CN109824729A - Fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound and preparation method thereof - Google Patents
Fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound and preparation method thereof Download PDFInfo
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- CN109824729A CN109824729A CN201910195457.5A CN201910195457A CN109824729A CN 109824729 A CN109824729 A CN 109824729A CN 201910195457 A CN201910195457 A CN 201910195457A CN 109824729 A CN109824729 A CN 109824729A
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- methyl
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- methoxyl group
- cyclic ester
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Abstract
The present invention relates to a kind of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compounds and preparation method thereof, and the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of three (thio phosphono sila ring methoxyl group) silane compound of fire retardant methyl and its preparation sides
Method, and in particular to a kind of fire retardant methane-siliconic acid three [1,1- dimethyl -1- sila -2,6- dioxa -4- sulfenyl -4- phosphine is miscellaneous -
(4)-methylene] ester compounds and preparation method thereof；The compound contains the triple ignition-proof elements of phosphorus, silicon, sulphur, can be used as poly- ammonia
The fire retardant of ester, polyvinyl chloride, polyvinyl alcohol, epoxy resin and unsaturated-resin etc..
Background technique
Due to the extensive use of inflammability synthesis high molecular material, the hidden danger of fire is also more and more, therefore promotes resistance
The fast development of combustible material industry.Currently, the emphasis of fire proofing research is more to focus on ring while improving flame retardant property
Protect and ecological safety, and phosphorus system and silicon-series five-retardant with it is efficient, less toxic, non-corrosive and with material compatibility it is good etc. excellent
Point；Polyphosphoric acid film is generated when phosphorus flame retardant burns, and has the function of that anoxybiotic is heat-insulated, silicon-series five-retardant is that a kind of processing performance is good
Efficient flame-retarding agent, fine and close silicon layer of charcoal can be formed and play fire retardation, effectively prevent the material melted by heating to drip and generate
Second-time burning.Therefore phosphorus silicon-series five-retardant is one of the important directions studied at present.
Fire retardant methyl three (thio phosphono sila ring methoxyl group) silane disclosed by the invention, in molecular structure containing phosphorus,
The triple ignition-proof elements of silicon, sulphur, phosphorus, silicon, sulphur cooperative flame retardant synergy, play a role from different fire retardant mechanisms, can produce preferably
Flame retardant effect can be such that material has the function of preferable fire-retardant and at charcoal.Possessed polyester structure in compound molecule, so that changing
The polarity for closing object is moderate, good with most of high molecular material compatibilities, there is preferable market application and development prospect.
Summary of the invention
It is an object of the present invention to propose a kind of fire retardant methyl three (thio phosphono sila ring methoxyl group) silanization
Close object, physical and chemical performance is stablized, and nontoxic, flame-retarded efficiency is high, good with high molecular material compatibility, can overcome it is in the prior art not
Foot.
For achieving the above object, present invention employs following technical solutions:
A kind of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound, which is characterized in that the compound
Structure be shown below:
Another object of the present invention is to propose a kind of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane
Preparation method, raw material is cheap and easy to get, and simple process, equipment investment is few, is easy to large-scale production, this method are as follows:
Blender, thermometer and high efficiency reflux condenser are being housed, and suitable for reading equipped with hydrogen chloride absorption device in condenser
Reactor in, displace the air in reactor with nitrogen, dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester be added and has
Solvent after the dissolution of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester is uniformly dispersed, then is added dropwise methyl trichlorosilane, controls
1: 3-1: 3.6, dropping temperature does not surpass the molar ratio of methyl trichlorosilane and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
60 DEG C are crossed, drips off and is warming up to 80-140 DEG C of insulation reaction 8-12h, vacuum distillation removes solvent, obtains muddy viscous liquid, cold
But it, then by crude product is poured into the ice water of product Theoretical Mass 3 times of volumes ml of grams, quickly stirs 30min, stand,
Lower layer's colorless viscous shape liquid is taken to obtain product fire retardant methyl three (thio phosphono sila ring methoxyl group) silane.
Dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxy
Miscellaneous miscellaneous -4- methylol the hexamethylene of -4- sulfenyl -4- phosphine, chemical structural formula are as follows:
Organic solvent as described above is glycol dimethyl ether, acetonitrile, dioxane, dimethyl sulfoxide, methyl phenyl ethers anisole, diethyl two
Diethylene glycol dimethyl ether or glycol dimethyl ether, the volume ml of organic solvent are dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic esters
3~4 times of quality grams.
Three (thio phosphono sila ring methoxyl group) silane of fire retardant methyl of the present invention is thick liquid body, insoluble in most poles
Property solvent and water, moisture-stable, yield is 75.5%~90.5%, and flash-point is 194 ± 5 DEG C.It is suitable as polyurethane, polychlorostyrene
The fire retardant of ethylene, polyvinyl alcohol, epoxy resin and unsaturated-resin etc..Its (thio phosphono sila ring first of fire retardant methyl three
Oxygroup) preparation principle of silane compound is shown below:
Compared with prior art, the invention has the beneficial effects that:
1. fire retardant methyl three (thio phosphono sila ring methoxyl group) silane structure of the present invention is novel, contain phosphorus, silicon, sulphur three
Weight ignition-proof element, flame-retarded efficiency is high, and good at charcoal effect, symmetrical configuration thermal stability is good, has a wide range of application.
2. fire retardant methyl three (thio phosphono sila ring methoxyl group) silane of the present invention is halogen-free, belong to environmental-friendly fire-retardant
Carbon forming agent.
3. fire retardant methyl three (thio phosphono sila ring methoxyl group) silane of the present invention prepares raw materials used dimethyl silicic acid
Itself is a excellent fire retardants for trihydroxy methyl phosphine sulfide cyclic ester, and the pole of hydroxyl is enclosed with three silane reaction of methyl
Property, make (the thio phosphono sila ring methoxyl group) silane of fire retardant methyl three overcome dimethyl silicic acid without free hydroxyl
The water imbibition of trihydroxy methyl phosphine sulfide cyclic ester, and increase the content of fire-retardant element silicon, improve with the compatibility of material, mention
It is high fire-retardant at charcoal efficiency, have also obtained plasticising performance.
4. the preparation method of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane of the present invention is single step reaction, work
Skill is simple, and synthesis process does not introduce impurity without adding catalyst；Equipment is simple, low in cost, is suitable for large-scale production, has very
Good application and development prospect.
5. the present invention prepares phosphorus, silicon, sulphur collaboration resistance by raw material of the by-product methyl trichlorosilane of dimethyldichlorosilane
Agent methyl three (thio phosphono sila ring methoxyl group) silane is fired, to solve the problems, such as that methyl trichlorosilane comprehensive utilization provides one
Effective way.
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 infrared spectrogram of methyl three (thio phosphono sila ring methoxyl group) silane；Fig. 1 shows 695cm-1It is P=
The stretching vibration peak of S key；858cm-1It is the stretching vibration peak of C-P；2936cm-1It is the stretching vibration peak of c h bond；998cm-1Place
It is the stretching vibration peak of Si-O-C key；1408cm-1It is the flexural vibrations peak of c h bond；1187cm-1Place is C-0 key stretching vibration
Peak；760cm-1Place is the stretching vibration peak of C-Si key.
Fig. 2 is the nuclear magnetic spectrum figure of methyl three (thio phosphono sila ring methoxyl group) silane；Fig. 2 shows with deuterated chloroform
It is-the CH that is connected with Si at δ 0.15-0.3 for solvent3The peak H；It is-the CH that is connected with oxygen at δ 4.15-4.32The peak H；δ7.25
Place is solvent peak.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 63.6g (0.3mol) dimethyl silicic acid is added
Trihydroxy methyl phosphine sulfide cyclic ester and 200ml glycol dimethyl ether are dissolved to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After being uniformly dispersed, then 14.95g (0.1mol) methyl trichlorosilane is added dropwise, dropping temperature is no more than 60 DEG C, drips off and is warming up to 85
DEG C, insulation reaction 12h, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 200ml ice
30min is quickly stirred in water, stands, lower layer's colorless viscous shape liquid is taken to obtain (the thio phosphono sila ring of product fire retardant methyl three
Methoxyl group) silane.Yield is 78.5%, and flash-point is 194 ± 5 DEG C.
Embodiment 2 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 65.72g (0.31mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 200ml acetonitrile, it is equal to the dissolution dispersion of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After even, then 14.95g (0.1mol) methyl trichlorosilane being added dropwise, dropping temperature is no more than 60 DEG C, and it drips off and is warming up to 80 DEG C, heat preservation
11h is reacted, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 200ml ice water fastly
Speed stirring 30min, stands, lower layer's colorless viscous shape liquid is taken to obtain product fire retardant methyl three (thio phosphono sila ring methoxyl group)
Silane.Yield is 85.5%, and flash-point is 194 ± 5 DEG C.
Embodiment 3 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 67.52g (0.32mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 200ml dioxane, to the dissolution point of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After dissipating uniformly, then 14.95g (0.1mol) methyl trichlorosilane being added dropwise, dropping temperature is no more than 60 DEG C, and it drips off and is warming up to 100 DEG C,
Insulation reaction 10h, vacuum distillation remove solvent, obtain muddy viscous liquid, cooling, then crude product is poured into 200ml ice water
In quickly stir 30min, stand, take lower layer's colorless viscous shape liquid to obtain (the thio phosphono sila ring first of product fire retardant methyl three
Oxygroup) silane.Yield is 88.2%, and flash-point is 194 ± 5 DEG C.
Embodiment 4 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 69.96g (0.33mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 200ml dimethyl sulfoxide, to the dissolution point of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After dissipating uniformly, then 14.95g (0.1mol) methyl trichlorosilane being added dropwise, dropping temperature is no more than 60 DEG C, and it drips off and is warming up to 130 DEG C,
Insulation reaction 9h, vacuum distillation remove solvent, obtain muddy viscous liquid, cooling, then crude product is poured into 200ml ice water
Quickly stirring 30min stands, lower layer's colorless viscous shape liquid is taken to obtain (the thio phosphono sila ring methoxy of product fire retardant methyl three
Base) silane.Yield is 89.1%, and flash-point is 194 ± 5 DEG C.
Embodiment 5 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 72.08g (0.34mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 200ml methyl phenyl ethers anisole dissolve to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester and disperse
After uniformly, then 14.95g (0.1mol) methyl trichlorosilane is added dropwise, dropping temperature is no more than 60 DEG C, drips off and is warming up to 120 DEG C, protects
Temperature reaction 9h, vacuum distillation removes solvent, obtains muddy viscous liquid, cooling, then crude product is poured into 200ml ice water fastly
Speed stirring 30min, stands, lower layer's colorless viscous shape liquid is taken to obtain product fire retardant methyl three (thio phosphono sila ring methoxyl group)
Silane.Yield is 90.0%, and flash-point is 194 ± 5 DEG C.
Embodiment 6 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 74.2g (0.35mol) dimethyl silicic acid is added
Trihydroxy methyl phosphine sulfide cyclic ester and 200ml diethylene glycol dimethyl ether, it is molten to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After solution is uniformly dispersed, then 14.95g (0.1mol) methyl trichlorosilane is added dropwise, dropping temperature is no more than 60 DEG C, drips off and is warming up to
140 DEG C, insulation reaction 8h, vacuum distillation removes solvent, obtains muddy viscous liquid, cooling, then crude product is poured into 200ml
30min is quickly stirred in ice water, stands, lower layer's colorless viscous shape liquid is taken to obtain (the thio phosphono sila of product fire retardant methyl three
Ring methoxyl group) silane.Yield is 90.5%, and flash-point is 194 ± 5 DEG C.
Embodiment 7 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 500ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 76.32g (0.36mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 200ml ethylene glycol diethyl ether, it is molten to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After solution is uniformly dispersed, then 14.95g (0.1mol) methyl trichlorosilane is added dropwise, dropping temperature is no more than 60 DEG C, drips off and is warming up to
110 DEG C, insulation reaction 8h, vacuum distillation removes solvent, obtains muddy viscous liquid, cooling, then crude product is poured into 200ml
30min is quickly stirred in ice water, stands, lower layer's colorless viscous shape liquid is taken to obtain (the thio phosphono sila of product fire retardant methyl three
Ring methoxyl group) silane.Yield is 88.0%, and flash-point is 194 ± 5 DEG C.
1 preparation example main technologic parameters of table
Inventor uses mould in fire retardant methyl three (thio phosphono sila ring methoxyl group) silane application epoxy resin
The glass epoxy of 3mm thickness is made in tool, then is cut into the batten that long 150mm, width 7mm, thickness 3mm is made, reference: GB/T2406-2008
The limit oxygen index of " Plastics Combustion method for testing performance-oxygen index method) " test sample item.Test result is as shown in table 2:
Table 2 methyl three (thio phosphono sila ring methoxyl group) silane application ethoxyline resin antiflaming test data
When additive amount of the fire retardant in glass reinforced plastic is 12.5%, oxygen index (OI) has reached 29% fire retardant rank,
When additive amount of the fire retardant in glass reinforced plastic is 16%, oxygen index (OI) is even more the fire retardant rank for reaching higher 32%, this says
Bright three (thio phosphono sila ring methoxyl group) silane of product methyl has good fire-retardant effectiveness to epoxy resin.
Claims (3)
1. a kind of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound compound, which is characterized in that the change
The structure for closing object is shown below:
2. the preparation side of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound according to claim 1
Method, which is characterized in that this method are as follows:
Blender, thermometer and high efficiency reflux condenser are being housed, and suitable for reading anti-equipped with hydrogen chloride absorption device in condenser
It answers in device, displaces the air in reactor with nitrogen, dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester and organic molten is added
Agent after the dissolution of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester is uniformly dispersed, then is added dropwise methyl trichlorosilane, controls methyl
For the molar ratio of trichlorosilane and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester 1: 3-1: 3.6, dropping temperature is no more than 60
DEG C, it dripping off and is warming up to 80-140 DEG C of insulation reaction 8-12h, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then
Crude product is poured into the ice water of product Theoretical Mass 3 times of volumes ml of grams, quickly stirs 30min, stood, take lower layer
Colorless viscous shape liquid obtains product fire retardant methyl three (thio phosphono sila ring methoxyl group) silane；
Dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxa -4-
Miscellaneous -4- methylol the hexamethylene of sulfenyl -4- phosphine, chemical structural formula are as follows:
3. the preparation side of fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound according to claim 2
Method, it is characterised in that:
Organic solvent as described above is glycol dimethyl ether, acetonitrile, dioxane, dimethyl sulfoxide, methyl phenyl ethers anisole, diethylene glycol two
Methyl ether or glycol dimethyl ether, the volume ml of organic solvent are dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester quality
3~4 times of grams.
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| CN201910195457.5A CN109824729A (en) | 2019-03-04 | 2019-03-04 | Fire retardant methyl three (thio phosphono sila ring methoxyl group) silane compound and preparation method thereof |
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