CN104031090A - Preparation method of cyclic phosphorus-nitrogen synergistic halogen-free flame retardant - Google Patents
Preparation method of cyclic phosphorus-nitrogen synergistic halogen-free flame retardant Download PDFInfo
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Abstract
The invention relates to a preparation method of a cyclic phosphorus-nitrogen synergistic halogen-free flame retardant, particularly a preparation method of 2,7-di(N,N-dimethylamino)-1,6,3,8,2,7-octahydrodioxadiazolyldiphosphinic acid, belonging to the field of preparation of novel halogen-free flame retardants. The method comprises the following steps: by using an organic solvent as a solvent and alkali as an acid-binding agent, stirring phosphorus oxychloride and dimethylamine hydrochloride to react at -25-0 DEG C until no white precipitate is generated; leaving the low-temperature environment, naturally heating the reaction system to room temperature, and continuing the reaction at room temperature for 2-5 hours; carrying out vacuum filtration to remove the precipitate, thereby obtaining a filtrate; and carrying out secondary heating, and carrying out vacuum filtration to remove the precipitate, thereby obtaining the 2,7-di(N,N-dimethylamino)-1,6,3,8,2,7-octahydrodioxadiazolyldiphosphinic acid. The method has the advantages of simple technique and low cost, can easily implement industrial production, and has wide market application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, be specifically related to a kind of 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2, the preparation method of 7-octahydro dioxadiazole diphosphinic acid, belongs to the preparation field of novel halogen-free flame-retardant agent.
Background technology
Along with the development of Macromolecular materials industry, the synthetic materialss such as plastics, rubber, fiber, more and more widely for fields such as weaving, building, chemical industry, military affairs and traffic.Meanwhile, due to the inflammableness of macromolecular material, make flame-retarded technology receive global concern.
At present, according to fire retardant and by the relation of ignition resistant substrate, fire retardant can be divided into addition type and the large class of response type two.The high polymer processing technique fire-retardant with additive flame retardant is simple, and the fire retardant that can meet service requirements is wide in variety, but need to solve the series of problems such as dispersiveness, consistency, interface property of fire retardant; Adopt flame retardant resistance that reactive flame retardant obtains to have relative permanent, on also less by the impact of the physicals of flame-retardant polymer.Halogenated flame retardant, particularly bromide fire retardant are based flame retardants of applying the earliest, but produce more smog and poisonous corrosive gases when burning, can affect people's immunity and regeneration system rapidly, cause secondary pollution, even have strong carcinogenesis.The developed countries such as current America and Europe have started to ban use of Halogen and heavy metal fire retardant.In recent years, response type phosphorus, phosphorus-nitrogen coordinated fire-retardant agent enjoy favor, because its flame retarding efficiency is high, do not produce poisonous or corrosive gases in fire-retardant process, and the growing amount of cigarette is also less, therefore very noticeable in flame retardant area.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, this fire retardant has two functionality (being applicable to doing the chainextender of polyreaction), has 4 P-N structures in ring shaped molecule structure, and flame retarding efficiency is high, and charring rate is high; The preparation method of this ring-type phosphorus nitrogen synergistic halogen-free flame retardants is simple, easy to operate, preparation feedback mild condition, and low for equipment requirements, production cost is low.
The object of the invention is to be achieved through the following technical solutions.
A ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid (ODDP); The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 ℃, and thermal weight loss decomposition mechanism place temperature is 198.14 ℃, in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32%, be applicable to doing fire retardant or the chainextender of macromolecular material.
A preparation method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, concrete steps are as follows:
Step 1, under protection of inert gas condition, with organic solvent, make solvent, alkali is made acid binding agent, phosphorus oxychloride and dimethylamine hydrochloride (mol ratio is 1:1～2:1) stirring reaction at-25～0 ℃ of temperature generates to no longer including white depositions; Then depart from low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2～5 hours at ambient temperature; Obtain the mixture that contains intermediate product 1;
Step 2, by the mixture that contains intermediate product 1 of step 1 gained, vacuum filtration disgorging, obtains filtrate;
Step 3, under protection of inert gas condition, in the filtrate of step 2 gained, add thanomin, still with alkali, do acid binding agent; Under ice-water bath, react to system color and no longer deepen; Then be warming up to 30～50 ℃, and at this temperature, react and to system, no longer include throw out and generate;
Step 4, vacuum filtration are removed the throw out in step 3, will after the purified processing of filtrate, obtain 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Described rare gas element is a kind of in argon gas, helium, nitrogen, preferentially selects nitrogen;
Described acid binding agent is a kind of in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, preferentially selects triethylamine;
Described organic solvent is a kind of in benzene,toluene,xylene, methylene dichloride, ether, sherwood oil, ethyl acetate, acetone, butanone, preferentially selects methylene dichloride;
Described purification process process is: first use sherwood oil wash filtrate 1-4 time, then vacuum filtration is removed insolubles, obtains product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid after underpressure distillation vacuum-drying.
Its preparation technology's principle is shown below:
Beneficial effect
1, a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants of the present invention, 2,7-, bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid compound structure has good symmetry, stability, and compound has higher phosphorus, nitrogen content, in molecular structure, comprise 4 P-N structures, phosphorus nitrogen synergistic effect is strong, and Heat stability is good, charring rate are high, and nontoxic, environmental protection.
2, a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants of the present invention, 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid ring compound is the new and effective halogen-free flame retardants of high phosphorus, nitrogen content, its Stability Analysis of Structures, charring rate high (>20%) phosphorus nitrogen synergistic effect are strong, show good flame retardant effect in aqueous polyurethane is flame-retardant modified.
3, the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants of the present invention, of the present invention 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2, preparation technology is simple for 7-octahydro dioxadiazole diphosphinic acid, and cost is low, is easy to suitability for industrialized production, and market application foreground is wide.
Accompanying drawing explanation
Fig. 1 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2, the infrared spectrogram of 7-octahydro dioxadiazole diphosphinic acid;
Fig. 2 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid
1h-NMR spectrogram;
Fig. 3 is 2,7-bis-(N, N dimethylamine base-1, the mass spectrum of 6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1
A ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 ℃, and thermal weight loss decomposition mechanism place temperature is 198.14 ℃, in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32%, be suitable for doing fire retardant or the chainextender of macromolecular material.As shown in Figure 1, Figure 2, Figure 3 shows; Fig. 1 represents, 3264cm
-1place is N-H stretching vibration absorption peak; 2930～2894cm
-1place is-CH
2-cH
2stretching vibration absorption peak; 1394cm
-1stretching vibration absorption peak for-P-NH; 1213.99cm
-1, 1310.41cm
-1, 1004cm
-1be respectively P=O ,-N-C and-charateristic avsorption band of P-N.Fig. 2 shows, at the acromion of 2.55ppm Chu You – NH-, in two groups of couplings at 3.3ppm and 3.5ppm place, splits the CH of swarming for being connected with nitrogen-atoms on encircling
2-on the characteristic peak of two H; In two groups of couplings at 4.1ppm and 4.3ppm place, split the CH of swarming for being connected with O on encircling
2-on the characteristic peak of two H; Near double spike 2.65ppm is-N-(CH
3)
2in H.Due to the impact of molecule ring texture, make two H on identical C atom produce multiple coupling and split minute, and appear in different displacements, but H in symmetrical structure appears in same displacement, therefore
1on HNMR, only show the H of 7 different displacements, and the ratio of peak area is 1:1:1:1:6:1.Fig. 3 shows, m/z323.1[M+Na on mass spectrum]
+place occurs unimodal, illustrates that molecular weight of product is 300, then coordinates nucleus magnetic hydrogen spectrum data, and deterministic adduct molecule formula is C
8h
22p
2n
4o
4.
N is being housed
2in the reactor of protector, thermometer, feeder, add 0.1mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 100ml methylene dichloride to make solvent simultaneously, 0.15mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise in reactor by triethylamine, make this system bathe in environment and react 1 hour at-5 ℃ of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then by 0.1mol thanomin, 100ml methylene dichloride, 0.15mol triethylamine, again be placed in the reactor that N2 protector, thermometer, feeder are housed, and drip above-mentioned filtrate under magnetic agitation effect, 0 ℃ of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 ℃ of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 400ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 40.6%, and thermal weight loss test decomposition mechanism place temperature is 198.14 ℃, and carbon yield is 20.12%.
Embodiment 2
A ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 ℃, thermal weight loss decomposition mechanism place temperature is 198.14 ℃, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
In the reactor of argon protective device, thermometer, feeder is housed, add 0.15mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 150ml toluene to make solvent simultaneously, 0.25mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise in reactor by triethylamine, make this system bathe in environment and react 1 hour at-5 ℃ of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then 0.1mol thanomin, 150ml methylene dichloride, 0.25mol triethylamine is again placed at N is housed
2in the reactor of protector, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 ℃ of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 ℃ of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 600ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 46.7%, and thermal weight loss test decomposition mechanism place temperature is 198.14 ℃, and carbon yield is 20.12%.
Embodiment 3
A ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 ℃, thermal weight loss decomposition mechanism place temperature is 198.14 ℃, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
N is being housed
2in the reactor of protector, thermometer, feeder, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml ethyl acetate to make solvent simultaneously, 0.9mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise in reactor by triethylamine, make this system bathe in environment and react 1 hour at-5 ℃ of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then by 0.6mol thanomin, 200ml ethyl acetate, 1.0mol triethylamine, is again placed at N is housed
2in the reactor of protector, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 ℃ of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 ℃ of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 900ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 45.3%, and thermal weight loss test decomposition mechanism place temperature is 198.14 ℃, and carbon yield is 20.12%.
Embodiment 4
A ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 ℃, thermal weight loss decomposition mechanism place temperature is 198.14 ℃, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
In the reactor of argon protective device, thermometer, feeder is housed, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml methylene dichloride to make solvent simultaneously, 0.5mol sodium hydroxide is slowly added in reactor under magnetic agitation, make this system bathe in environment and react 1 hour at-8 ℃ of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed insolubles, obtains filtrate again; Then by 0.6mol thanomin, 200ml methylene dichloride, 0.9mol triethylamine is placed in the reactor that argon protective device, thermometer, feeder are housed again, and under magnetic agitation effect, drip above-mentioned filtrate, under 0 ℃ of reaction 1 hour, room temperature, react 2 hours; Finally be warming up to 40 ℃ of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 1000ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 38.2%, and thermal weight loss test decomposition mechanism place temperature is 198.14 ℃, and carbon yield is 20.12%.
Claims (9)
1. a preparation method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, is characterized in that: concrete steps are as follows:
Step 1, under protection of inert gas condition, with organic solvent, make solvent, alkali is made acid binding agent, phosphorus oxychloride and dimethylamine hydrochloride (mol ratio is 1:1～2:1) stirring reaction at-25～0 ℃ of temperature generates to no longer including white depositions; Then depart from low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2～5 hours at ambient temperature; Obtain the mixture that contains intermediate product 1;
Step 2, by the mixture that contains intermediate product 1 of step 1 gained, vacuum filtration disgorging, obtains filtrate;
Step 3, under protection of inert gas condition, in the filtrate of step 2 gained, add thanomin, still with alkali, do acid binding agent; Under ice-water bath, react to system color and no longer deepen; Then be warming up to 30～50 ℃, and at this temperature, react and to system, no longer include throw out and generate;
Step 4, vacuum filtration are removed the throw out in step 3, will after the purified processing of filtrate, obtain 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
2. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: described rare gas element is a kind of in argon gas, helium, nitrogen.
3. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1 or 2, is characterized in that: described rare gas element is nitrogen.
4. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: described acid binding agent is a kind of in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide.
5. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as described in claim 1 or 4, is characterized in that: described acid binding agent is triethylamine.
6. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: described organic solvent is a kind of in benzene,toluene,xylene, methylene dichloride, ether, sherwood oil, ethyl acetate, acetone, butanone.
7. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as described in claim 1 or 6, is characterized in that: described organic solvent is methylene dichloride.
8. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, it is characterized in that: described purification process process is: first use sherwood oil wash filtrate 1-4 time, then vacuum filtration is removed insolubles, obtains product 2,7-bis-(N after underpressure distillation vacuum-drying, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
9. the preparation method of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: its preparation technology's principle is shown below:
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Cited By (3)
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| CN105538451A (en) * | 2016-01-28 | 2016-05-04 | 河南森远科技有限公司 | Method for preparing phosphorous-nitrogen synergistic wood fire retardant |
| CN115806771A (en) * | 2022-11-30 | 2023-03-17 | 国网安徽省电力有限公司亳州供电公司 | Special anticorrosive flame-retardant paint for electrical equipment and preparation method thereof |
| CN115850712A (en) * | 2022-11-30 | 2023-03-28 | 国网安徽省电力有限公司亳州供电公司 | Phosphorus-nitrogen intumescent flame-retardant resin, preparation method thereof and application thereof in special paint for power equipment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115806771A (en) * | 2022-11-30 | 2023-03-17 | 国网安徽省电力有限公司亳州供电公司 | Special anticorrosive flame-retardant paint for electrical equipment and preparation method thereof |
| CN115850712A (en) * | 2022-11-30 | 2023-03-28 | 国网安徽省电力有限公司亳州供电公司 | Phosphorus-nitrogen intumescent flame-retardant resin, preparation method thereof and application thereof in special paint for power equipment |
| CN115806771B (en) * | 2022-11-30 | 2024-03-22 | 国网安徽省电力有限公司亳州供电公司 | Special anti-corrosion flame-retardant paint for power equipment and preparation method thereof |
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