CN109824733A - Fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and preparation method thereof - Google Patents
Fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and preparation method thereof, which is shown below:
Description
Technical field
The present invention relates to a kind of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and its systems
Preparation Method, and in particular to and a kind of tri o cresyl thiophosphate [1,1- dimethyl -1- sila -2,6- dioxa -4- oxygroup -4- phosphine is miscellaneous-and (4) -
Methylene] ester compounds and preparation method thereof, the compound be suitable as polyester, polyurethane, epoxy resin, unsaturated-resin,
The fire retardant of the materials such as polyolefin.
Background technique
With the fast development of high molecular material, the application range of fire proofing is also constantly widened, and due to people's environmental protection
The enhancing of consciousness has higher requirement to fire retardant again, while wishing that fire proofing has good flame retardant property, also
Emphasize that it has friendly to environment, so non-halogen one of the hot spot for having become the area research of fire retardant, promotes as a result,
The development of the environmental types fire retardants such as phosphorus, nitrogen, silicon.Although traditional halogenated flame retardant has preferable flame retardant property and valence
Lattice are moderate, but the toxic gases such as its dioxin generated in burning can cause secondary hazards to the life security of people.Therefore,
Environmentally friendly fire retardant increasingly has been favored by people, and especially organic phosphine, silicon-series five-retardant are because it is with efficient, low toxicity
The advantages that, it in environmental requirement higher and higher today, is gradually valued by people, the research to organic phosphine, silicon-series five-retardant
Have become most promising one of direction.
The invention discloses a kind of organic phosphine, silicon, sulphur fire retardant tri o cresyl thiophosphates (dimethyl-silicon phosphono heterocycle methylene)
Ester compounds and preparation method thereof, preparation method are to be with phosphorus thiochloride and dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
Raw material, one-step method prepare the compound, and simple process, equipment investment is few, easy to operate, at low cost, are easily converted into industrial metaplasia
It produces；Fire retardant of the present invention is more phosphorus, polycide, and introduces ignition-proof element sulphur, phosphorus, silicon, sulphur element cooperative flame retardant effect
More preferably, 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene)
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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene)
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 oxide cyclic ester and
After dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester is completely dissolved dispersion, then phosphorus thiochloride is added dropwise in organic solvent, control three
The molar ratio of chlorothion and dimethyl silicic acid trihydroxy methyl phosphine oxide 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 100-150 DEG C, insulation reaction 8-12h 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 the product sulfur generation
Tricresyl phosphate (dimethyl-silicon phosphono heterocycle methylene) ester.
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 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester of the present invention is white solid, and product yield is
90.2%-94.6%, fusing point are 155 ± 2 DEG C, and decomposition temperature is 294 ± 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene)
The synthesis technology principle of ester is shown below:
Compared with prior art, the beneficial effects of the present invention are:
1. fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds phosphorus content of the present invention is up to
19.1%, silicon content reaches 13%, and sulfur content reaches 4.9%, and total effectively ignition-proof element amount up to 37%, assist by phosphorus, silicon, sulphur element
With flame-retarded efficiency height, product is stablized, and decomposition temperature is high.
2. the raw material two that fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) 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 oxide cyclic ester, with phosphorus thiochloride
Reaction, and the content of phosphorus is improved, ignition-proof element sulphur is also introduced, polycyclic, polyester structure is formd, symmetry is good, polarity is suitable
In, assigning product and material has preferable compatibility.
3. the preparation method of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester；2991cm-1Place
For the stretching vibration peak of c h bond；976cm-1Place is the stretching vibration peak of P-O key；850cm-1Place is the stretching vibration peak of C-P key；
784cm-1Place is the stretching vibration peak of P=S key；1251cm-1Place is the stretching vibration peak of P=O double bond；1178cm-1Place is Si-O
Stretching vibration peak；802cm-1Place is the stretching vibration peak of C-Si key；1217cm-1And 1193cm-1Place is the flexible vibration of C-O key
Dynamic peak；1408cm-1It is the flexural vibrations peak of c h bond.
Fig. 2 is the nuclear magnetic spectrum figure of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester；δ0.1-0.25
Place is the peak H on the methyl being connected with Si；It is the peak H on the methylene being connected with S=P-O at δ 3.6-3.85；At δ 3.9-4.1
It is the peak H on the methylene being connected with Si-O；It is solvent peak at δ 7.25.
Fig. 3 is the differential thermal figure of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester；Temperature is 155 DEG C
When, there is an apparent endothermic peak, fusing point is 155 DEG C；Temperature is that 294 DEG C of beginnings are weightless；When weight-loss ratio 50%, temperature 432
℃；Still there is 29% residue when to 800 DEG C of final temperature, illustrates that product has preferable thermal stability.
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, 29.4g (0.15mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine oxide cyclic ester and 90ml diethylene glycol dimethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After being completely dissolved dispersion, then 8.47g (0.05mol) phosphorus thiochloride 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 10h 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 tri o cresyl thiophosphate
(dimethyl-silicon phosphono heterocycle methylene) ester.Yield is 90.2%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 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, 30.38g (0.155mol) diformazan is added
Base silicic acid trihydroxy methyl phosphine oxide cyclic ester and 120ml methyl phenyl ethers anisole, it is complete to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissolution dispersion, then 8.47g (0.05mol) phosphorus thiochloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 150
DEG C, insulation reaction 11h 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 tri o cresyl thiophosphate (two
Methyl silicon phosphono heterocycle methylene) ester.Yield is 91.5%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 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, 31.36g (0.16mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine oxide cyclic ester and 140ml dimethylbenzene, it is completely molten to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After solution dispersion, then 8.47g (0.05mol) phosphorus thiochloride being added dropwise, control dropwise addition process is no more than 60 DEG C, and it drips off and is warming up to 140 DEG C,
Insulation reaction 9h, discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy viscous liquid；Crude product is poured into 100ml again
30min is quickly stirred in ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tri o cresyl thiophosphate (dimethyl-silicon
Phosphono heterocycle methylene) ester.Yield is 92.4%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 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, 32.34g (0.165mol) diformazan is added
Base silicic acid trihydroxy methyl phosphine oxide cyclic ester and 130ml chlorobenzene, it is completely molten to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After solution dispersion, then 8.47g (0.05mol) phosphorus thiochloride being added dropwise, control dropwise addition process is no more than 60 DEG C, and it 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 100ml again
30min is quickly stirred in ice water, is filtered, and is eluted with 50ml water, and filter cake is dried in vacuo to obtain product tri o cresyl thiophosphate (dimethyl-silicon
Phosphono heterocycle methylene) ester.Yield is 92.0%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 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, 33.32g (0.17mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine oxide cyclic ester and 100ml dimethyl sulfoxide, it is complete to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After dissolution dispersion, then 8.47g (0.05mol) phosphorus thiochloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to 150
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 tri o cresyl thiophosphate (two
Methyl silicon phosphono heterocycle methylene) ester.Yield is 93.5%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 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, 34.3g (0.175mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine oxide cyclic ester and 110ml ethylene glycol diethyl ether, to dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester
After being completely dissolved dispersion, then 8.47g (0.05mol) phosphorus thiochloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off and is warming up to
100 DEG C, insulation reaction 10h 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 tri o cresyl thiophosphate
(dimethyl-silicon phosphono heterocycle methylene) ester.Yield is 92.6%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 5 DEG C.
Embodiment 7 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, 35.28g (0.18mol) dimethyl is added
Silicic acid trihydroxy methyl phosphine oxide cyclic ester and 100ml diethylene glycol dimethyl ether, it is cyclic annular to dimethyl silicic acid trihydroxy methyl phosphine oxide
After ester is completely dissolved dispersion, then 8.47g (0.05mol) phosphorus thiochloride is added dropwise, control dropwise addition process is no more than 60 DEG C, drips off heating
To 110 DEG C, insulation reaction 12h 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 tri o cresyl thiophosphate
(dimethyl-silicon phosphono heterocycle methylene) ester.Yield is 94.6%, and fusing point is 155 ± 2 DEG C, and decomposition temperature is 294 ± 5 DEG C.
Table 1 prepares embodiment main technologic parameters
Inventor by fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester application epoxy resin,
The glass epoxy of 3mm thickness is made of mold, then is cut into the batten of long 15mm, width 7mm, thickness 3mm, 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:
2 tri o cresyl thiophosphate of table (dimethyl-silicon phosphono heterocycle methylene) ester is used for 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 tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester has good fire-retardant effectiveness to epoxy resin.
Claims (3)
1. a kind of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds, which is characterized in that the chemical combination
The structure of object is shown below:
2. the system of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds according to claim 1
Preparation Method, which is characterized in that this method are as follows:
Equipped with blender, thermometer, high efficiency reflux condenser and in the condenser reaction suitable for reading for being connected to hydrogen chloride absorption device
In device, the air in most reactor is caught up with nitrogen, and at 20 DEG C, dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester and organic is added
After dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester is completely dissolved dispersion, then phosphorus thiochloride is added dropwise in solvent, controls trichlorine sulphur
The molar ratio of phosphorus and dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester is 1: 3-1: 3.6, and process control temp is added dropwise and is no more than
It 60 DEG C, drips off and is warming up to 100-150 DEG C, insulation reaction 8-12h discharges hydrogen chloride, and vacuum distillation removes solvent, obtains muddy
Viscous liquid；Crude product is poured into again in the ice water of product theory quality 3 times of volumes ml of grams and quickly stir 30min, taken out
Filter, and eluted with the water of 1.5 times of volumes ml of product theory quality grams, filter cake is dried in vacuo to obtain product tri o cresyl thiophosphate
(dimethyl-silicon phosphono heterocycle methylene) ester；
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 system of fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds according to claim 2
Preparation Method, it is characterised in that: organic solvent as described above is diethylene glycol dimethyl ether, methyl phenyl ethers anisole, dimethylbenzene, chlorobenzene, diformazan
Sulfoxide or ethylene glycol diethyl ether, dosage volume ml are dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester quality grams
3-5 times.
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| CN201910195521.XA CN109824733A (en) | 2019-03-04 | 2019-03-04 | Fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and preparation method thereof |
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| CN201910195521.XA CN109824733A (en) | 2019-03-04 | 2019-03-04 | Fire retardant tri o cresyl thiophosphate (dimethyl-silicon phosphono heterocycle methylene) ester compounds and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117117328A (en) * | 2023-10-23 | 2023-11-24 | 深圳华驰新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
Citations (2)
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|---|---|---|---|---|
| JPH0753582A (en) * | 1993-08-12 | 1995-02-28 | Sanko Chem Co Ltd | Organic phosphorous compound and its production |
| CN108948087A (en) * | 2018-07-06 | 2018-12-07 | 苏州科技大学 | More silicon phosphine 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof |
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2019
- 2019-03-04 CN CN201910195521.XA patent/CN109824733A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753582A (en) * | 1993-08-12 | 1995-02-28 | Sanko Chem Co Ltd | Organic phosphorous compound and its production |
| CN108948087A (en) * | 2018-07-06 | 2018-12-07 | 苏州科技大学 | More silicon phosphine 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| RAETZ, RUDI F. W ET AL.: "4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane 1-sulfide and derived compounds", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117117328A (en) * | 2023-10-23 | 2023-11-24 | 深圳华驰新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN117117328B (en) * | 2023-10-23 | 2024-01-12 | 深圳华驰新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
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Application publication date: 20190531 |