A kind of organic phospha phenanthrene derivative and preparation method and application | |
| Jia et al. | TG-FTIR and TG-MS analysis applied to study the flame retardancy of PVC–castor oil-based chlorinated phosphate ester blends | |
| CN110563765B (en) | Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant | |
| CN104311876A (en) | Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant | |
| CN113861241B (en) | Bridged DOPO phosphorus nitrogen flame retardant, and preparation method and application thereof | |
| CN108659040A (en) | A kind of Phenylphosphine diamide derivative and its synthetic method and application | |
| Liu et al. | Synthesis and performance of three flame retardant additives containing diethyl phosphite/phenyl phosphonic moieties | |
| CN110643066B (en) | Phosphorus-nitrogen flame retardant and preparation method thereof | |
| Deng et al. | Synthesis and effect of hyperbranched (3-hydroxyphenyl) phosphate as a curing agent on the thermal and combustion behaviours of novolac epoxy resin | |
| CN104131463A (en) | Metal ion-modified ammonium polyphosphate and its preparation method and use | |
| CN103881333B (en) | A kind of fire retardant PBT with no halogen process for preparing resins of DOPO base | |
| CN105237674A (en) | Method for preparing phosphorus-containing flame-retardant acrylic resin | |
| CN115678103B (en) | Long-chain alkane cyclotriphosphazene flame retardant, and preparation method and application thereof | |
| CN107652324B (en) | Three-source-in-one expansion type fire retardant and its synthetic method and application | |
| Qian et al. | Synthesis, characterization and performance evaluation of a flame retardant plasticizer for poly (vinyl chloride) derived from biobased vanillic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |