CN109810144A - Flame retardant tris(dimethylsilylthiophosphonoheterocyclic methylene) phosphate compound and preparation method thereof - Google Patents
Flame retardant tris(dimethylsilylthiophosphonoheterocyclic methylene) phosphate compound and preparation method thereof Download PDFInfo
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- CN109810144A CN109810144A CN201910191428.1A CN201910191428A CN109810144A CN 109810144 A CN109810144 A CN 109810144A CN 201910191428 A CN201910191428 A CN 201910191428A CN 109810144 A CN109810144 A CN 109810144A
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Abstract
本发明涉及一种阻燃剂磷酸三(二甲基硅硫代膦酰杂环亚甲基)酯化合物及其制备方法，该化合物结构如下式所示：制备方法为：用氮气保护下，20℃下，将二甲基硅酸三羟甲基硫化膦环状酯溶于有机溶剂中，再滴加三氯氧磷，控制三氯氧磷与二甲基硅酸三羟甲基硫化膦环状酯的摩尔比为1∶3‑1∶3.6，滴加过程控制温度不超过60℃，滴完升温到80‑130℃，保温反应8‑10h，使氯化氢放完，经纯化处理，得磷酸三(二甲基硅硫代膦酰杂环亚甲基)酯。本发明化合物磷、硅、硫三元素协同阻燃，阻燃效能高，适合用作聚酯、聚氨酯、环氧树脂、不饱和树脂、聚烯烃等的阻燃剂。并且制备方法为一步反应，工艺简单，设备投资少，易于实现工业化生产。The present invention relates to a kind of flame retardant tris(dimethylsilylthiophosphonoheterocyclic methylene) phosphate compound and a preparation method thereof. The compound structure is shown in the following formula: The preparation method is as follows: under the protection of nitrogen, at 20° C., dissolving trimethylol phosphine sulfide cyclic ester dimethyl silicate in an organic solvent, then adding phosphorus oxychloride dropwise to control phosphorus oxychloride and dimethyl sulfide. The molar ratio of trimethylol phosphine sulfide cyclic ester based on silicate is 1: 3-1: 3.6, the temperature of the dropwise addition process is controlled not to exceed 60°C, the temperature is raised to 80-130°C after dropping, and the reaction is kept for 8-10h for 8-10h. After the hydrogen chloride is released, after purification, tris(dimethylsilylthiophosphonyl heterocyclic methylene) phosphate is obtained. The compound of the present invention, phosphorus, silicon and sulfur, is synergistically flame retardant, has high flame retardant performance, and is suitable for use as a flame retardant for polyester, polyurethane, epoxy resin, unsaturated resin, polyolefin and the like. In addition, the preparation method is a one-step reaction, the process is simple, the equipment investment is low, and the industrialized production is easy to be realized.
Description
Technical field
The present invention relates to a kind of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester compounds and its systems
Preparation Method, and in particular to and a kind of tricresyl phosphate [1,1- dimethyl -1- sila -2,6- dioxa -4- sulfenyl -4- phosphine is miscellaneous-(4)-methylene
Base] ester compounds and preparation method thereof, which is suitable as polyester, polyurethane, epoxy resin, unsaturated-resin, polyene
The fire retardant of the materials such as hydrocarbon.
Background technique
With the fast development of organic synthesis high molecular material, the research of fire proofing and application development also quickly, and by
In the enhancing of people's environmental consciousness, there is higher requirement again to fire retardant, while requiring good flame retardant property,
More focus on its friendly to environment, greatly advance the non-halogen process of fire retardant, so that it is green to promote phosphorus, silicon, nitrogen etc.
The development of color environment friendly flame retardant.Therefore, environmentally friendly fire retardant increasingly has been favored by people, especially organic phosphine,
Silicon-series five-retardant is because it has many advantages, such as efficient, low toxicity, in environmental requirement higher and higher today, gradually by the weight of people
Depending on having become one of most promising direction to the research of organic phosphine, silicon-series five-retardant.
The invention discloses a kind of organic phosphine, silicon, sulphur fire retardant tricresyl phosphates (the thio phosphono heterocycle methylene of dimethyl-silicon)
Ester compounds and preparation method thereof, preparation method are to be with phosphorus trichloride and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
Raw material, one-step method prepare the compound, and simple process, equipment investment is few, easy to operate, are easily converted into industrialized production；This hair
Bright fire retardant is more phosphorus, more silicon, polysulfide structure, and phosphorus, silicon, sulphur element cooperative flame retardant effect are more preferable, there is preferable application and development
Prospect.
Summary of the invention
It is an object of the present invention to propose a kind of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon)
Ester compounds, physical and chemical performance is stablized, nontoxic, and phosphorus, silicon, sulphur element cooperative flame retardant efficiency are high, with high molecular material compatibility
It is good, deficiency in the prior art can be overcome.
For achieving the above object, present invention employs following technical solutions:
A kind of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester compounds, which is characterized in that the change
The structure for closing object is shown below:
Another object of the present invention is to propose a kind of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon)
The preparation method of ester compounds, this method are single step reaction, and simple process, equipment investment is few, are easy to large-scale production, and raw material
It is cheap and easy to get, it is low in cost.Its technical solution is as follows:
This method are as follows:
Equipped with blender, thermometer, high efficiency reflux condenser and in the condenser hydrogen chloride absorption device suitable for reading of being connected to
In reactor, catch up with the air in most reactor with nitrogen, at 20 DEG C, be added dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester and
After dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester is completely dissolved dispersion, then phosphorus oxychloride is added dropwise in organic solvent, control three
The molar ratio of chlorethoxyfos and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester is 1: 3-1: 3.6, and process control temp is added dropwise not
It more than 60 DEG C, drips off and is warming up to 90-130 DEG C, insulation reaction 8-10h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy
Turbid viscous liquid；Crude product is poured into again in the ice water of product theory quality 3 times of volumes ml of grams and is quickly stirred
30min is filtered, and is eluted with the water of 1.5 times of volumes ml of product theory quality grams, and filter cake is dried in vacuo to obtain product phosphoric acid
Three (the thio phosphono heterocycle methylene of dimethyl-silicon) esters.
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 diethylene glycol dimethyl ether, methyl phenyl ethers anisole, dimethylbenzene, chlorobenzene, dimethyl sulfoxide or second two
Diethylene glycol diethyl ether, dosage volume ml are 3-5 times of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester quality grams.
Fire retardant tricresyl phosphate (dimethyl-silicon phosphono heterocycle methylene) ester of the present invention is white solid, and product yield is
90.2%-94.6%, fusing point are 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.It is suitable as polyester, polyurethane, asphalt mixtures modified by epoxy resin
The fire retardant of the materials such as rouge, unsaturated-resin, polyolefin, the fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon)
The synthesis technology principle of ester is shown below:
Compared with prior art, the beneficial effects of the present invention are:
1. fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester compounds phosphorus content of the present invention is up to
18.24%, silicon content reaches 12.4%, and sulfur content reaches 14.1%, and effective ignition-proof element total amount is up to 44.74%, phosphorus, silicon, sulphur
Three element cooperative flame retardant efficiency are high.
2. the raw material two that fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester compounds of the present invention use
Inherently a kind of excellent response type organic phosphine silicon fire retardant of methane-siliconic acid trihydroxy methyl phosphine sulfide cyclic ester, with phosphorus oxychloride
Reaction, and the content of phosphorus is improved, the polarity of hydroxyl is also enclosed, its hygroscopic property is overcome, forms polycyclic, polyester knot
Structure, symmetry is good, polarity is moderate, and assigning product and material has preferable compatibility.
3. the preparation method of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester compounds of the present invention is
Single step reaction, simple process, equipment investment is few, easy to operate, at low cost, is easy to scale conversion and production.
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 tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester；Fig. 1 shows
746cm-1Place is the flexural vibrations peak of P=S key；826cm-1Place is the stretching vibration peak of C-P key；2998cm-1And 2902cm-1Place
For the stretching vibration peak of c h bond；956cm-1Place is the stretching vibration peak of P-O key；1478cm-1And 1366cm-1It is the curved of c h bond
Bent vibration peak；802cm-1Place is the stretching vibration peak of C-Si key；1258cm-1Place is the stretching vibration peak of P=O double bond；1204cm-1And 1096cm-1It is the stretching vibration peak of C-O key；1018cm-1It is the stretching vibration peak of Si-O-C key.
Fig. 2 is the nuclear magnetic spectrum figure of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester；Fig. 2 shows δ
It is-the CH that is connected with Si at 0.1-0.33The peak H；It is-the CH that is connected with Si-O at δ 3.5-3.652The peak H；It is at δ 3.8-3.9
- the CH being connected with O=P2The peak H.
Fig. 3 is the differential thermal figure of fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester；Fig. 3 shows temperature
There is an obvious endothermic peak when being 175 DEG C, fusing point is 175 ± 2 DEG C, and temperature is that the beginning of 292 DEG C of products is weightless；To final temperature
Still there is 29% carbon residual at 800 DEG C, illustrates the good thermal stability of product.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 31.8g (0.15mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 90ml diethylene glycol dimethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After being completely dissolved dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off heating
To 100 DEG C, insulation reaction 10h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Again by crude product
It pours into 100ml ice water and quickly stirs 30min, filter, and eluted with 50ml water, filter cake is dried in vacuo to obtain product tricresyl phosphate (two
The thio phosphono heterocycle methylene of methyl silicon) ester.Yield is 90.2%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 2 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 32.86g (0.155mol) diformazan is added
Base silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 120ml methyl phenyl ethers anisole, it is complete to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After dissolution dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 130
DEG C, insulation reaction 9h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is poured into again
30min is quickly stirred in 100ml ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tricresyl phosphate (dimethyl
The thio phosphono heterocycle methylene of silicon) ester.Yield is 91.5%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 3 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 33.92g (0.16mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 140ml dimethylbenzene, it is completely molten to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After solution dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 120
DEG C, insulation reaction 9h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is poured into again
30min is quickly stirred in 100ml ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tricresyl phosphate (dimethyl
The thio phosphono heterocycle methylene of silicon) ester.Yield is 92.4%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 4 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 34.98g (0.165mol) diformazan is added
Base silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 130ml chlorobenzene, it is completely molten to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After solution dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 110
DEG C, insulation reaction 8h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is poured into again
30min is quickly stirred in 100ml ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tricresyl phosphate (dimethyl
The thio phosphono heterocycle methylene of silicon) ester.Yield is 92.0%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 5 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 36.04g (0.17mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 100ml dimethyl sulfoxide, it is complete to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After dissolution dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 130
DEG C, insulation reaction 8h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is poured into again
30min is quickly stirred in 100ml ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tricresyl phosphate (dimethyl
The thio phosphono heterocycle methylene of silicon) ester.Yield is 93.5%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 6 is being equipped with blender, thermometer, high performance reflux condenser and is inhaling in the condenser pipe hydrogen chloride suitable for reading that is connected to
In the 250ml four-hole boiling flask of receiving apparatus, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 37.1g (0.175mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine sulfide cyclic ester and 110ml ethylene glycol diethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After being completely dissolved dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off heating
To 90 DEG C, insulation reaction 9h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is fallen again
Enter and quickly stir 30min in 100ml ice water, filter, and eluted with 50ml water, filter cake is dried in vacuo to obtain product tricresyl phosphate (diformazan
The thio phosphono heterocycle methylene of base silicon) ester.Yield is 91.6%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Embodiment 7 equipped with blender, thermometer, high performance reflux condenser and is being connected to hydrogen chloride absorption condenser pipe is suitable for reading
In the 250ml four-hole boiling flask of device, the air in most bottle is caught up with nitrogen, and at 20 DEG C, 38.16g (0.18mol) dimethyl-silicon is added
Sour trihydroxy methyl phosphine sulfide cyclic ester and 100ml diethylene glycol dimethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester
After being completely dissolved dispersion, then 7.675g (0.05mol) phosphorus oxychloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off heating
To 90 DEG C, insulation reaction 10h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Again by crude product
It pours into 100ml ice water and quickly stirs 30min, filter, and eluted with 50ml water, filter cake is dried in vacuo to obtain product tricresyl phosphate (two
The thio phosphono heterocycle methylene of methyl silicon) ester.Yield is 94.6%, and fusing point is 175 ± 2 DEG C, and decomposition temperature is 292 ± 5 DEG C.
Table 1 prepares embodiment main technologic parameters
Inventor by fire retardant tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester application epoxy resin,
The glass epoxy of 3mm thickness is made of mold, then is cut into the batten that long 150mm, width 7mm, thickness 3mm is made, reference: GB/T2406-
The limit oxygen index of 2008 " Plastics Combustion method for testing performance-oxygen index method " test sample items.Test result is as shown in table 2:
2 tricresyl phosphate of table (the thio phosphono heterocycle methylene of dimethyl-silicon) ester 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 product tricresyl phosphate (the thio phosphono heterocycle methylene of dimethyl-silicon) ester has good fire-retardant effectiveness to epoxy resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625249A (en) * | 2020-11-20 | 2021-04-09 | 江苏集萃先进高分子材料研究所有限公司 | Novel phosphorus-nitrogen-sulfur flame retardant and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625249A (en) * | 2020-11-20 | 2021-04-09 | 江苏集萃先进高分子材料研究所有限公司 | Novel phosphorus-nitrogen-sulfur flame retardant and preparation method thereof |
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Application publication date: 20190528 |