CN105037437B - The preparation method of the miscellaneous young laying ducks in cage compound of 4 thio phosphono of fire retardant - Google Patents
The preparation method of the miscellaneous young laying ducks in cage compound of 4 thio phosphono of fire retardant Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the miscellaneous young laying ducks in cage compound of 4 thio phosphono of fire retardant, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-, specifically
It is related to a kind of 1- oxygen -4- thio -2, the preparation method of 6, the 7- trioxas-phosphabicyclo of Isosorbide-5-Nitrae-two [2.2.2] octane compound should
Compound is suitable as the fire retardant of the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin, polyolefin.
Background technology
In today of scientific and technical fast development, high-molecular organic material is widely applied, while its inflammability
Bring great fire safety evaluating hidden danger.In order to change the inflammability of high-molecular organic material, resistance is added in high polymer material
Combustion agent carries out flame-retardant modified be particularly important to high polymer material.Flame-retardant modified research is carried out to high polymer material in recent years
With application also in accelerated development, the consumption of fire retardant is also growing day by day, and it has been developed into is only second to be plasticized in plastic additive
The second largest auxiliary agent of agent.Traditional halogenated flame retardant has obtained widely should very much due to advantages such as its function admirable, moderate costs
With, but it can release poisonous and corrosive gas in burning and cause secondary injury to human body, some fire-retardant methods with European Union
The appearance of rule, the application of traditional halogenated flame retardant are limited by very large.Phosphorus flame retardant particularly Organic phosphonate system fire retardant,
Have the advantages that the high and low cigarette of fire resistance, low toxicity, non-corrosiveness gas produce, occupied in halogen-free flame retardants increasingly heavier
The status wanted.
The invention discloses a kind of preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-.Should
Method is single step reaction, simple to operate, easy to control.Product of the present invention is cage structure, with phosphorus content is high, stability is good, resistance
The advantages that fuel efficiency energy height and good material compatibility.Organic phosphine key (C-P keys) in molecule can bring stability, sulphur to compound
The introducing of element makes flame-retarded efficiency higher.Therefore, product of the present invention has extraordinary development prospect.
The content of the invention
It is an object of the invention to propose a kind of system of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-
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：
Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add etc. rub
Your trihydroxy methyl phosphine sulfide and triphenyl phosphate, adds the catalyst relative to trihydroxy methyl phosphine sulfide quality 1%-2%,
120-160 DEG C is warming up to, reacts 10-14h, stops reaction, is evaporated under reduced pressure and removes phenol, is cooled to less than 20 DEG C, adds product
The frozen water of 2-3 times of volume milliliter number of Theoretical Mass grams, 30min is stirred, is dispersed in water faint yellow solid product, filtered,
Frozen water is eluted, drains, is dried in vacuo, and obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-.
This method can also be：
Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add it is organic
Solvent, equimolar trihydroxy methyl phosphine sulfide and triphenyl phosphate, under stirring, add relative to trihydroxy methyl phosphine sulfide quality
1%-2% catalyst, 120-160 DEG C is warming up to, reacts 8-12h, be evaporated under reduced pressure and remove organic solvent and phenol, be cooled to 20
Below DEG C, the frozen water of product Theoretical Mass 2-3 times of volume milliliter number of grams is added, stirs 30min, makes faint yellow solid product point
Dissipate in water, filter, frozen water is eluted, drains, is dried in vacuo, and obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-.
This method can also be：
Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add etc. rub
Your trihydroxy methyl phosphine sulfide and triphenyl phosphate, adds the catalyst relative to trihydroxy methyl phosphine sulfide quality 1%-2%,
120-160 DEG C is warming up to, reacts 10-14h, stops reaction, adds the water of product Theoretical Mass 1 times of volume milliliter number of grams, liquid
Water flowing steam under face, steam distillation is carried out, after phenol all steams, stirring is cooled to less than 10 DEG C, makes faint yellow solid
Product is separated out, and filtering, frozen water is eluted, drains, is dried in vacuo, and obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-.
This method can also be：
Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add it is organic
Solvent, equimolar trihydroxy methyl phosphine sulfide and triphenyl phosphate, under stirring, add relative to trihydroxy methyl phosphine sulfide quality
1%-2% catalyst, 120-160 DEG C is warming up to, reacts 8-12h, be evaporated under reduced pressure and remove organic solvent, add product theory matter
The water of 1 times of volume milliliter number of grams is measured, water flowing steam under liquid level, carries out steam distillation, after phenol all steams, stirring is cold
But to less than 10 DEG C, separate out faint yellow solid product, filtering, frozen water is eluted, drains, is dried in vacuo, and obtains the thio phosphines of product 4-
The miscellaneous young laying ducks in cage of acyl.
Organic solvent as described above is methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene, its
Dosage volume milliliter number is 4-8 times of trihydroxy methyl phosphine sulfide quality grams.
Catalyst as described above is sodium methoxide, triethylamine, pyridine, dimethylamino pyridine or sodium hydroxide.
The miscellaneous young laying ducks in cage of the thio phosphonos of organic phosphine fire retardant 4- of the present invention is faint yellow solid, and product yield is
81.9%-93.8%, fusing point：66 ± 2 DEG C, decomposition temperature：257 ± 5 DEG C, it is suitable as polyester, polyurethane, epoxy resin, no
The fire retardant of the materials such as saturated resin, polyolefin, the preparation technology of the miscellaneous young laying ducks in cage of the thio phosphonos of organic phosphine fire retardant 4-
Principle is shown below：
Compared with prior art, the beneficial effects of the present invention are：
1. the miscellaneous young laying ducks in cage compound phosphorus content of the thio phosphonos of organic phosphine fire retardant 4- of the present invention is up to 31%, sulfur content
Reach 16%, total effectively ignition-proof element content is up to 47%, and it contains cage ring structure, and symmetry is good, and stability is good, decomposition temperature
Height, and it is good with the compatibility of high polymer material, and processing characteristics is excellent.
2. the raw material trihydroxy methyl sulphur that the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4- of the present invention uses
Change inherently a kind of excellent response type organic phosphine fire retardant of phosphine, reacted with triphenyl phosphate, introduce more ester structures again, simultaneously
The content of phosphorus is improved again, and phosphorus sulphur dual element cooperative flame retardant efficiency is high.
3. caused benzene in the preparation technology of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4- of the present invention
Phenol can be recycled all, have good environmental benefit and economic benefit.
4. the preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4- of the present invention is single step reaction,
Technique is simple, and equipment investment is few, easy to operate, and cost is low, is easy to scale conversion and production.
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 the miscellaneous young laying ducks in cage of the thio phosphonos of 4-, refers to Figure of description Fig. 1；
Fig. 1 shows, in 2966cm-1Locate as the stretching vibration peak of methylene c h bond；1482cm-1Locate as methylene c h bond
Flexural vibrations peak；1264cm-1Locate as the stretching vibration peak of P=O double bonds；1170cm-1And 1145cm-1Locate as the flexible of C-O keys
Vibration peak；1011cm-1Locate as the stretching vibration peak of P-O keys；875cm-1Locate as the stretching vibration peak of C-P keys；806cm-1Locate as P
The stretching vibration peak of=S double bonds.
2nd, the nuclear magnetic spectrum figure of the miscellaneous young laying ducks in cage of the thio phosphonos of 4-, refers to Figure of description Fig. 2；
Fig. 2 shows that deuterated dimethyl sulfoxide makees solvent, is the H peaks of methylene at δ 4.73-5.02；It is deuterated two at δ 2.50
The H peaks of first sulfoxide solvent.
3rd, the differential thermal figure of the miscellaneous young laying ducks in cage of the thio phosphonos of 4-, refers to Figure of description Fig. 3；
Fig. 3 shows that temperature is 257 DEG C and starts weightlessness；During weight-loss ratio 50%, temperature is 488 DEG C；To 800 DEG C of final temperature
When still have 31% 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, efficient backflow device 100ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 15.60g (0.1mol) trihydroxy methyls phosphine sulfide, 32.63g (0.1mol) triphenyl phosphates and 0.30g pyrroles
Pyridine catalyst, heating stirring are simultaneously continually fed into nitrogen, are warming up to 120 DEG C of insulation reaction 14h, stop reaction, add 20ml water, liquid
Water flowing steam under face, steam distillation is carried out, after phenol all steams, stirring is cooled to 0 DEG C, analyses faint yellow solid product
Go out, filter, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, obtains the miscellaneous caged phosphoric acid of the thio phosphonos of product 4-
Ester, yield 83.2%, fusing point：66 ± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 2 equipped with agitator, thermometer, efficient backflow device 100ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 15.60g (0.1mol) trihydroxy methyls phosphine sulfide, 32.63g (0.1mol) triphenyl phosphates and 0.18g first
Alcohol sodium catalyst, heating stirring are simultaneously continually fed into nitrogen, are warming up to 160 DEG C of insulation reaction 10h, stop reaction, add 20ml water,
Water flowing steam under liquid level, steam distillation is carried out, after phenol all steams, stirring is cooled to 0 DEG C, makes faint yellow solid product
Separate out, filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, obtains the miscellaneous caged phosphoric acid of the thio phosphonos of product 4-
Ester, yield 86.5%, fusing point：66 ± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 3 equipped with agitator, thermometer, efficient backflow device 100ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 15.60g (0.1mol) trihydroxy methyls phosphine sulfide, 32.63g (0.1mol) triphenyl phosphates and 0.26g hydrogen
Sodium oxide catalyst, heating stirring are simultaneously continually fed into nitrogen, are warming up to 150 DEG C of insulation reaction 12h, stop reaction, are evaporated under reduced pressure
Phenol (recovery uses) is eliminated, less than 20 DEG C is cooled to, adds 50ml frozen water, stir 30min, disperse faint yellow solid product
Yu Shuizhong, filtering, filter cake are eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, obtain the miscellaneous caged phosphorus of the thio phosphonos of product 4-
Acid esters, yield 81.9%, fusing point：66 ± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 4 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 110ml ethylene glycol diethyl ethers, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g (0.1mol)
Triphenyl phosphate.Under stirring, 0.20g Triethylamine catalysts are added, heats and is continually fed into nitrogen, it is anti-to be warming up to 120 DEG C of insulations
12h is answered, stops reaction, vacuum distillation eliminates ethylene glycol diethyl ether and phenol (recovery uses), is cooled to less than 20 DEG C, adds
45ml frozen water, 30min is stirred, is dispersed in water faint yellow solid product, filtered, filter cake is eluted with 10ml frozen water, and compacting is taken out
It is dry, filter cake vacuum drying, obtain the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 88.4%, fusing point：66 ± 2 DEG C, decompose temperature
Degree：257±5℃.
Embodiment 5 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 90ml dimethylbenzene, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g (0.1mol) tricresyl phosphate
Phenyl ester.Under stirring, 0.24g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 140 DEG C of insulation reaction 9h, stop
Only react, vacuum distillation eliminates dimethylbenzene and phenol (recovery uses), is cooled to less than 20 DEG C, adds 40ml frozen water, stirring
30min, faint yellow solid product is dispersed in water, filtered, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum is done
It is dry, obtain the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 90.1%, fusing point：66 ± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 6 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 70ml chlorobenzenes, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g (0.1mol) phosphoric acid triphen
Ester.Under stirring, 0.16g pyridine catalysts are added, heats and is continually fed into nitrogen, be warming up to 130 DEG C of insulation reaction 10h, stopped
Reaction, vacuum distillation eliminate chlorobenzene and phenol (recovery uses), are cooled to less than 20 DEG C, add 50ml frozen water, stir 30min,
Faint yellow solid product is dispersed in water, is filtered, filter cake is eluted with 10ml frozen water, and compacting is drained, and filter cake vacuum drying, must be produced
The miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 90.5%, fusing point：66 ± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 7 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 100ml diethylene glycol dimethyl ethers, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g
(0.1mol) triphenyl phosphate.Under stirring, 0.28g sodium hydroxide catalysts are added, heats and is continually fed into nitrogen, be warming up to
160 DEG C of insulation reaction 8h, stop reaction, and vacuum distillation eliminates diethylene glycol dimethyl ether and phenol (recovery uses), is cooled to 20
Below DEG C, 40ml frozen water is added, 30min is stirred, is dispersed in water faint yellow solid product, is filtered, filter cake 10ml frozen water
Elution, compacting are drained, and filter cake vacuum drying, obtain the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 91.9%, fusing point：66
± 2 DEG C, decomposition temperature：257±5℃.
Embodiment 8 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 80ml chlorobenzenes, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g (0.1mol) phosphoric acid triphen
Ester.Under stirring, 0.30g dimethylamino pyridine catalyst is added, heats and is continually fed into nitrogen, be warming up to 130 DEG C of insulation reactions
10h, it is evaporated under reduced pressure and removes organic solvent, add 20ml water, water flowing steam under liquid level, carry out steam distillation, treats phenol whole
After steaming, stirring is cooled to less than 10 DEG C, separates out faint yellow solid product, and filtering, filter cake is eluted with 10ml frozen water, and compacting is taken out
It is dry, filter cake vacuum drying, obtain the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 92.4%, fusing point：66 ± 2 DEG C, decompose temperature
Degree：257±5℃.
Embodiment 9 equipped with agitator, thermometer, efficient backflow device 250ml four-hole boiling flasks in, with nitrogen catch up with to the greatest extent
Air in bottle, add 100ml methyl phenyl ethers anisoles, 15.60g (0.1mol) trihydroxy methyl phosphine sulfides and 32.63g (0.1mol) tricresyl phosphate
Phenyl ester.Under stirring, 0.24g sodium methoxide catalysts are added, heats and is continually fed into nitrogen, be warming up to 150 DEG C of insulation reaction 8h, subtract
Pressure is distilled off organic solvent, adds 20ml water, water flowing steam under liquid level, carries out steam distillation, after phenol all steams,
Stirring is cooled to less than 10 DEG C, separates out faint yellow solid product, and filtering, filter cake is eluted with 10ml frozen water, and compacting is drained, filter cake
Vacuum drying, obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, yield 93.8%, fusing point：66 ± 2 DEG C, decomposition temperature：257
±5℃。
Table 1 prepares embodiment main technologic parameters
The miscellaneous young laying ducks in cage of the thio phosphonos of product 4- 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：
The fire-retardant data that the miscellaneous young laying ducks in cage of the table thio phosphonos of 2 product 4- is used in PBT
| Addition % | LOI% | Drippage situation | Into charcoal |
| 0 | 21 | Fast drippage | Not into charcoal |
| 10 | 24 | Slow drippage | Not into charcoal |
| 20 | 30 | Do not drip | Into charcoal |
| 30 | 34 | Do not drip | Into charcoal |
As shown in Table 2, when the addition when the miscellaneous young laying ducks in cage of the thio phosphonos of product 4- in PBT is 20%, limit oxygen
Exponential quantity is 30%, has reached fire retardant rank, and fine without melting drippage, carbon-forming performance.
The miscellaneous young laying ducks in cage of the thio phosphonos of product 4- of table 3 and MCA are compounded for the fire-retardant data in PBT
As shown in Table 3, the miscellaneous young laying ducks in cage of the thio phosphonos of product 4- has preferable synergy with MCA compoundings, also very
Good dilatancy, when product mixes with MCA equal proportions, and total addition level for 25% when, limited oxygen index is up to 34%, also very
Good carbon-forming performance；MCA price is very cheap, and the production cost of fire proofing can be greatly lowered.Thus it can be seen that production
No matter the miscellaneous young laying ducks in cage of the thio phosphonos of product 4- is single use, or is compounded with MCA, has to PBT material preferably fire-retardant
Effect.
Claims (6)
- A kind of 1. preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-, it is characterised in that the party Method is：Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add it is equimolar Trihydroxy methyl phosphine sulfide and triphenyl phosphate, the catalyst relative to trihydroxy methyl phosphine sulfide quality 1%-2% is added, heated up To 120-160 DEG C, 10-14h is reacted, stops reaction, is evaporated under reduced pressure and removes phenol, is cooled to less than 20 DEG C, it is theoretical to add product The frozen water of 2-3 times of volume milliliter number of quality grams, 30min is stirred, is dispersed in water faint yellow solid product, filtered, frozen water Elute, drain, be dried in vacuo, obtain the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, the structure of the compound is shown below：
- A kind of 2. preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-, it is characterised in that the party Method is：Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add organic solvent, Equimolar trihydroxy methyl phosphine sulfide and triphenyl phosphate, under stirring, add relative to trihydroxy methyl phosphine sulfide quality 1%- 2% catalyst, is warming up to 120-160 DEG C, reacts 8-12h, is evaporated under reduced pressure and removes organic solvent and phenol, be cooled to 20 DEG C with Under, the frozen water of product Theoretical Mass 2-3 times of volume milliliter number of grams is added, 30min is stirred, is scattered in faint yellow solid product In water, filtering, frozen water is eluted, drains, is dried in vacuo, and obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, the structure of the compound It is shown below：
- A kind of 3. preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-, it is characterised in that the party Method is：Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add it is equimolar Trihydroxy methyl phosphine sulfide and triphenyl phosphate, the catalyst relative to trihydroxy methyl phosphine sulfide quality 1%-2% is added, heated up To 120-160 DEG C, 10-14h is reacted, stopping is reacted, the water of addition product Theoretical Mass 1 times of volume milliliter number of grams, under liquid level Water flowing steam, steam distillation is carried out, after phenol all steams, stirring is cooled to less than 10 DEG C, makes faint yellow solid product Separate out, filtering, frozen water is eluted, drains, is dried in vacuo, and obtains the miscellaneous young laying ducks in cage of the thio phosphonos of product 4-, the structure of the compound It is shown below：
- A kind of 4. preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of organic phosphine fire retardant 4-, it is characterised in that the party Method is：Equipped with agitator, thermometer, efficient backflow condensing unit reactor in, under nitrogen protection, add organic solvent, Equimolar trihydroxy methyl phosphine sulfide and triphenyl phosphate, under stirring, add relative to trihydroxy methyl phosphine sulfide quality 1%- 2% catalyst, 120-160 DEG C is warming up to, reacts 8-12h, be evaporated under reduced pressure and remove organic solvent, add product Theoretical Mass gram The water of 1 times of volume milliliter number of number, water flowing steam under liquid level, steam distillation is carried out, after phenol all steams, stirring is cooled to Less than 10 DEG C, separate out faint yellow solid product, filtering, frozen water is eluted, drains, is dried in vacuo, and it is miscellaneous to obtain the thio phosphonos of product 4- Young laying ducks in cage, the structure of the compound are shown below：
- 5. the preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of the 4- as described in claim 2 or 4, it is characterised in that：Institute It is methyl phenyl ethers anisole, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene or chlorobenzene to state organic solvent, its dosage volume milliliter number For 4-8 times of trihydroxy methyl phosphine sulfide quality grams.
- 6. the preparation method of the miscellaneous young laying ducks in cage compound of the thio phosphonos of 4-, its feature exist as described in claim 1,2,3 or 4 In：The catalyst is sodium methoxide, triethylamine, pyridine, dimethylamino pyridine or sodium hydroxide.
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