CN106478727B - Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof - Google Patents

Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof Download PDF

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CN106478727B
CN106478727B CN201610850680.5A CN201610850680A CN106478727B CN 106478727 B CN106478727 B CN 106478727B CN 201610850680 A CN201610850680 A CN 201610850680A CN 106478727 B CN106478727 B CN 106478727B
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trioxa
phosphabicyclo
sulfenyl
phenylmethoxy
silicic acid
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CN106478727A (en
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孙艳艳
贺婧
杨海军
王令端
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Suzhou University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574Esters of oxyacids of phosphorus
    • C07F9/65746Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34928Salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/548Silicon-containing compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

Abstract

The present invention relates to a kind of double -1- sulfenyl phosphas -2,6 of fire retardant Phenylmethoxy silicic acid, and 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound and preparation method thereof, the structure of the compound is shown below:

Description

Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl esters chemical combination Object and preparation method thereof
Technical field
The present invention relates to a kind of silicon, phosphorus, double -1- sulfenyl phospha -2 of sulphur element synergistic fire retardant Phenylmethoxy silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl -4- methyl compound and preparation method thereof, which is suitable as polyester, poly- ammonia The fire-retardant carbon forming agent of ester, epoxy resin, unsaturated-resin etc..
Background technique
With the improvement of people ' s living standards and the enhancing of fire safety consciousness, fire retardant industry are developed rapidly, Demand especially to new and effective nontoxic fire retardant more has urgency.Phosphorus flame retardant is studied before more.Due to silicon systems Fire retardant has good thermal stability, effective anti-melt drippage and smoke suppressing, and becomes current low smoke and non-toxic fire proofing One of hot spot of exploitation.Element sulphur can change the decomposition course of high molecular material, play fire retardation, and and P elements in condensed phase There is good synergetic, is ignition-proof element newly developed.If silicon, phosphorus and sulphur are designed into same compound structure, allow It plays cooperative flame retardant synergistic effect, can greatly improve its flame-retarded efficiency.
The invention discloses with phenyltrimethoxysila,e, 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane is that primary raw material prepares the double -1- sulfenyl phosphas-of silicon, phosphorus, sulphur element synergistic fire retardant Phenylmethoxy silicic acid The method of 2,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl -4- methyl compound.Fire retardant of the present invention has multiple fire retardant mechanism, Wherein P elements can generate polyphosphoric acid film in burning, block invasion of the air to combustible;Element silicon can generate fine and close silicon Layer of charcoal has preferable anti-molten drop effect;Element sulphur can change the decomposition course of material, fire-retardant in condensed phase.The collaboration resistance of three elements Combustion can generate excellent flame retardant effect.Fire retardant efficiency of the present invention is high, good at charcoal effect, has a wide range of application, and has well Development prospect.
Summary of the invention
It is an object of the present invention to propose the double -1- of a kind of silicon, phosphorus, sulphur cooperative flame retardant carbon forming agent Phenylmethoxy silicic acid Sulfenyl phospha -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound, flame-retarded efficiency is high, can overcome the prior art In deficiency.
For achieving the above object, present invention employs following technical solutions:
Double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound, It is characterized in that, the structure of the compound is shown below:
Another object of the present invention is to propose the double -1- sulfenyls of a kind of silicon, phosphorus, sulphur synergistic fire retardant Phenylmethoxy silicic acid Phospha -2,6, the preparation method of 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl compound, simple process, equipment investment It is few, it is easy to large-scale production, and raw material is cheap and easy to get, low in cost, this method are as follows:
Equipped with blender, thermometer and fractionating device reactor in, nitrogen catches up with most air, 25 DEG C at a temperature of, One times mole of phenyltrimethoxysila,e and 2-4 times mole of 1- sulfenyl phospha -4- methylol -2,6 is added, 7- trioxa is double Ring [2.2.2] octane, is warming up to 120 DEG C~160 DEG C, and solid gradually dissolves, finally be in colourless transparent liquid, fractionation reaction 4h~ 9h keeps micro-vacuum (- 0.02Mpa) in reactor during the reaction, in order to which the methanol of generation is separated in time, point After distillating quantitative methanol, 40 DEG C or so are cooled to, adds the methanol of product theory quality 1~5 times of volume ml of grams Or ethyl alcohol is dispersed with stirring 1h, filters, and it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid, 7- tri- Oxabicyclo [2.2.2] octyl -4- methyl esters.
This method may be used also are as follows:
Equipped with blender, thermometer and fractionating device reactor in, nitrogen catches up with most air, 25 DEG C at a temperature of, 1 times mole of phenyltrimethoxysila,e, 2-4 times mole of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo is added [2.2.2] octane and relative to 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane quality grams 2~ The organic solvent of 6 times of volumes ml, is warming up to 80 DEG C of -160 DEG C of reflux, and fractionation reaction 5h~10h isolates generation in time Methanol;After separating quantitative methanol, it is cooled to 25 DEG C, filters, then with 1~2 times of volume ml of product theory quality grams Methanol or ethanol washing filter, dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid, tri- oxygen of 7- Miscellaneous bicyclic [2.2.2] octyl -4- methyl esters.
Organic solvent described in method two as above is acetonitrile, dioxane or diethylene glycol dimethyl ether.
Double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid of the invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- first Ester is white solid powder, and product yield is 90.2%~93.1%, and fusing point is 169 ± 2 DEG C, and decomposition temperature is 322 ± 5 DEG C. Its fire-retardant carbon forming agent for being suitable as the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin.The Phenylmethoxy silicic acid The preparation process principle of double -1- sulfenyl phosphas -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters is shown below:
Compared with prior art, the beneficial effects of the present invention are:
1. double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- first Ester is siliceous, three kinds of phosphorus, sulphur ignition-proof elements, and cooperative flame retardant efficiency is high, and element silicon has into charcoal effect, can effectively prevent material by Heat fusing drips and the second-time burning of generation, and P elements can generate polyphosphoric acid film in burning, blocks combustible and air, sulphur member Element can change the decomposition course of high molecular material, and condensed phase is fire-retardant.
2. double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- first Connect on silicon atom in ester structure there are two phenyl, there is C-Si key, is organosilicon structures, organosilicon structures stability is good, water-fast Property it is strong, when burning, is more easily generated fine and close charcoal-silicon layer, and flame retardant effect is more excellent.
3. double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- first Ester symmetry is good, physical and chemical performance is stablized, and decomposition temperature is high, and the phenyl ring contained has the polytropism of electronic structure, with height Molecular material compatibility is good, is conducive to the mechanical property for improving material, adapts to the high temperature process of engineering material.
4. double -1- sulfenyl the phosphas -2,6 of Phenylmethoxy silicic acid of the present invention, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- first The preparation process of ester is simple, does not introduce impurity without adding catalyst, and equipment is simple, low in cost, is suitable for large-scale production, has Good application and development prospect.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the double -1- sulfenyl phosphas -2,6 of Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters Infrared spectrogram;Fig. 1 shows 993cm-1Place is the stretching vibration peak of P-O key, 2843cm-1-2968cm-1Place is methyl and methylene The stretching vibration peak of the C-H of base, 3069cm-1Place is the stretching vibration peak of C-H on phenyl ring, 696cm-1The feature that place is P=S is inhaled Receive peak, 1021cm-1Place is the stretching vibration peak of C-O key, 811cm-1Place is the stretching vibration peak of Si-C key, 1407cm-1、 1542cm-1And 1689cm-1Place is the characteristic absorption peak of phenyl ring skeleton, 1103cm-1Place is the characteristic absorption peak of Si-O-C key.
Fig. 2 is the double -1- sulfenyl phosphas -2,6 of Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters Nuclear magnetic spectrogram;Fig. 2 shows to make solvent with deuterated dimethyl sulfoxide, is hydrogen peak on phenyl ring at chemical shift δ 7.41-7.64;δ It is C (CH at 4.64-4.682O hydrogen peak on the methylene being connected on) with oxygen;It is CCH at δ 3.64-3.702The Asia that OSi is connected with oxygen Hydrogen peak on methyl is CH at δ 3.23-3.283The upper methyl hydrogen peak O;It is the proton of solvent deuterated dimethyl sulfoxide exchange at δ 2.51 Peak.
Fig. 3 is the double -1- sulfenyl phosphas -2,6 of Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters Thermal multigraph;When Fig. 3 shows that temperature is 318 DEG C, product starts to decompose;When temperature is 322 or so, decomposition rate reach to peak value, and And with strong heat release;After temperature reaches 330 DEG C, the decomposition first stage terminates substantially, and it is 64% that residue at this time, which remains rate,;When After temperature is increased to 500 DEG C, the layer of charcoal of generation starts slowly to decompose, and to after 700 DEG C, residue, which remains rate, still 44%.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen Air, 25 DEG C at a temperature of, be added 21.56g (0.11mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and 9.91g (0.05mol) phenyltrimethoxysila,e, are warming up to 150 DEG C, and solid gradually dissolves, and are finally in nothing Color transparency liquid, fractionation reaction 6h, keeps micro-vacuum (- 0.02Mpa) in reactor, during the reaction in order to the first of generation Alcohol is separated in time, after fractionating out quantitative methanol, is cooled to 40 DEG C or so, adds 60mL ethyl alcohol and is dispersed with stirring 1h, It filters, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 92.7%.
Embodiment 2 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen Air, 25 DEG C at a temperature of, be added 39.23g (0.20mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and 9.91g (0.05mol) phenyltrimethoxysila,e, are warming up to 120 DEG C, and solid gradually dissolves, and are finally in nothing Color transparency liquid, fractionation reaction 9h, keeps micro-vacuum (- 0.02Mpa) in reactor, during the reaction in order to the first of generation Alcohol is separated in time, after fractionating out quantitative methanol, is cooled to 40 DEG C or so, adds 130mL methanol and is dispersed with stirring 1h, It filters, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 91.9%.
Embodiment 3 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, catch up in most bottle by nitrogen Air, 25 DEG C at a temperature of, be added 19.61g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and 9.91g (0.05mol) phenyltrimethoxysila,e, are warming up to 160 DEG C, and solid gradually dissolves, and are finally in nothing Color transparency liquid, fractionation reaction 4h, keeps micro-vacuum (- 0.02Mpa) in reactor, during the reaction in order to the first of generation Alcohol is separated in time, after fractionating out quantitative methanol, is cooled to 40 DEG C or so, adds 50mL ethyl alcohol and is dispersed with stirring 1h, It filters, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 90.7%.
For embodiment 4 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, nitrogen catches up with most sky Gas, 25 DEG C at a temperature of, be added 24.51g (0.125mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and 9.91g (0.05mol) phenyltrimethoxysila,e, are warming up to 140 DEG C, and solid gradually dissolves, and are finally in nothing Color transparency liquid, fractionation reaction 7h, keeps micro-vacuum (- 0.02Mpa) in reactor, during the reaction in order to the first of generation Alcohol is separated in time, after fractionating out quantitative methanol, is cooled to 40 DEG C or so, adds 100mL methanol and is dispersed with stirring 1h, It filters, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 93.1%.
For embodiment 5 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, nitrogen catches up with most sky Gas, 25 DEG C at a temperature of, be added 29.42g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane and 9.91g (0.05mol) phenyltrimethoxysila,e, are warming up to 130 DEG C, and solid gradually dissolves, and are finally in nothing Color transparency liquid, fractionation reaction 8h, keeps micro-vacuum (- 0.02Mpa) in reactor, during the reaction in order to the first of generation Alcohol is separated in time, after fractionating out quantitative methanol, is cooled to 40 DEG C or so, adds 120mL ethyl alcohol and is dispersed with stirring 1h, It filters, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 92.3%.
For embodiment 6 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, nitrogen catches up with most sky Gas, 25 DEG C at a temperature of, be added 29.42g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane, 9.91g (0.05mol) phenyltrimethoxysila,e and 80mL diethylene glycol dimethyl ether are warming up to 160 DEG C and return Stream, fractionation reaction 5h, isolates the methanol of generation in time;After separating quantitative methanol, 25 DEG C are cooled to, is filtered, then use 50mL Methanol washing, filters, dry, obtains the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters, yield 92.3%.
For embodiment 7 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, nitrogen catches up with most sky Gas, 25 DEG C at a temperature of, be added 19.61g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane, 9.91g (0.05mol) phenyltrimethoxysila,e and 120mL dioxane are warming up to 100 DEG C of reflux, point Reaction 8h is evaporated, isolates the methanol of generation in time;After separating quantitative methanol, 25 DEG C are cooled to, is filtered, then washed with 40mL ethyl alcohol It washs, filters, it is dry, obtain the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters, yield 90.2%.
For embodiment 8 in tetra- mouthfuls of reaction flasks of 250ml equipped with blender, thermometer and fractionating device, nitrogen catches up with most sky Gas, 25 DEG C at a temperature of, be added 39.32g (0.20mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane, 9.91g (0.05mol) phenyltrimethoxysila,e and 100mL acetonitrile are warming up to 80 DEG C of reflux, fractionation reaction 10h isolates the methanol of generation in time;After separating quantitative methanol, it is cooled to 25 DEG C, filters, then uses 80mL ethanol washing, pumping Filter, it is dry, the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid are obtained, 7- trioxa-l-phosphabicyclo [2.2.2] is pungent Base -4- methyl esters, yield 91.3%.
Inventor is by the double -1- sulfenyl phosphas -2,6 of the Phenylmethoxy silicic acid of above-mentioned preparation, 7- trioxa-l-phosphabicyclo [2.2.2] octyl -4- methyl esters (PSMDSPE) individually or with melamine polyphosphate (MPP) carries out composite usage in fire-retardant poly- In mutual-phenenyl two acid bromide two alcohol ester (PBT).Reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " is surveyed The limit oxygen index (LOI) of sample.Take PSMDSPE be uniformly mixed or take in varing proportions with PBT PSMDSPE, MPP and PBT with Different proportion is uniformly mixed, and is squeezed out with extruder, and diameter is made and is the batten of 3mm, and is surveyed to its fire-retardant melt-dropping property Examination, lists part test result as shown in table 1~2:
The flame retardant property data of the independent flame-retardant PBT of 1 PSMDSPE of table
Sequence Additive amount/% LOI/% Molten drop situation At charcoal situation
1 0 21 Drippage Not at charcoal
2 10 23 Slow drippage At charcoal
3 20 28 It does not drip At charcoal
4 30 31 It does not drip At charcoal
The flame retardant property data of 2 PSMDSPE of table and MPP compositional flame-retardant PBT
According to table 1 as can be seen that when additive amount of the product PSMDSPE individually in PBT reaches 10%, it can delay to hinder Fire drippage of the PBT in burning;After additive amount reaches 20%, the LOI of PBT belongs to fire retardant rank up to 28%.It can according to table 2 To find out, when PSMDSPE is compounded with MPP, the addition total amount in PBT is 20%, PSMDSPE and MPP mass ratio is 1: 1 When, the LOI of flame-retardant PBT is up to 34%, and melting can be effectively prevent to drip rapidly at charcoal.It can be seen that PSMDSPE is to PBT material Material have well it is fire-retardant at charcoal effect, compound with MPP be used for PBT in equally show synergetic.

Claims (1)

1. double -1- sulfenyl the phosphas -2,6 of a kind of silicon, phosphorus, sulphur element cooperative flame retardant carbon forming agent Phenylmethoxy silicic acid, tri- oxygen of 7- The preparation method of miscellaneous bicyclic [2.2.2] octyl -4- methyl esters, which is characterized in that this method are as follows:
Equipped with blender, thermometer and fractionating device reactor in, nitrogen catches up with most air, 25 DEG C at a temperature of, be added 1 Times mole phenyltrimethoxysila,e and 2-4 times mole of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2] octane, is warming up to 120 DEG C -160 DEG C, and solid gradually melts, and is finally in colourless transparent liquid, and 4h-9h is reacted in fractionation, Keeping reactor pressure during the reaction is that -0.02Mpa fractionates out in order to which the methanol of generation is separated in time After quantitative methanol, 40 DEG C or so are cooled to, adds the methanol or second of 1~5 times of volume ml of product theory quality grams Alcohol is dispersed with stirring 1h, filters, dry, obtains the double -1- sulfenyl phosphas -2,6 of white solid powder Phenylmethoxy silicic acid, 7- trioxa Bicyclic [2.2.2] octyl -4- methyl esters, the structure of the compound are shown below:
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