CN104926874B - The oxygen of fire retardant 4 is with double phosphorus bi-ester of phosphite of cage and preparation method thereof - Google Patents
The oxygen of fire retardant 4 is with double phosphorus bi-ester of phosphite of cage and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of oxygen of fire retardant 4 with double phosphorus bi-ester of phosphite of cage and preparation method thereof, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of organic phosphine fire retardant 4- oxygen with double phosphorus bi-ester of phosphite of cage and preparation method thereof, specifically
It is related to a kind of 4- oxygen -2,6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound and preparation method thereof, the chemical combination
Thing is suitable as the fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
In recent years, organic synthesis high polymer material is widely used in the every field of national economy, by the fire of its initiation
Calamity causes serious threat to the security of the lives and property of people, and fire retardant is added into these materials come to reduce fire be to have
The means of effect, thus promote the fast development of fire retardant.The current consumption maximum of China is halogenated flame retardant, although it has aobvious
Ground advantage is write, but the toxic gas and flue dust that are produced in burning are there is also very big potential safety hazard, with European Union member countries pair
The promulgation of some flame retardant regulations, the application of halogenated flame retardant is further restricted.Therefore, novel halogen-free flame-retardant agent
Research and development seem even more important, and phosphorus flame retardant with its low toxicity, low cigarette, decomposition temperature is high the advantages of increasingly by the weight of people
Depending on.Wherein Organic phosphonate system fire retardant is more favored by people, and the based flame retardant contains C-P keys, chemical stability enhancing, with resistance
The advantages of high and low cigarette of fuel efficiency energy, machinery and physical property nontoxic, on material influence small, therefore, to Organic phosphonate system fire retardant
Research is as one of most promising direction.
The invention discloses a kind of organic phosphine fire retardant 4- oxygen with double phosphorus bi-ester of phosphite of cage and preparation method thereof, sheet
Invention compound is that the organic phosphine key (C-P keys) in cage structure, molecule brings stability to compound, and cage ring structure is to chemical combination
The stability of thing is also contributed, and its stability is good, phosphorus content is high, flame retardant effect is excellent, be beneficial to material processing, has and preferably opens
Hair prospect.
The content of the invention
An object of the present invention is to propose a kind of organic phosphine fire retardant 4- oxygen with the double phosphorus bi-ester of phosphite of cage, its
Flame-retarded efficiency is high, and good processability can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
A kind of organic phosphine fire retardant 4- oxygen is with the double phosphorus bi-ester of phosphite of cage, it is characterised in that the structure of the compound
It is shown below：
Another object of the present invention is to propose a kind of organic phosphine fire retardant 4- oxygen with the double phosphorus bi-ester of phosphite of cage
Preparation method, its technique is simple, equipment investment is few, it is easy to large-scale production, and raw material is cheap and easy to get, with low cost, this method
For：
In the reactor equipped with efficient fractionating device, under nitrogen protection, equimolar trihydroxy methyl phosphine oxide is added
And tris phosphite, under stirring, a certain amount of catalyst is added, 100-160 DEG C of reaction 5-10h is warming up to, controls capital temperature
Spend to separate generation alcohol boiling temperature, stop reaction when the alcohol fractionated out reaches theoretical amount, be cooled to less than 20 DEG C, pass through
Purification process, obtains product 4- oxygen with the double phosphorus phosphite esters of cage.
This method can also be：
In the reactor equipped with efficient fractionating device, under nitrogen protection, organic solvent, equimolar three hydroxyls first are added
Base phosphine oxide and tris phosphite, under stirring, add a certain amount of catalyst, are warming up to 100-160 DEG C of reaction 5-8h, control
Column top temperature by separate generation alcohol boiling temperature, stop reaction, then vacuum distillation when the alcohol fractionated out reaches theoretical amount
Organic solvent is removed, less than 20 DEG C are cooled to, purified processing obtains product 4- oxygen with the double phosphorus phosphite esters of cage.
Tris phosphite as described above is Trimethyl phosphite or triethyl phosphite.
Organic solvent as described above is dioxane, methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, two
Toluene or chlorobenzene, its consumption volume milliliter number are 3-8 times of trihydroxy methyl phosphine oxide quality grams.
A certain amount of catalyst as described above is sodium methoxide, triethylamine, pyridine or sodium hydroxide, and its consumption is trihydroxy methyl
The 1%-2% of phosphine oxide quality.
Purification process as described above stirs to add the frozen water of 2-3 times of volume milliliter number of product Theoretical Mass grams
30min, is dispersed in water white particulate solid product, and filtering, frozen water is eluted, drains, is dried in vacuo.
Organic phosphine fire retardant 4- oxygen of the present invention is white solid with the double phosphorus phosphite esters of cage, and product yield is 90.7%-
96.2%, fusing point：82 ± 2 DEG C, decomposition temperature：273 ± 5 DEG C, it is suitable as polyester, polyurethane, epoxy resin, unsaturated tree
The fire retardant of the materials such as fat, polyolefin, the organic phosphine fire retardant 4- oxygen is as follows with the preparation technology principle of the double phosphorus phosphite esters of cage
Shown in formula：
Compared with prior art, the beneficial effects of the present invention are：
1. organic phosphine fire retardant 4- oxygen of the present invention is up to 36.9%, fire-retardant effect with the double phosphorus bi-ester of phosphite phosphorus contents of cage
Can be high, it contains cage ring structure, and symmetry is good, and stability is good, and decomposition temperature is high, and good with the compatibility of high polymer material,
Product is not separated out.
2. the raw material trihydroxy methyl oxidation that organic phosphine fire retardant 4- oxygen of the present invention is used with the double phosphorus bi-ester of phosphite of cage
Inherently a kind of excellent response type organic phosphine fire retardant of phosphine, with phosphite reactions, introduces many ester structures, while carry again again
The high content of phosphorus, makes product add antioxidant capacity again while obtaining preferable anti-flammability.
3. the alcohol produced in preparation technology of the organic phosphine fire retardant 4- oxygen of the present invention with the double phosphorus bi-ester of phosphite of cage can
All recycle, with good environmental benefit and economic benefit.
4. organic phosphine fire retardant 4- oxygen of the present invention is simple with the preparation technology and equipment of the double phosphorus bi-ester of phosphite of cage, just
It is with low cost in operation, it is easy to which that scale is converted and produced.
Brief description of the drawings
In order to which the structure and performance spy that further illustrate product provide drawings described below.
1st, 4- oxygen refers to Figure of description Fig. 1 with the infrared spectrogram of the double phosphorus phosphite esters of cage；
Fig. 1 shows, in 2924cm-1Locate as the stretching vibration peak of methylene c h bond；1425cm-1Locate as methylene c h bond
Flexural vibrations peak；1316cm-1Locate as the stretching vibration peak of P=0 double bonds；1176cm-1And 1135cm-1Locate as the flexible of C-0 keys
Vibration peak；1022cm-1Locate as the stretching vibration peak of P-0 keys；897cm-1Locate as the stretching vibration peak of C-P keys.
2nd, 4- oxygen refers to Figure of description Fig. 2 with the nuclear magnetic spectrum figure of the double phosphorus phosphite esters of cage；
Fig. 2 shows that deuterated dimethyl sulfoxide makees the H peaks for methylene at solvent, δ 4.15-4.40；It is deuterated two at δ 2.50
The H peaks of first sulfoxide solvent.
3rd, 4- oxygen refers to Figure of description Fig. 3 with the differential thermal figure of the double phosphorus phosphite esters of cage；
Fig. 3 shows that temperature is 273 DEG C and starts weightlessness；During weight-loss ratio 50%, temperature is 504 DEG C；To 800 DEG C of final temperature
When still have 37% residue, illustrate that product has preferable heat endurance.
Specific embodiment
Technical scheme is described further below in conjunction with embodiment.
Embodiment 1 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) Trimethyl phosphite.Under stirring,
0.28g Triethylamine catalysts are added, heats and is continually fed into nitrogen, 110 DEG C of insulation reaction 9h are warming up to, column top temperature is controlled
Not higher than 65 DEG C, the methanol (recovery is used) that reaction is produced is fractionated out, stops reaction, cooling when methanol fraction reaches theoretical amount
To less than 20 DEG C, 50ml frozen water is added, 30min is stirred, is dispersed in water white particulate solid product, is filtered, filter cake is used
10ml frozen water is eluted, and compacting is drained, filter cake vacuum drying, obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is
92.5%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 2 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) Trimethyl phosphite.Under stirring,
0.14g pyridine catalysts are added, heats and is continually fed into nitrogen, 120 DEG C of reaction 8h is warming up to, controls column top temperature not all the time
Higher than 65 DEG C, the methanol (recovery is used) that reaction is produced is fractionated out, stops reaction when methanol fraction reaches theoretical amount, is cooled to
Less than 20 DEG C, 45ml frozen water is added, 30min is stirred, is dispersed in water white particulate solid product, is filtered, filter cake 10ml
Frozen water is eluted, and compacting is drained, filter cake vacuum drying, obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is 93.3%, is melted
Point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 3 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) Trimethyl phosphite.Under stirring,
0.15g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, 130 DEG C of reaction 7h is warming up to, column top temperature is controlled all the time
Not higher than 65 DEG C, the methanol (recovery is used) that reaction is produced is fractionated out, stops reaction, cooling when methanol fraction reaches theoretical amount
To less than 20 DEG C, 40ml frozen water is added, 30min is stirred, is dispersed in water white particulate solid product, is filtered, filter cake is used
10ml frozen water is eluted, and compacting is drained, filter cake vacuum drying, obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is
94.9%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 4 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 110m1 dioxane, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) phosphorous acid
Trimethyl.Under stirrings, 0.19g Triethylamine catalysts are added, heats and is continually fed into nitrogen, be warming up to 100 DEG C of insulation reaction 7h,
Control column top temperature is not higher than 65 DEG C, the methanol (recovery is used) that reaction is produced is fractionated out, when methanol fraction reaches theoretical amount
Stop reaction, then vacuum distillation eliminates dioxane, is cooled to less than 20 DEG C, adds 35ml frozen water, stirs 30min, makes white
Granular solids product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid
Body 4- oxygen is with the double phosphorus phosphite esters of cage, and yield is 92.8%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 5 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 80ml methyl phenyl ethers anisoles, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) phosphorous acid three
Methyl esters.Under stirring, 0.22g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 150 DEG C of reaction 5h, control all the time
Column top temperature processed is not higher than 65 DEG C, fractionates out the methanol (recovery is used) that reaction is produced, stops when methanol fraction reaches theoretical amount
Only react, then vacuum distillation eliminates stupid methyl ether, is cooled to less than 20 DEG C, adds 45ml frozen water, stirs 30min, makes white particulate
Solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid 4-
Oxygen is with the double phosphorus phosphite esters of cage, and yield is 96.2%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 6 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 60ml diethylene glycol dimethyl ethers, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol)
Trimethyl phosphite.Under stirring, 0.28g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 160 DEG C instead
5h is answered, controls column top temperature to be not higher than 65 DEG C all the time, the methanol (recovery is used) that reaction is produced is fractionated out, when methanol fraction reaches
Stop reaction during theoretical amount, then vacuum distillation eliminates diethylene glycol dimethyl ether, is cooled to less than 20 DEG C, adds 40ml frozen water, stirs
30min is mixed, white particulate solid product is dispersed in water, filtered, filter cake is eluted with 10ml frozen water, compacting is drained, and filter cake is true
Sky is dried, and obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is 95.5%, fusing point：82 ± 2 DEG C, decomposition temperature：273
±5℃。
Embodiment 7 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 90ml ethylene glycol diethyl ethers, and 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) are sub-
Trimethyl phosphate.Under stirring, 0.20g pyridine catalysts are added, heats and is continually fed into nitrogen, be warming up to 120 DEG C of reaction 7h, begin
Control column top temperature is not higher than 65 DEG C eventually, the methanol (recovery is used) that reaction is produced is fractionated out, when methanol fraction reaches theoretical amount
When stop reaction, then vacuum distillation eliminates ethylene glycol diethyl ether, is cooled to less than 20 DEG C, adds 35ml frozen water, stirring 30min,
White particulate solid product is dispersed in water, is filtered, filter cake is eluted with 10ml frozen water, compacting is drained, filter cake vacuum drying is obtained
White solid 4- oxygen is with the double phosphorus phosphite esters of cage, and yield is 93.9%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 8 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 110ml toluene, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) phosphorous acid front three
Ester.Under stirring, 0.15g pyridine catalysts are added, heats and is continually fed into nitrogen, be warming up to 110 DEG C of insulation reaction 7h, control column
Top temperature is not higher than 65 DEG C, fractionates out the methanol (recovery is used) that reaction is produced, and stops when methanol fraction reaches theoretical amount anti-
Answer, then vacuum distillation eliminates toluene, is cooled to less than 20 DEG C, adds 50ml frozen water, stirs 30min, produces white particulate solid
Product are dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtain the same cage of white solid 4- oxygen
Double phosphorus phosphite esters, yield is 93.2%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 9 catches up with most bottle with nitrogen in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device
Interior air, adds 50ml dimethylbenzene, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) phosphorous acid three
Methyl esters.Under stirring, 0.20g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 140 DEG C of reaction 6h, control all the time
Column top temperature processed is not higher than 65 DEG C, fractionates out the methanol (recovery is used) that reaction is produced, stops when methanol fraction reaches theoretical amount
Only react, then vacuum distillation eliminates dimethylbenzene, is cooled to less than 20 DEG C, adds 35ml frozen water, stirs 30min, makes white particulate
Solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid 4-
Oxygen is with the double phosphorus phosphite esters of cage, and yield is 95.2%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 10 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 70ml chlorobenzenes, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 12.40g (0.1mol) phosphorous acid three
Methyl esters.Under stirring, 0.26g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 130 DEG C of reaction 6h, all the time
Control column top temperature is not higher than 65 DEG C, the methanol (recovery is used) that reaction is produced is fractionated out, when methanol fraction reaches theoretical amount
Stop reaction, then vacuum distillation eliminates chlorobenzene, is cooled to less than 20 DEG C, adds 45ml frozen water, stirs 30min, makes white particulate
Solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid 4-
Oxygen is with the double phosphorus phosphite esters of cage, and yield is 94.7%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 11 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) triethyl phosphite.Stirring
Under, 0.18g pyridine catalysts are added, heats and is continually fed into nitrogen, 120 DEG C of insulation reaction 10h are warming up to, capital temperature is controlled
Not higher than 78 DEG C of degree, fractionates out the ethanol (recovery is used) that reaction is produced, and stops reaction, drop when ethanol fraction reaches theoretical amount
Temperature adds 40ml frozen water to less than 20 DEG C, stirs 30min, is dispersed in water white particulate solid product, filters, and filter cake is used
10ml frozen water is eluted, and compacting is drained, filter cake vacuum drying, obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is
90.7%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 12 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) triethyl phosphite.Stirring
Under, 0.24g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, 140 DEG C of insulation reaction 9h, control column are warming up to
Top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, and stops when ethanol fraction reaches theoretical amount anti-
Should, less than 20 DEG C are cooled to, 45ml frozen water is added, 30min is stirred, is dispersed in water white particulate solid product, is filtered, filter
Cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is
92.3%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 13 is caught up with to the greatest extent in equipped with agitator, thermometer, the 100ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) triethyl phosphite.Stirring
Under, 0.16g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, 150 DEG C of insulation reaction 8h are warming up to, capital is controlled
Temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, stops reaction when ethanol fraction reaches theoretical amount,
Less than 20 DEG C are cooled to, 40ml frozen water is added, 30min is stirred, is dispersed in water white particulate solid product, is filtered, filter cake
Eluted with 10ml frozen water, compacting is drained, filter cake vacuum drying, obtain white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is
93.8%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 14 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 100ml dioxane, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) phosphorous
Triethylenetetraminehexaacetic acid ester.Under stirring, 0.19g Triethylamine catalysts are added, heats and is continually fed into nitrogen, be warming up to 100 DEG C of insulation reactions
8h, control column top temperature is not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theoretical amount
When stop reaction, then vacuum distillation eliminates dioxane, is cooled to less than 20 DEG C, adds 35ml frozen water, and stirring 30min makes white
Color tablets shape solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white
Solid 4- oxygen is with the double phosphorus phosphite esters of cage, and yield is 92.2%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 15 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 80ml methyl phenyl ethers anisoles, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) phosphorous acid
Triethyl.Under stirrings, 0.22g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 150 DEG C of insulation reaction 6h,
Control column top temperature is not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theoretical amount
Stop reaction, then vacuum distillation eliminates methyl phenyl ethers anisole, is cooled to less than 20 DEG C, adds 45ml frozen water, stirs 30min, makes leucoplastid
Shape solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid
4- oxygen is with the double phosphorus phosphite esters of cage, and yield is 95.8%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 16 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 60ml diethylene glycol dimethyl ethers, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g
(0.1mol) triethyl phosphite.Under stirring, 0.18g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, be warming up to
160 DEG C of insulation reaction 6h, control column top temperature is not higher than 78 DEG C, fractionates out the ethanol (recovery is used) that reaction is produced, works as ethanol
Cut stops reaction when reaching theoretical amount, then vacuum distillation eliminates diethylene glycol dimethyl ether, is cooled to less than 20 DEG C, adds 40ml
Frozen water, stirs 30min, is dispersed in water white particulate solid product, filters, and filter cake is eluted with 10ml frozen water, and compacting is drained,
Filter cake is dried in vacuo, and obtains white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is 94.6%, fusing point：82 ± 2 DEG C, decompose temperature
Degree：273±5℃.
Embodiment 17 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 90ml ethylene glycol diethyl ethers, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol)
Triethyl phosphite.Under stirring, 0.16g pyridine catalysts are added, heats and is continually fed into nitrogen, be warming up to 120 DEG C of insulations anti-
7h is answered, control column top temperature is not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theory
Stop reaction during amount, then vacuum distillation eliminates ethylene glycol diethyl ether, is cooled to less than 20 DEG C, adds 40ml frozen water, stirring
30min, is dispersed in water white particulate solid product, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum
Dry, obtain white solid 4- oxygen with the double phosphorus phosphite esters of cage, yield is 92.7%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5
℃。
Embodiment 18 is caught up with to the greatest extent in equipped with agitator, thermometer, the 150ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 50ml dimethylbenzene, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) phosphorous acid
Triethyl.Under stirrings, 0.20g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 140 DEG C of insulation reaction 6h,
Control column top temperature is not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theoretical amount
Stop reaction, then vacuum distillation eliminates dimethylbenzene, is cooled to less than 20 DEG C, adds 35ml frozen water, stirs 30min, makes leucoplastid
Shape solid product is dispersed in water, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid
4- oxygen is with the double phosphorus phosphite esters of cage, and yield is 94.0%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Embodiment 19 is caught up with to the greatest extent in equipped with agitator, thermometer, the 250ml four-hole boiling flasks of efficient fractionating device with nitrogen
Air in bottle, adds 70ml chlorobenzenes, 14.00g (0.1mol) trihydroxy methyl phosphine oxides and 16.60g (0.1mol) phosphorous acid three
Ethyl ester.Under stirrings, 0.25g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 7h,
Control column top temperature is not higher than 78 DEG C, the ethanol (recovery is used) that reaction is produced is fractionated out, when ethanol fraction reaches theoretical amount
Stop reaction, then vacuum distillation eliminates chlorobenzene, is cooled to less than 20 DEG C, adds 50ml frozen water, stirs 30min, makes white particulate
Solid product is dispersed in water, and filtering, filter cake is eluted with 10mi frozen water, and compacting is drained, filter cake vacuum drying, obtains white solid 4-
Oxygen is with the double phosphorus phosphite esters of cage, and yield is 93.4%, fusing point：82 ± 2 DEG C, decomposition temperature：273±5℃.
Table 1 prepares embodiment main technologic parameters
The product 4- oxygen of above-mentioned preparation is also applied in polyester PBT by inventor with the double phosphorus phosphite esters of cage.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 different proportions in PBT, 225
At DEG C, extruded with extruder, a length of 15cm, a diameter of 3mm batten is made, and its fire resistance is tested, measured
LOI results as shown in table 2 and table 3：
The product 4- oxygen of table 2 is with double fire-retardant data of the phosphorus phosphite ester in PBT of cage
| Addition % | LOI% | Drippage situation | Into charcoal |
| 0 | 21 | Fast drippage | Not into charcoal |
| 10 | 23 | Slow drippage | Not into charcoal |
| 20 | 28 | Do not drip | Into charcoal |
| 25 | 30 | Do not drip | Into charcoal |
As shown in Table 2, when 4- oxygen is 20% with addition of the double phosphorus phosphite esters of cage in PBT, limited oxygen index value
For 28%, fire retardant rank has been reached, and without melting drippage, carbon-forming performance is fine.
The product 4- oxygen of table 3 is with the double fire-retardant data of phosphorus phosphite ester and MCA in PBT of cage
| Addition % | LOI% | Molten drop situation | Into charcoal | Expansion status |
| 12 product+8MCA | 27 | Do not drip | Into charcoal | Expansion |
| 15 product+10MCA | 30 | Do not drip | Into charcoal | Expansion |
| 8 product+12MCA | 25 | Drippage | Not into charcoal | Do not expand |
| 10 product+10MCA | 26 | Drippage | Not into charcoal | Do not expand |
| 12.5 product+12.5MCA | 29 | Do not drip | Into charcoal | Expansion |
As shown in Table 3,4- oxygen has preferable synergy with the double phosphorus phosphite esters of cage and MCA compoundings, also has swollen well
Swollen property, optimal addition proportioning is 3: 2, when total addition level is 25%, limited oxygen index up to 30%, also have 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 product 4-
No matter oxygen is single use with the double phosphorus phosphite esters of cage, or is compounded with MCA, there is preferable flame-retarded efficiency to PBT material.
Claims (3)
1. a kind of organic phosphine fire retardant 4- oxygen is with the preparation method of the double phosphorus bi-ester of phosphite of cage, it is characterised in that this method
For：
In the reactor equipped with efficient fractionating device, under nitrogen protection, equimolar trihydroxy methyl phosphine oxide and Asia are added
Trimethyl phosphate or triethyl phosphite, under stirring, add the methanol relative to trihydroxy methyl phosphine oxide quality 1%-2%
Sodium, triethylamine, pyridine or sodium hydroxide are warming up to 100-160 DEG C of reaction 5-10h, control column top temperature to want as catalyst
The boiling temperature of generated alcohol is separated, stops reaction when the alcohol fractionated out reaches theoretical amount, is cooled to less than 20 DEG C, add product
The frozen water of 2-3 times of volume milliliter number of Theoretical Mass grams, stirs 30min, is dispersed in water white solid product, filter, ice
Water wash, drain, be dried in vacuo, obtaining product 4- oxygen with the double phosphorus phosphite esters of cage, the structure of the compound is shown below：
2. a kind of organic phosphine fire retardant 4- oxygen is with the preparation method of the double phosphorus bi-ester of phosphite of cage, it is characterised in that this method
For：
In the reactor equipped with efficient fractionating device, under nitrogen protection, organic solvent, equimolar trihydroxy methyl oxygen are added
Change phosphine and Trimethyl phosphite or triethyl phosphite, under stirring, add relative to trihydroxy methyl phosphine oxide quality 1%-2%
Sodium methoxide, triethylamine, pyridine or sodium hydroxide as catalyst, be warming up to 100-160 DEG C reaction 5-8h, control column top temperature
By to separate generation alcohol boiling temperature, when the alcohol fractionated out reach theoretical amount when stop reaction, then vacuum distillation remove it is organic
Solvent, is cooled to less than 20 DEG C, adds the frozen water of 2-3 times of volume milliliter number of product Theoretical Mass grams, stirs 30min, make white
Color solid product is dispersed in water, and filtering, frozen water is eluted, drains, is dried in vacuo, and obtains product 4- oxygen with the double phosphorus phosphite esters of cage,
The structure of the compound is shown below：
3. 4- oxygen as claimed in claim 2 is with the preparation method of the double phosphorus bi-ester of phosphite of cage, it is characterised in that：It is described organic
Solvent is dioxane, methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene or chlorobenzene, its consumption body
Product milliliter number is 3-8 times of trihydroxy methyl phosphine oxide quality grams.
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| 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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