CN104031090B - A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants - Google Patents
A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants Download PDFInfo
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Abstract
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, TMSDMA N dimethylamine base)-1,6,3,8, the preparation method of 2,7-octahydro dioxadiazole diphosphinic acid, belongs to the preparation field of novel halogen-free flame-retardant agent. Make solvent with organic solvent, alkali is made acid binding agent, and POCl3 and dimethylamine hydrochloride stirring reaction at-25～0 DEG C 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; Vacuum filtration is removed sediment, obtains filtrate; After secondary temperature elevation, vacuum filtration is removed sediment and is obtained 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid again again. This method preparation technology is simple, and cost is low, is easy to suitability for industrialized production, and market application foreground is wide.
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,TMSDMA N dimethylamine base)-1,6,3,8,2, the preparation method of 7-octahydro dioxadiazole diphosphinic acid, belongs to the system of novel halogen-free flame-retardant agentStandby field.
Background technology
Along with the development of Macromolecular materials industry, the synthetic materials such as plastics, rubber, fiber, more and more widely for spinningKnit, the field such as building, chemical industry, military affairs and traffic. Meanwhile, due to the inflammability of macromolecular material, flame-retarded technology is subject toTo 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. WithThe fire-retardant high polymer processing technique of additive flame retardant is simple, and the fire retardant that can meet instructions for use is wide in variety, but needs to solveThe series of problems such as the dispersiveness of fire retardant, compatibility, interface property; The tool of anti-flammability that adopts reactive flame retardant to obtainHave relative permanent, on also less by the impact of the physical property of flame-retardant polymer. Halogenated flame retardant, particularly bromine are fire-retardantAgent is a based flame retardant of applying the earliest, but produces more smog and poisonous corrosive gas in the time of burning, can affect peopleImmunity and regenerative system, cause secondary pollution, even has strong carcinogenesis. The developed countries such as current America and Europe have started to prohibitOnly use Halogen and heavy metal fire retardant. In recent years, response type phosphorus, phosphorus-nitrogen coordinated fire-retardant agent enjoy favor, due to its flame retarding efficiencyHeight, does not produce poisonous or corrosive gas in fire-retardant process, the growing amount of cigarette is also less, therefore extremely induces one in flame retardant areaGaze at.
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 twoDegree of functionality (being applicable to doing the chain extender of polymerisation), has 4 P-N structures in ring shaped molecule structure, flame retarding efficiency is high, charring rateHigh; The preparation method of this ring-type phosphorus nitrogen synergistic halogen-free flame retardants is simple, easy to operate, and preparation feedback mild condition, to equipment requirementLow, production cost is low.
The object of the invention is to be achieved through the following technical solutions.
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-eightHydrogen dioxadiazole diphosphinic acid (ODDP); The structure of this compound is as follows:
2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or pale yellow colored solidBody, product yield is 35%～50%, and fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, moleculeIn structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, and 7.33% and 32%, be applicable to doing macromolecular materialFire retardant or chain extender.
A preparation method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, concrete steps are as follows:
Step 1, under inert gas shielding condition, make solvent with organic solvent, alkali is made acid binding agent, POCl3 and twoMethylamine hydrochloride (mol ratio is 1:1～2:1) stirring reaction at-25～0 DEG C of temperature generates to no longer including white depositions; SoRear disengaging low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2～5 hours at ambient temperature; In obtaining containingBetween the mixture of product 1;
Step 2, by the mixture that contains intermediate product 1 of step 1 gained, vacuum filtration is removed sediment, obtains filtrate;
Step 3, under inert gas shielding condition, in the filtrate of step 2 gained, add monoethanolamine, still tie up with alkaliAcid agent; Under ice-water bath, react to system color and no longer deepen; Then be warming up to 30～50 DEG C, and react to body at this temperatureSystem no longer includes sediment and generates;
Step 4, vacuum filtration are removed the sediment in step 3, will after purified filtrate processing, obtain 2,7-bis-(N, N-Dimethylamino)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Described inert gas is the one in argon gas, helium, nitrogen, preferentially selects nitrogen;
Described acid binding agent is the one in triethylamine, tri-n-butylamine, NaOH, potassium hydroxide, calcium hydroxide, preferentialSelect triethylamine;
Described organic solvent is benzene,toluene,xylene, carrene, ether, benzinum, ethyl acetate, acetone, fourthOne in ketone, preferentially selects carrene;
Described purification process process is: first use benzinum wash filtrate 1-4 time, then vacuum filtration is removed insoluble matter,After decompression distillation vacuum drying, obtain product 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole secondary phosphineAcid.
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, TMSDMA 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 to containAmount, comprises 4 P-N structures in molecular structure, 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, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid cyclic 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 is strong, shows 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-bis-Methylamino)-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, cityField has a extensive future.
Brief description of the drawings
Fig. 1 is 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2, the infrared spectrum of 7-octahydro dioxadiazole diphosphinic acidFigure;
Fig. 2 is 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid1H-NMR spectrumFigure;
Fig. 3 is 2,7-bis-(N, TMSDMA N dimethylamine base-1, the mass spectrogram of 6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Detailed description of the invention
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-eightHydrogen dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or pale yellow colored solidBody, product yield is 35%～50%, and fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, moleculeIn structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, and 7.33% and 32%, be suitable for doing macromolecular materialFire retardant or chain extender. As shown in Figure 1, Figure 2, Figure 3 shows; Fig. 1 represents, 3264cm-1Place is N-H stretching vibration absworption peak;2930～2894cm-1Place is-CH2-CH2Stretching vibration absworption peak; 1394cm-1For the stretching vibration absworption peak of-P-NH;1213.99cm-1，1310.41cm-1，1004cm-1Be respectively P=O ,-N-C and-characteristic absorption peak of P-N. Fig. 2 shows,The acromion of 2.55ppm Chu You – NH-, splitting swarming in two groups of couplings at 3.3ppm and 3.5ppm place is to be connected with nitrogen-atoms on ringCH2-On the characteristic peak of two H; Splitting swarming in two groups of couplings at 4.1ppm and 4.3ppm place is the CH being connected with O on ring2-OnThe characteristic peak of two H; Near double spike 2.65ppm is-N-(CH3)2In H. Due to the impact of molecule circulus,Make two H on identical C atom produce multiple coupling and split point, and appear in different displacements, but H in symmetrical structureAppear in same displacement, therefore1On HNMR, only show the H of 7 different displacements, and the ratio of peak area is 1:1:1:1:6:1. Fig. 3Show 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,Deterministic adduct molecule formula is C8H22P2N4O4。
N is being housed2In the reactor of protective device, thermometer, feeder, add 0.1mol POCl3 and 0.1mol bis-Methylamine hydrochloride adds 100ml carrene to make solvent simultaneously, by 0.15mol triethylamine as in feeder, in magnetic agitationUnder, triethylamine is slowly added drop-wise in reactor, make this system bathe in environment and react 1 hour at-5 DEG C of cryosels, then at room temperature barUnder part, react 4 hours, vacuum filtration is removed triethylamine hydrochloride sediment, obtains filtrate; Then by 0.1mol monoethanolamine, 100ml bis-Chloromethanes, 0.15mol triethylamine, is placed in the reactor that N2 protective device, thermometer, feeder are housed again, and at magneticUnder power stirring action, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions 1 hourAfter, product is shifted out, vacuum filtration is removed triethylamine hydrochloride sediment, uses 400ml benzinum wash filtrate 2 times, then vacuumSuction filtration is removed insoluble matter, by filtrate decompression distillation, obtains white solid, obtains product 2,7-bis-(N, TMSDMA N dimethylamine after vacuum dryingBase)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 40.6%, thermal weight loss test decomposition mechanism place temperatureDegree is 198.14 DEG C, and carbon yield is 20.12%.
Embodiment 2
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-eightHydrogen dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or pale yellow colored solidBody, product yield is 35%～50%, and fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, moleculeIn structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, and 7.33% and 32% is suitable for doing macromolecular materialFire retardant or chain extender.
Being equipped with in the reactor of argon protective device, thermometer, feeder, add 0.15mol POCl3 and0.1mol dimethylamine hydrochloride adds 150ml toluene to make solvent simultaneously, by 0.25mol triethylamine as in feeder, at magnetic forceUnder stirring, triethylamine is slowly added drop-wise in reactor, makes this system bathe in environment and react 1 hour at-5 DEG C of cryosels, then in chamberUnder temperature condition, react 4 hours, vacuum filtration is removed triethylamine hydrochloride sediment, obtains filtrate; Then 0.1mol monoethanolamine, 150mlCarrene, 0.25mol triethylamine is again placed at N is housed2In the reactor of protective device, thermometer, feeder, and at magneticUnder power stirring action, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions 1 hourAfter, product is shifted out, vacuum filtration is removed triethylamine hydrochloride sediment, uses 600ml benzinum wash filtrate 2 times, then vacuumSuction filtration is removed insoluble matter, by filtrate decompression distillation, obtains white solid, obtains product 2,7-bis-(N, TMSDMA N dimethylamine after vacuum dryingBase)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 46.7%, thermal weight loss test decomposition mechanism place temperatureDegree is 198.14 DEG C, and carbon yield is 20.12%.
Embodiment 3
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-eightHydrogen dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or pale yellow colored solidBody, product yield is 35%～50%, and fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, moleculeIn structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, and 7.33% and 32% is suitable for doing macromolecular materialFire retardant or chain extender.
N is being housed2In the reactor of protective device, thermometer, feeder, add 0.6mol POCl3 and 0.4mol bis-Methylamine hydrochloride adds 300ml ethyl acetate to make solvent simultaneously, by 0.9mol triethylamine as in feeder, in magnetic agitationUnder, triethylamine is slowly added drop-wise in reactor, make this system bathe in environment and react 1 hour at-5 DEG C of cryosels, then at room temperature barUnder part, react 4 hours, vacuum filtration is removed triethylamine hydrochloride sediment, obtains filtrate; Then by 0.6mol monoethanolamine, 200ml secondAcetoacetic ester, 1.0mol triethylamine, is again placed at N is housed2In the reactor of protective device, thermometer, feeder, and at magnetic forceUnder stirring action, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions 1 hourAfter, product is shifted out, vacuum filtration is removed triethylamine hydrochloride sediment, uses 900ml benzinum wash filtrate 2 times, then vacuumSuction filtration is removed insoluble matter, by filtrate decompression distillation, obtains white solid, obtains product 2,7-bis-(N, TMSDMA N dimethylamine after vacuum dryingBase)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 45.3%, thermal weight loss test decomposition mechanism place temperatureDegree is 198.14 DEG C, and carbon yield is 20.12%.
Embodiment 4
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-eightHydrogen dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or pale yellow colored solidBody, product yield is 35%～50%, and fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, moleculeIn structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, and 7.33% and 32% is suitable for doing macromolecular materialFire retardant or chain extender.
Being equipped with in the reactor of argon protective device, thermometer, feeder, add 0.6mol POCl3 and 0.4molDimethylamine hydrochloride adds 300ml carrene to make solvent simultaneously, and 0.5mol NaOH is slowly added under magnetic agitationIn reactor, make this system bathe in environment and react 1 hour at-8 DEG C of cryosels, then react at ambient temperature vacuum filtration 4 hoursRemove insoluble matter, obtain filtrate; Then by 0.6mol monoethanolamine, 200ml carrene, 0.9mol triethylamine is again placed at and is equipped withIn the reactor of argon protective device, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 DEG C of reaction 1Hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions after 1 hour, product is shifted out, vacuum filtration is removed hydrochloric acid threeEthamine sediment, uses 1000ml benzinum wash filtrate 2 times, and then vacuum filtration is removed insoluble matter, by filtrate decompression distillation,White solid, obtains product 2,7-bis-(N, TMSDMA N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole secondary phosphine after vacuum dryingAcid, yield is 38.2%, and thermal weight loss test decomposition mechanism place temperature is 198.14 DEG C, 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 inert gas shielding condition, make solvent with organic solvent, alkali is made acid binding agent, mol ratio is 1:1～2:1POCl3 and dimethylamine hydrochloride at-25～0 DEG C of temperature stirring reaction to no longer include white depositions generate; Then de-From low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2～5 hours at ambient temperature; In the middle of obtaining containing, produceThe mixture of thing 1;
Step 2, by the mixture that contains intermediate product 1 of step 1 gained, vacuum filtration is removed sediment, obtains filtrate;
Step 3, under inert gas shielding condition, in the filtrate of step 2 gained, add monoethanolamine, still tie up acid with alkaliAgent; Under ice-water bath, react to system color and no longer deepen; Then be warming up to 30～50 DEG C, and react to system at this temperatureNo longer including sediment generates;
Step 4, vacuum filtration are removed the sediment in step 3, will after purified filtrate processing, obtain ODDP;
The structural formula of described ODDP is
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: describedInert gas is the one 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: instituteThe inert gas of stating 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: describedAcid binding agent is the one in triethylamine, tri-n-butylamine, NaOH, 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: instituteThe acid binding agent of stating 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: describedOrganic solvent is the one in benzene,toluene,xylene, carrene, ether, benzinum, 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: instituteThe organic solvent of stating is carrene.
8. 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 pureChanging processing procedure is: first use benzinum wash filtrate 1-4 time, then vacuum filtration is removed insoluble matter, decompression distillation vacuumAfter dry, obtain product ODDP.
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 preparationTechnological principle is shown below:
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| CN115850712B (en) * | 2022-11-30 | 2024-05-24 | 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 electric equipment and 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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