CN105037432B - Double phosphorus young laying ducks in cage compounds of the oxygen of fire retardant 1 and preparation method thereof - Google Patents
Double phosphorus young laying ducks in cage compounds of the oxygen of fire retardant 1 and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to double phosphorus young laying ducks in cage compounds of the oxygen of a kind of fire retardant 1 and preparation method thereof, the compound structure is shown below：
Description
Technical field
The present invention relates to double phosphorus young laying ducks in cage compounds of a kind of organic phosphine fire retardant 1- oxygen and preparation method thereof, specifically relate to
And a kind of 1- oxygen -2,6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound and preparation method thereof, the compound
It is suitable as the fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
High-molecular organic material is mainly made up of carbon, two kinds of elements of hydrogen, cracking easily occurs when being heated and burns, and is applying
There is potential fire safety evaluating problem in journey.Therefore, while ensureing that macromolecular material has premium properties, design enhancing is high
The fire safety evaluating performance of molecular material is also one of important topic of material science.The lifting of material fire safety evaluating performance it is main according to
Realized by flame-retarded technology, flame-retarded technology is exactly using additive flame retardant or the introducing fire-retardant group change in macromolecular structure
The inflammability of macromolecular material, improves macromolecular material fire resistance in combustion, to slow down the burning of macromolecular material
Speed.Halogenated flame retardant flame retarding efficiency is high, heat endurance is good, great variety of goods and cost performance is high, wide in fire retardant industry at present
It is general to use, but as the promulgation of RoHS Directive causes that its range of application is restricted, this has just promoted New Phosphorus system
The development of fire retardant.Particularly Organic phosphonate system fire retardant has the advantages that low cigarette, low toxicity because of it, in safety and environmental protection requirement increasingly
Today high, the attention of people is more exposed to, the research to Organic phosphonate system fire retardant has turned into most promising direction
One of.
The invention discloses a kind of preparation method of the double phosphorus young laying ducks in cage compounds of organic phosphine fire retardant 1- oxygen.The present invention
It is that with tris hydroxymethyl phosphine as raw material, prepared by one-step method, process is simple is easy to operate；Fire retardant of the present invention, with phosphorus content it is high,
Flame-retarded efficiency is high and the advantages of good material compatibility.Therefore, product of the present invention has preferable development prospect.
The content of the invention
An object of the present invention is to propose a kind of double phosphorus young laying ducks in cage compounds of organic phosphine fire retardant 1- oxygen, its resistance
Fuel efficiency can be high, and good processability can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
The double phosphorus young laying ducks in cage compounds of a kind of organic phosphine fire retardant 1- oxygen, it is characterised in that the structure of the compound is such as
Shown in following formula：
System another object of the present invention is to propose a kind of double phosphorus young laying ducks in cage compounds of organic phosphine fire retardant 1- oxygen
Preparation Method, the method is single step reaction, and process is simple is easy to operate, and equipment investment is few, it is easy to large-scale production, and the method is：
In the reactor equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device, nitrogen protection
Under, equimolar tris hydroxymethyl phosphine and POCl3 are sufficiently mixed below 0 DEG C of nonreactive temperature uniform, it is warming up to 15 DEG C
Start substantially to release hydrogen chloride, be warming up to 30 DEG C of insulation 2h, then be warming up to 80-100 DEG C of reaction 4-7h, produced to without hydrogen chloride,
Vacuum drains hydrogen chloride again, purified treatment, obtains the double phosphorus young laying ducks in cage of product 1- oxygen.
The method can also be：
In the reactor equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device, nitrogen protection
Under, organic solvent and tris hydroxymethyl phosphine are added, less than 0 DEG C is cooled to, identical with tris hydroxymethyl phosphine mole of POCl3 is added dropwise,
It is sufficiently mixed at nonreactive temperature uniformly, is then warming up to 15 DEG C and starts substantially to release hydrogen chloride, is warming up to 30 DEG C of insulations
2h, then 80-100 DEG C of reaction 3-6h is warming up to, being produced to without hydrogen chloride, vacuum distillation removes organic solvent, and purified treatment is obtained
The double phosphorus young laying ducks in cage of product 1- oxygen.
Organic solvent as described above is dioxane, dichloroethanes, acetonitrile or propionitrile, and its consumption volume milliliter number is three
2-5 times of methylol phosphine quality grams.
Purification process as described above is to add 2-3 times of frozen water of volume milliliter number of product Theoretical Mass grams, under stirring,
5% sodium carbonate liquor is added dropwise, reaction system pH=7, product solid is dispersed in water, filters, frozen water drip washing, drain, very
Sky is dried.
The double phosphorus young laying ducks in cage of organic phosphine fire retardant 1- oxygen of the present invention are white solid, and product yield is 75.2%-
91.3%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.It is suitable as polyester, polyurethane, epoxy resin, unsaturated tree
The fire retardant of the materials such as fat, polyolefin, the preparation technology principle such as following formula of the double phosphorus young laying ducks in cage of organic phosphine fire retardant 1- oxygen
It is shown：
Compared with prior art, the beneficial effects of the present invention are：
1. the double phosphorus young laying ducks in cage compound phosphorus contents of organic phosphine fire retardant 1- oxygen of the present invention are up to 36.9%, flame-retarded efficiency
Height, it contains cage ring structure, and symmetry is good, and the organic phosphine key (C-P keys) in molecule can bring stability to compound, decompose temperature
Degree is high, and good with the compatibility of macromolecular material, and processing characteristics is excellent.
2. the nitrogenated flame retardant compounding such as the double phosphorus young laying ducks in cage compounds of organic phosphine fire retardant 1- oxygen of the present invention and MCA have compared with
Good synergy, also good dilatancy can effectively reduce fire proofing production cost, there is good application prospect.
3. the preparation method of the double phosphorus young laying ducks in cage compounds of organic phosphine fire retardant 1- oxygen of the present invention is single step reaction, and instead
Should be active high, yield is high, and process is simple is easy to operate, low cost, it is easy to which scale is converted and produced.
Brief description of the drawings
In order to the structure and performance spy that further illustrate product provide drawings described below.
1st, the infrared spectrogram of the double phosphorus young laying ducks in cage of 1- oxygen, refers to Figure of description Fig. 1；
Fig. 1 shows, in 2973cm-1It is the stretching vibration peak of methylene c h bond to locate；1455cm-1It is methylene c h bond to locate
Flexural vibrations peak；1272cm-1It is the stretching vibration peak of P=O double bonds to locate；1153cm-1And 1126cm-1Locate stretching for C-O keys
Vibration peak；1024cm-1It is the stretching vibration peak of P-O keys to locate；818cm-1It is the stretching vibration peak of C-P keys to locate.
2nd, the nuclear magnetic spectrum figure of the double phosphorus young laying ducks in cage of 1- oxygen, refers to Figure of description Fig. 2；
Fig. 2 shows, solvent is made with deuterated dimethyl sulfoxide, is the H peaks of methylene at δ 4.06-4.43；It is deuterated at δ 2.50
The H peaks of dimethylsulfoxide solvent.
Specific embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 100ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 30ml dioxane, 12.40g (0.1mol)
Tris hydroxymethyl phosphine, is cooled to less than 0 DEG C, and stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, rises
Temperature begins with hydrogen chloride releasing to 15 DEG C, is warming up to 30 DEG C of insulation 2h, then is warming up to 100 DEG C of insulation reaction 3h, treats without hydrogen chloride
Release, vacuum distillation removes dioxane (recovery is used), adds 50ml frozen water, under stirring, the sodium carbonate for being added dropwise 5% is molten
Liquid, is dispersed in water reaction system pH=7, product solid, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, and filter cake is true
Empty dry the double phosphorus young laying ducks in cage of white solid 1- oxygen, yield is 91.3%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5
℃。
Embodiment 2 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 100ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 40ml propionitrile, the hydroxyls of 12.40g (0.1mol) three
Methylphosphine, is cooled to less than 0 DEG C, and stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, is warming up to
15 DEG C, hydrogen chloride releasing is begun with, is warming up to 30 DEG C of insulation 2h, then be warming up to 95 DEG C of insulation reaction 4h, treat to be released without hydrogen chloride,
Vacuum distillation removes propionitrile (recovery is used), adds 45ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, and makes reactant
It is pH=7, product solid is dispersed in water, filtering, filter cake 10ml frozen water drip washing, compacting is drained, and filter cake is vacuum dried in vain
The double phosphorus young laying ducks in cage of color solid 1- oxygen, yield is 90.5%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 3 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 150ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 50ml dichloroethanes, 12.40g (0.1mol)
Tris hydroxymethyl phosphine, is cooled to less than 0 DEG C, and stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, rises
Temperature begins with hydrogen chloride releasing to 15 DEG C, is warming up to 30 DEG C of insulation 2h, then is warming up to 85 DEG C of insulation reaction 5h, treats without hydrogen chloride
Release, vacuum distillation removes dichloroethanes (recovery is used), adds 35ml frozen water, under stirring, the sodium carbonate for being added dropwise 5% is molten
Liquid, is dispersed in water reaction system pH=7, product solid, and filtering, filter cake 10ml frozen water drip washing, compacting is drained, and filter cake is true
Empty dry the double phosphorus young laying ducks in cage of white solid 1- oxygen, yield is 89.0%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5
℃。
Embodiment 4 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 150ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 60ml acetonitriles, the hydroxyls of 12.40g (0.1mol) three
Methylphosphine, is cooled to less than 0 DEG C, and stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, is warming up to
15 DEG C, hydrogen chloride releasing is begun with, is warming up to 30 DEG C of insulation 2h, then be warming up to 80 DEG C of insulation reaction 6h, treat to be released without hydrogen chloride,
Vacuum distillation removes acetonitrile (recovery is used), adds 40ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, and makes reactant
It is pH=7, product solid is dispersed in water, filtering, filter cake 10ml frozen water drip washing, compacting is drained, and filter cake is vacuum dried in vain
The double phosphorus young laying ducks in cage of color solid 1- oxygen, yield is 86.9%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 5 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 100ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 12.40g (0.1mol) tris hydroxymethyl phosphine, it is cold
But to less than 0 DEG C, stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, is warming up to 15 DEG C, starts
There is hydrogen chloride to release, be warming up to 30 DEG C of insulation 2h, then be warming up to 100 DEG C of insulation reaction 4h, treat to be released without hydrogen chloride, then vacuum makes
Hydrogen chloride is drained, and adds 50ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, and makes reaction system pH=7, product solid point
Dissipate in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake is vacuum dried to obtain the double phosphorus caged of white solid 1- oxygen
Phosphate, yield is 80.4%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Embodiment 6 equipped with agitator, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to hydrogen chloride inhale
In the 100ml four-hole boiling flasks of receiving apparatus, the air in most bottle is caught up with nitrogen, add 12.40g (0.1mol) tris hydroxymethyl phosphine, it is cold
But to less than 0 DEG C, stirring is lower to be added dropwise 15.33g (0.1mol) POCl3, it is sufficiently mixed uniformly, is warming up to 15 DEG C, starts
There is hydrogen chloride to release, be warming up to 30 DEG C of insulation 2h, then be warming up to 80 DEG C of insulation reaction 7h, treat to be released without hydrogen chloride, then vacuum makes
Hydrogen chloride is drained, and adds 40ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, and makes reaction system pH=7, product solid point
Dissipate in water, filter, filter cake 10ml frozen water drip washing, compacting is drained, filter cake is vacuum dried to obtain the double phosphorus caged of white solid 1- oxygen
Phosphate, yield is 75.2%, fusing point：77 ± 2 DEG C, decomposition temperature：269±5℃.
Table 1 prepares embodiment main technologic parameters
Also be applied to the double phosphorus young laying ducks in cage of the product 1- oxygen of above-mentioned preparation in polyester PBT by inventor.Reference：
GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limited oxygen index of test sample product.Added not in PBT
Product in proportion, or after product and MCA are compounded in different proportions, then be added in PBT in different proportions, with extrusion
Machine is extruded, and is made a length of 15cm, the batten of a diameter of 3mm, and its fire resistance is tested, and the LOI results for measuring are such as
Shown in table 2 and table 3：
Double fire-retardant data of the phosphorus young laying ducks in cage in PBT of the product 1- oxygen of table 2
| Addition % | LOI% | Drippage situation | Into charcoal |
| 0 | 21 | Fast drippage | Not into charcoal |
| 10 | 24 | Slow drippage | Not into charcoal |
| 20 | 29 | Do not drip | Into charcoal |
| 25 | 31 | Do not drip | Into charcoal |
As shown in Table 2, when product 1- oxygen addition of double phosphorus young laying ducks in cage in PBT is 20%, limited oxygen index
It is 29% to be worth, and has reached fire retardant rank, and is dripped without melting, and carbon-forming performance is fine.
The double fire-retardant data of phosphorus young laying ducks in cage and MCA in PBT of the product 1- oxygen of table 3
As shown in Table 3, the double phosphorus young laying ducks in cage of product 1- oxygen have preferably synergy with MCA compoundings, also well
Dilatancy, optimal addition proportioning accounts for 3/5 for product, when total addition level is 25%, limited oxygen index up to 31%, also
Good carbon-forming performance, and the price of MCA is very cheap, and the production cost of fire proofing can be greatly lowered.Can thus see
Go out no matter the double phosphorus young laying ducks in cage of product 1- oxygen are single use, or compounded with MCA, there is preferably fire-retardant to PBT material
Efficiency.
Claims (3)
1. the preparation method of the double phosphorus young laying ducks in cage compounds of a kind of organic phosphine fire retardant 1- oxygen, it is characterised in that the method is：
In the reactor equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device, under nitrogen protection,
Equimolar tris hydroxymethyl phosphine and POCl3 are sufficiently mixed uniformly below 0 DEG C, 15 DEG C are warming up to and are started substantially to release chlorine
Change hydrogen, be warming up to 30 DEG C of insulation 2h, then be warming up to 80-100 DEG C of reaction 4-7h, produced to without hydrogen chloride, then vacuum makes hydrogen chloride
Drain, add 2-3 times of frozen water of volume milliliter number of product Theoretical Mass grams, under stirring, 5% sodium carbonate liquor is added dropwise, make
Reaction system pH=7, product solid is dispersed in water, filtering, frozen water drip washing, drains, is vacuum dried, and obtains the double phosphorus cages of product 1- oxygen
Shape phosphate, the structure of the compound is shown below：
2. the preparation method of the double phosphorus young laying ducks in cage compounds of a kind of organic phosphine fire retardant 1- oxygen, it is characterised in that the method is：
In the reactor equipped with agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device, under nitrogen protection,
Organic solvent and tris hydroxymethyl phosphine are added, less than 0 DEG C is cooled to, identical with tris hydroxymethyl phosphine mole of POCl3 is added dropwise, filled
Divide well mixed, be then warming up to 15 DEG C and start substantially to release hydrogen chloride, be warming up to 30 DEG C and be incubated 2h, then be warming up to 80-100 DEG C
Reaction 3-6h, produces to without hydrogen chloride, and vacuum distillation removes organic solvent, adds 2-3 times of volume of product Theoretical Mass grams in the least
The frozen water of number is risen, under stirring, 5% sodium carbonate liquor is added dropwise, be dispersed in water reaction system pH=7, product solid, mistake
Filter, frozen water drip washing, drains, is vacuum dried, and obtains the double phosphorus young laying ducks in cage of product 1- oxygen.
3. the preparation method of the double phosphorus young laying ducks in cage compounds of 1- oxygen as claimed in claim 2, it is characterised in that：Described is organic
Solvent is dioxane, dichloroethanes, acetonitrile or propionitrile, and its consumption volume milliliter number is the 2-5 of tris hydroxymethyl phosphine quality grams
Times.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
| CN102140118A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof |
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2015
- 2015-07-07 CN CN201510404479.XA patent/CN105037432B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
| CN102140118A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| NMR PARAMETERS AND BONDING IN METAL, CHALCONIDE, BORANE AND CARBONIUM DERIVATIVES OF POLYCYCLIC PHOSPHORUS LIGANDS;D. A. ALLISON, et al.;《Phosphorus》;19731231;第2卷;257-264 * |
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Inventor after: Wang Yuxia Inventor after: Yang Keke Inventor after: Zhou Jingyi Inventor after: Wang Yanlin Inventor before: Wang Yanlin Inventor before: Yang Keke |
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Effective date of registration: 20170525 Address after: 475001 School of chemistry and chemical engineering, Henan University, Jinming District, Jinming District, Kaifeng, Henan Applicant after: Henan University Address before: 215011 science and Technology Park, Suzhou, Jiangsu province high tech Zone Binhe Road, No. 1701 Applicant before: SUZHOU KINGMAN CHEMICAL TECHNOLOGY CO., LTD. |
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