CN109824732A - Fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound and preparation method thereof - Google Patents
Fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound and preparation method thereof Download PDFInfo
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- CN109824732A CN109824732A CN201910195495.0A CN201910195495A CN109824732A CN 109824732 A CN109824732 A CN 109824732A CN 201910195495 A CN201910195495 A CN 201910195495A CN 109824732 A CN109824732 A CN 109824732A
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Abstract
The present invention relates to a kind of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis 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 fire-retardant four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound of carbon forming agent and its preparations
Method, and in particular to a kind of fire-retardant carbon forming agent silicic acid four [1,1- dimethyl -1- sila -2,6- dioxa -4- oxygroup -4- phosphine is miscellaneous -
(4)-methylene] ester compounds and preparation method thereof, the compound is phosphorous, the dual ignition-proof element of silicon, can be used as polyvinyl alcohol, gathers
The fire-retardant carbon forming agent of ester, polyvinyl chloride, polyurethane, epoxy resin and unsaturated-resin etc..
Background technique
With the development of polymer material science, plastics, rubber and fiber etc. have obtained widely answering in daily life
With, but these materials are easy to burn mostly, often bring security risk to the life of people and property.Therefore, fire retardant and resistance
The research and development of combustion high molecular material are subject to the people's attention.Due to being gradually improved and people's environmental consciousness for flame retardant regulation
Enhancing, have certain limitation to halogenated flame retardant, while enhancing the research and development application of environment friendly flame retardant, especially
More urgent demand is welcome to novel, efficient, less toxic phosphorus, silicon, nitrogenated flame retardant, phosphorus flame retardant has anoxybiotic heat-insulated
Effect, nitrogenated flame retardant has an expansion heat insulating function, and silicon-series five-retardant can form fine and close silicon layer of charcoal and play fire retardation, can
The second-time burning for effectivelying prevent material melted by heating to drip and generating.At phosphorus, silicon synergistic fire retardant, especially P, Si ignition-proof element
The developmental research of synergistic fire retardant in same molecular structure has important practical significance.
Fire-retardant carbon forming agent four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silane of the present invention belongs to more phosphorus, more silicon, polycyclic symmetrical junction
Structure, the dual ignition-proof element cooperative flame retardant of phosphorus silicon, keeps material flame-retarded efficiency higher, greatly improve flame-retardant system at charcoal and resistance
Fire performance；And the circularly symmetric structure in molecular structure, there is splendid thermal stability, have with high molecular material compatible well
Property, and basic material is cheap and easy to get, has wide range of applications, and has market in urgent need, there is application and development prospect well.
Summary of the invention
It is an object of the present invention to propose a kind of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane
Compound, physical and chemical performance is stablized, nontoxic, and flame-retarded efficiency is high, good with high molecular material compatibility, can overcome in the prior art
It is insufficient.
For achieving the above object, present invention employs following technical solutions:
A kind of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound, which is characterized in that the chemical combination
The structure of object is shown below:
Another object of the present invention is to propose a kind of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane
Preparation method, raw material is cheap and easy to get, and low in cost, 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 oxide cyclic ester be added and has
Solvent after the dissolution of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester is uniformly dispersed, then is added dropwise silicon tetrachloride, controls tetrachloro
SiClx and the molar ratio of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester are 1: 4-1: 4.7, and dropping temperature is no more than 50 DEG C, drop
Complete to be warming up to 80-150 DEG C, insulation reaction 7-12h, vacuum distillation removes solvent, obtains muddy viscous liquid, cooling, then will be thick
Product is poured into the ice water of product Theoretical Mass 3 times of volumes ml of grams, quickly stirs 30min, is stood, is taken lower layer colourless
Viscous liquid obtains fire-retardant carbon forming agent four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silane of product.
Dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxy
Miscellaneous miscellaneous -4- methylol the hexamethylene of -4- oxygroup -4- phosphine, chemical structural formula are as follows:
Organic solvent as described above is glycol dimethyl ether, acetonitrile, dioxane, dimethyl sulfoxide, tetrachloroethanes, diethyl
Glycol dimethyl ether, ethylene glycol diethyl ether or methyl phenyl ethers anisole, the volume ml of organic solvent are dimethyl silicic acid trihydroxy methyl oxygen
2.5~3 times for changing phosphine cyclic ester quality grams.
Fire-retardant four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silane of carbon forming agent of the present invention is thick liquid, not soluble in water.It produces
Product yield is 80.3~93.5%, flash-point: 226 ± 5 DEG C, is suitable as polyvinyl alcohol, polyester, polyvinyl chloride, polyurethane, ring
The fire-retardant carbon forming agent of oxygen resin and unsaturated-resin etc..Its fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silanization
The preparation principle for closing object is shown below:
Compared with prior art, the invention has the beneficial effects that:
1. fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane structure of the invention is novel, phosphorous, silicon is dual
Ignition-proof element；Symmetrical configuration is good, and stability is high, has wide range of applications.
2. fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane of the invention is halogen-free, belong to environmentally friendly
Fire-retardant carbon forming agent.
3. fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane of the invention prepares raw materials used dimethyl-silicon
Itself is a excellent fire-retardant carbon forming agents for sour trihydroxy methyl phosphine oxide cyclic ester, but its reaction sealed with silicon tetrachloride hydroxyl
The polarity of base makes fire-retardant four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane of carbon forming agent without free hydroxyl, overcomes two
The water imbibition of methane-siliconic acid trihydroxy methyl phosphine oxide cyclic ester, and the content of ignition-proof element silicon is increased, it improves and material
Compatibility improves fire-retardant at charcoal efficiency, has also obtained plasticising performance.
4. the preparation method of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane of the invention is single step reaction,
Simple process, synthesis process do not introduce impurity without adding catalyst；Equipment is simple, low in cost, is suitable for large-scale production, has
Good application and development prospect.
5. the present invention prepares phosphorus, four (phosphono of silicon cooperative flame retardant carbon forming agent by raw material of the silicon tetrachloride as by-product of polysilicon
Heterocycle shape esters of silicon acis methoxyl group) silane, to solve the problems, such as that silicon tetrachloride comprehensive utilization provides an 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 fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane；1272cm-1It is P
The stretching vibration peak of=O key；820cm-1Place is the stretching vibration peak of P-C key；2975cm-1It is the stretching vibration peak of c h bond；
1018cm-1Place is the stretching vibration peak of C-Si key；1455cm-1It is the flexural vibrations peak of c h bond；750cm-1Place is C-Si key
Flexural vibrations peak；996cm-1Place is the stretching vibration peak of Si-O-C key.
Fig. 2 is the nuclear magnetic spectrum figure of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane；With deuterated chloroform
It is the peak H of-CHx of being connected with Si for solvent, at δ 0.1-0.4；It is-CH at δ 4.15-4.352The peak H；It is solvent at δ 7.25
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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 39.2g (0.2mol) dimethyl silicic acid is added
Trihydroxy methyl phosphine oxide cyclic ester and 120ml glycol dimethyl ether are dissolved to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After being uniformly dispersed, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 85 DEG C, heat preservation
12h is reacted, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice water fastly
Speed stirring 30min, stands, lower layer's colorless viscous shape liquid is taken to obtain fire-retardant four (the phosphono heterocycle shape esters of silicon acis methoxy of carbon forming agent of product
Base) silane.Yield is 80.3%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 40.18g (0.205mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml acetonitrile, it is equal to the dissolution dispersion of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After even, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 80 DEG C, insulation reaction
12h, vacuum distillation remove solvent, obtain muddy viscous liquid, cooling, then crude product is poured into 120ml ice water and is quickly stirred
30min is mixed, stands, lower layer's colorless viscous shape liquid is taken to obtain fire-retardant carbon forming agent four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silicon of product
Alkane.Yield is 86.5%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 41.16g (0.21mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml dioxane, to the dissolution point of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissipating uniformly, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 100 DEG C, heat preservation
10h is reacted, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice water fastly
Speed stirring 30min, stands, lower layer's colorless viscous shape liquid is taken to obtain fire-retardant four (the phosphono heterocycle shape esters of silicon acis methoxy of carbon forming agent of product
Base) silane.Yield is 90.2%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 42.14g (0.215mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml dimethyl sulfoxide, to the dissolution point of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissipating uniformly, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 130 DEG C, heat preservation
8h is reacted, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice water quickly
30min is stirred, stands, lower layer's colorless viscous shape liquid is taken to obtain the fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) of product
Silane.Yield is 91.4%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 43.12g (0.22mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml tetrachloroethanes, to the dissolution point of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissipating uniformly, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 120 DEG C, heat preservation
9h is reacted, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice water quickly
30min is stirred, stands, lower layer's colorless viscous shape liquid is taken to obtain the fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) of product
Silane.Yield is 92.7%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 44.1g (0.225mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml diethylene glycol dimethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissolution is uniformly dispersed, then 8.5g (0.05mo l) silicon tetrachloride is added dropwise, dropping temperature is no more than 50 DEG C, drips off and is warming up to 140
DEG C, insulation reaction 7h, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice
30min is quickly stirred in water, stands, lower layer's colorless viscous shape liquid is taken to obtain fire-retardant four (the miscellaneous cyclic silicate of phosphono of carbon forming agent of product
Ester methoxyl group) silane.Yield is 93.5%, and flash-point is 226 ± 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 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 45.08g (0.23mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml ethylene glycol diethyl ether, it is molten to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After solution is uniformly dispersed, then 8.5g (0.05mol) silicon tetrachloride being added dropwise, dropping temperature is no more than 50 DEG C, and it drips off and is warming up to 110 DEG C,
Insulation reaction 11h, vacuum distillation remove solvent, obtain muddy viscous liquid, cooling, then crude product is poured into 120ml ice water
In quickly stir 30min, stand, take lower layer's colorless viscous shape liquid to obtain fire-retardant four (the phosphono heterocycle shape esters of silicon acis of carbon forming agent of product
Methoxyl group) silane.Yield is 90.0%, and flash-point is 226 ± 5 DEG C.
Embodiment 8 is being equipped with blender, thermometer and high performance reflux condenser, and suitable for reading equipped with hydrogen chloride in condenser pipe
In the 250ml four-hole boiling flask of absorption plant, with the air in nitrogen displacement bottle falling, 46.06g (0.235mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine oxide cyclic ester and 120ml methyl phenyl ethers anisole dissolve to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester and disperse
After uniformly, then 8.5g (0.05mol) silicon tetrachloride is added dropwise, dropping temperature is no more than 50 DEG C, drips off and is warming up to 150 DEG C, heat preservation is anti-
7h is answered, vacuum distillation removes solvent, obtains muddy viscous liquid, and it is cooling, then crude product is poured into 120ml ice water and is quickly stirred
30min is mixed, stands, lower layer's colorless viscous shape liquid is taken to obtain fire-retardant carbon forming agent four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silicon of product
Alkane.Yield is 93.3%, and flash-point is 226 ± 5 DEG C.
1 preparation example main technologic parameters of table
Inventor uses in fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane application epoxy resin
The glass epoxy of 3mm thickness is made in mold, then is cut into the batten of long 15mm, width 7mm, thickness 3mm, reference: GB/T2406-2008 " modeling
Expect combustibility test method-oxygen index method " test sample item limit oxygen index.Test result is as shown in table 2:
Table 2 four (phosphono heterocycle shape esters of silicon acis 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 27% 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 30%, this says
Bright four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane of product has good fire-retardant effectiveness to epoxy resin.
Claims (3)
1. a kind of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound, which is characterized in that the compound
Structure be shown below:
2. the preparation of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis 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 oxide cyclic ester and organic molten is added
Agent after the dissolution of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester is uniformly dispersed, then is added dropwise silicon tetrachloride, controls silicon tetrachloride
For molar ratio with dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester 1: 4-1: 4.7, dropping temperature is no more than 50 DEG C, drips off liter
Temperature arrives 80-150 DEG C, insulation reaction 7-12h, and vacuum distillation removes solvent, obtains muddy viscous liquid, cooling, then by crude product
It is poured into the ice water of product Theoretical Mass 3 times of volumes ml of grams, quickly stirs 30min, stand, take lower layer's colorless viscous
Shape liquid obtains fire-retardant carbon forming agent four (the phosphono heterocycle shape esters of silicon acis methoxyl group) silane of product；
Dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester as described above is 1,1- dimethyl -1- sila -2,6- dioxa -4-
Miscellaneous -4- methylol the hexamethylene of oxygroup -4- phosphine, chemical structural formula are as follows:
3. the preparation of fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound according to claim 2
Method, it is characterised in that: the organic solvent be glycol dimethyl ether, acetonitrile, dioxane, dimethyl sulfoxide, tetrachloroethanes,
Diethylene glycol dimethyl ether, ethylene glycol diethyl ether or methyl phenyl ethers anisole, the volume ml of organic solvent are three hydroxyl first of dimethyl silicic acid
2.5~3 times of base phosphine oxide cyclic ester quality grams.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910195495.0A CN109824732A (en) | 2019-03-04 | 2019-03-04 | Fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910195495.0A CN109824732A (en) | 2019-03-04 | 2019-03-04 | Fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound and preparation method thereof |
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Application publication date: 20190531 |