CN105037433B - The preparation method of fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite - Google Patents
The preparation method of fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite, the compound structure is shown below：
Description
Technical field
The present invention relates to a kind of preparation method of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite, specifically
It is related to one kind 2, the preparation method of 6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound, the compound is adapted to use
Make the fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
Organic high molecular polymer material, there is excellent mechanical performance and chemical stability, thus extensively should
Its application is restricted for fields such as automobile, building and electronic apparatus, but due to inflammability.Universal method is to make
It is carried out with halogen compounds it is fire-retardant, it is poisonous due to being released when it burns although the flame retardant effect of halogen compounds is preferable
Cause the dispute of environmental issue with corrosive gas.Therefore, develop novel halogen-free flame-retardant agent, change flame retardant products structure,
Improve product specification, promote the construction of flame retardant regulation and standard, turn into the hair of following fire retardant and flame retarded polymeric material industry
Open up direction.Organic phosphine fire retardant have the characteristics that it is environment-friendly and efficient and be recognized be can replace halogenated flame retardant important product
Kind.It is while imparting material good anti-flammability, also with advantages such as low cigarette, low toxicities.In recent years, to organic phosphine fire retardant
Research have become fire retardant research and development field heat subject.
The invention discloses a kind of preparation method of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite.
K.J.Coskran and J.G.Verkade discloses in nineteen sixty-five prepares three hydroxyls with tris hydroxymethyl phosphine and Trimethyl phosphite reaction
The method of methylphosphine caged phosphite ester, ultimate yield only have 35%, without the value of industrialization；The present invention is with equimolar
Tris hydroxymethyl phosphine is raw material with phosphorus trichloride, and one-step method prepares the compound, and reactivity is high, and technique is simple, easy to operate, into
This is low, is readily converted to industrialized production.The compounds of this invention is cage structure, and the organic phosphine key (C-P keys) in molecule is to changing
Compound brings stability, and caged ring also contributes to the stability of compound, and its stability is good, phosphorus content is high, flame retardant effect is excellent
It is good, be beneficial to material processing, have preferable DEVELOPMENT PROSPECT.
The content of the invention
It is an object of the invention to propose a kind of system of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite
Preparation Method, this method are single step reaction, and technique is simple, and equipment investment is few, is easy to large-scale production, can be overcome of the prior art
Deficiency.Its technical scheme is as follows：
This 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 phosphorus trichloride are sufficiently mixed uniformly below nonreactive 0 DEG C of temperature, are warming up to 5 DEG C
Start obvious releasing hydrogen chloride, be warming up to 20 DEG C of insulation 1h, then be warming up to 60-80 DEG C of reaction 3-6h, produced to without hydrogen chloride, then
Vacuum drains hydrogen chloride, purified processing, obtains product tris hydroxymethyl phosphine caged phosphite ester.
This 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, is cooled to less than 0 DEG C, is added dropwise and the equimolar phosphorus trichloride of tris hydroxymethyl phosphine,
It is sufficiently mixed at nonreactive temperature uniformly, is then warming up to 5 DEG C and starts obvious releasing hydrogen chloride, be warming up to 20 DEG C of insulation 1h,
60-80 DEG C of reaction 3-6h is warming up to again, is produced to without hydrogen chloride, is evaporated under reduced pressure and removes organic solvent, purified processing, obtain product
Tris hydroxymethyl phosphine young laying ducks in cage.
Organic solvent as described above is acetonitrile, benzene, tetrahydrofuran or chloroform, and its dosage volume milliliter number is trihydroxy methyl
2-5 times of phosphine quality grams.
Purification process as described above is adds the frozen water of theoretical 2-4 times of volume milliliter number of product quality grams, under stirring,
5% sodium carbonate liquor is added dropwise, makes reaction system pH=7, product solid is dispersed in water, and filtering, frozen water is eluted, drained, very
Sky is dried.
Organic phosphine fire retardant tris hydroxymethyl phosphine caged phosphite ester of the present invention is white solid, product yield 76.3%-
92.5%, fusing point：72 ± 2 DEG C, decomposition temperature：259±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 of the organic phosphine fire retardant tris hydroxymethyl phosphine caged phosphite ester is such as
Shown in following formula：
Compared with prior art, the beneficial effects of the present invention are：
1. organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite phosphorus amount of the present invention is up to 40.8%, fire-retardant effect
Can be high, the organic phosphine key (P-C keys) in its molecule brings stability, cage structure and hexa-atomic phosphine ring structure symmetry to compound
It is good, the stability of compound is also contributed, product is stable, and decomposition temperature is high, and good with the compatibility of high polymer material, has
Fine processing characteristics.
2. the nitrogenated flame retardants such as organic phosphine fire retardant tris hydroxymethyl phosphine caged phosphite ester of the present invention and MCA compounding has preferably
Synergy, also good dilatancy, fire proofing production cost can be effectively reduced, there is good application prospect.
3. the preparation technology of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite of the present invention is single step reaction,
Using phosphorus trichloride as raw material, phosphorus trichloride reactivity is high, and technique is simple, easy to operate, and equipment investment is few, is easy to scale and turns
Change and produce.
Brief description of the drawings
In order to further illustrate that the structure of product and performance spy provide drawings described below.
1st, the infrared spectrogram of tris hydroxymethyl phosphine caged phosphite ester, Figure of description Fig. 1 is referred to；
Fig. 1 shows, in 2896cm-1Locate as the stretching vibration peak of methylene c h bond；1415cm-1Locate as methylene c h bond
Flexural vibrations peak；1197cm-1And 1146cm-1Locate as the stretching vibration peak of C-O keys；989cm-1Locate as the stretching vibration of P-O keys
Peak；874cm-1Locate as the stretching vibration peak of C-P keys.
2nd, the nuclear magnetic spectrum figure of tris hydroxymethyl phosphine caged phosphite ester, refers to Figure of description Fig. 2；
Fig. 2 shows that deuterated dimethyl sulfoxide makees solvent, is the H peaks of methylene at δ 3.75-3.98；It is deuterated two at δ 2.50
The H peaks of first sulfoxide solvent.
3rd, the differential thermal figure of tris hydroxymethyl phosphine caged phosphite ester, Figure of description Fig. 3 is referred to；
Fig. 3 shows that temperature is 259 DEG C and starts weightlessness；During weight-loss ratio 50%, temperature is 512 DEG C；To 800 DEG C of final temperature
When still have 39% residue, illustrate that product has preferable heat endurance.
Specific embodiment
Technical scheme is described further below in conjunction with 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, adds 30ml acetonitriles, the hydroxyls of 12.40g (0.1mol) three
Methylphosphine, less than 0 DEG C is cooled to, stirs lower dropwise addition 13.73g (0.1mol) phosphorus trichloride, it is sufficiently mixed uniformly, be warming up to
5 DEG C, hydrogen chloride releasing is begun with, is warming up to 20 DEG C of insulation 1h, then is warming up to 80 DEG C of insulation reaction 3h, treats that no hydrogen chloride is released,
It is evaporated under reduced pressure and removes acetonitrile (recovery uses), adds 40ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, makes reactant
It is pH=7, product solid is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, is obtained white
Color solid tris hydroxymethyl phosphine caged phosphite ester, yield 92.5%, fusing point：72 ± 2 DEG C, decomposition temperature：259±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, adds 40ml benzene, the hydroxyl first of 12.40g (0.1mol) three
Base phosphine, less than 0 DEG C is cooled to, stirs lower dropwise addition 13.73g (0.1mol) phosphorus trichloride, it is sufficiently mixed uniformly, be warming up to 5
DEG C, hydrogen chloride releasing is begun with, is warming up to 20 DEG C of insulation 1h, then 75 DEG C of insulation reaction 3h are warming up to, treat that no hydrogen chloride is released, subtract
Benzene (recovery uses) is distilled off in pressure, adds 45ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, makes reaction system pH
=7, product solid is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, is obtained white solid
Body tris hydroxymethyl phosphine caged phosphite ester, yield 91.7%, fusing point：72 ± 2 DEG C, decomposition temperature：259±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, adds 50ml tetrahydrofurans, 12.40g (0.1mol)
Tris hydroxymethyl phosphine, less than 0 DEG C is cooled to, stirs lower dropwise addition 13.73g (0.1mol) phosphorus trichloride, it is sufficiently mixed uniformly, rise
Temperature begins with hydrogen chloride releasing to 5 DEG C, is warming up to 20 DEG C of insulation 1h, then is warming up to 65 DEG C of insulation reaction 4h, treats that no hydrogen chloride is put
Go out, be evaporated under reduced pressure and remove tetrahydrofuran (recovery uses), add 35ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise,
Make reaction system pH=7, product solid is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum
Dry, obtain white solid tris hydroxymethyl phosphine caged phosphite ester, yield 89.6%, fusing point：72 ± 2 DEG C, decomposition temperature：259
±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, adds 60ml chloroforms, the hydroxyls of 12.40g (0.1mol) three
Methylphosphine, less than 0 DEG C is cooled to, stirs lower dropwise addition 13.73g (0.1mol) phosphorus trichloride, it is sufficiently mixed uniformly, be warming up to
5 DEG C, hydrogen chloride releasing is begun with, is warming up to 20 DEG C of insulation 1h, then is warming up to 60 DEG C of insulation reaction 5h, treats that no hydrogen chloride is released,
It is evaporated under reduced pressure and removes chloroform (recovery uses), adds 50ml frozen water, under stirring, 5% sodium carbonate liquor is added dropwise, makes reactant
It is pH=7, product solid is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, is obtained white
Color solid tris hydroxymethyl phosphine caged phosphite ester, yield 88.4%, fusing point：72 ± 2 DEG C, decomposition temperature：259±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, adds 12.40g (0.1mol) tris hydroxymethyl phosphine, it is cold
But to less than 0 DEG C, lower dropwise addition 13.73g (0.1mol) phosphorus trichloride is stirred, it is sufficiently mixed uniformly, is warming up to 5 DEG C, start
There is hydrogen chloride releasing, be warming up to 20 DEG C of insulation 1h, then be warming up to 80 DEG C of insulation reaction 4h, treat that no hydrogen chloride is released, then vacuum makes
Hydrogen chloride drains, and adds 55ml 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 is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, obtains white solid tris hydroxymethyl phosphine cage
Shape phosphite ester, yield 80.9%, fusing point：72 ± 2 DEG C, decomposition temperature：259±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, adds 12.40g (0.1mol) tris hydroxymethyl phosphine, it is cold
But to less than 0 DEG C, lower dropwise addition 13.73g (0.1mol) phosphorus trichloride is stirred, it is sufficiently mixed uniformly, is warming up to 5 DEG C, start
There is hydrogen chloride releasing, be warming up to 20 DEG C of insulation 1h, then be warming up to 60 DEG C of insulation reaction 6h, treat that no hydrogen chloride is released, then vacuum makes
Hydrogen chloride drains, 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 is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, obtains white solid tris hydroxymethyl phosphine cage
Shape phosphite ester, yield 76.3%, fusing point：72 ± 2 DEG C, decomposition temperature：259±5℃.
Table 1 prepares embodiment main technologic parameters
The product tris hydroxymethyl phosphine caged phosphite ester of above-mentioned preparation is also applied in polyester PBT by inventor.Ginseng
According to：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limited oxygen index of test sample product.Added in PBT
The product of different proportion, or after product and MCA are compounded in different proportions, then be added in different proportions in PBT,
At 225 DEG C, extruded with extruder, a length of 15cm, a diameter of 3mm batten is made, and its fire resistance is tested, surveyed
The LOI results obtained are as shown in table 2 and table 3：
Fire-retardant data of the tris hydroxymethyl phosphine caged phosphite ester of table 2 in PBT
| 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 |
| 30 | 35 | Do not drip | Into charcoal |
As shown in Table 2, when the addition when tris hydroxymethyl phosphine caged phosphite ester in PBT is 20%, limited oxygen index
It is worth for 29%, has reached fire retardant rank, and it is fine without melting drippage, carbon-forming performance.
The fire-retardant data of the tris hydroxymethyl phosphine caged phosphite ester of table 3 and MCA in PBT
| Addition % | LOI% | Molten drop situation | Into charcoal | Expansion status |
| 13.3 product+6.7MCA | 29 | Do not drip | Into charcoal | Expansion |
| 20 product+10MCA | 35 | Do not drip | Into charcoal | Expansion |
| 8 product+12MCA | 26 | Drippage | Not into charcoal | Do not expand |
| 10 product+10MCA | 29 | Do not drip | Into charcoal | Expansion |
| 15 product+15MCA | 32 | Do not drip | Into charcoal | Expansion |
As shown in Table 3, tris hydroxymethyl phosphine caged phosphite ester has preferable synergy with MCA compoundings, also has good
Dilatancy, when product addition accounts for 2/3, and total addition level is 30%, limited oxygen index is up to 35%, also well into charcoal
Performance, and MCA price is very cheap, and the production cost of fire proofing can be greatly lowered.Thus it can be seen that the hydroxyl of product three
No matter methylphosphine caged phosphite ester is single use, or is compounded with MCA, there is preferable flame retardant effect to PBT material.
Claims (3)
- A kind of 1. preparation method of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite, it is characterised in that the party 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 phosphorus trichloride are sufficiently mixed uniformly below 0 DEG C, 5 DEG C is warming up to and starts obvious releasing chlorination Hydrogen, 20 DEG C of insulation 1h are warming up to, then are warming up to 60-80 DEG C of insulation reaction 3-6h, produced to without hydrogen chloride, then vacuum makes hydrogen chloride Drain, add the frozen water of product Theoretical Mass 2-4 times of volume milliliter number of grams, under stirring, 5% sodium carbonate liquor is added dropwise, makes Reaction system pH=7, product solid are dispersed in water, and filtering, frozen water is eluted, drains, is dried in vacuo, and obtains product tris hydroxymethyl phosphine Caged phosphite ester, the structure of the compound are shown below：
- A kind of 2. preparation method of organic phosphine fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite, it is characterised in that the party 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, is cooled to less than 0 DEG C, identical with tris hydroxymethyl phosphine mole of phosphorus trichloride is added dropwise, fills Divide and be well mixed, be then warming up to 5 DEG C and start obvious releasing hydrogen chloride, be warming up to 20 DEG C and be incubated 1h, then be warming up to 60-80 DEG C instead 3-6h is answered, is produced to without hydrogen chloride, is evaporated under reduced pressure and removes organic solvent, adds product Theoretical Mass 2-4 times of volume milliliter of grams Several frozen water, under stirring, 5% sodium carbonate liquor being added dropwise, make reaction system pH=7, product solid is dispersed in water, filtering, Frozen water is eluted, drains, is dried in vacuo, and obtains product tris hydroxymethyl phosphine caged phosphite ester, and the structure of the compound is shown below：
- 3. the preparation method of tris hydroxymethyl phosphine caged bi-ester of phosphite as claimed in claim 2, it is characterised in that：It is described to have Solvent is acetonitrile, benzene, tetrahydrofuran or chloroform, and its dosage volume milliliter number is 2-5 times of tris hydroxymethyl phosphine quality grams.
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