CN109912657A - Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds and preparation method thereof - Google Patents
Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds and preparation method thereof Download PDFInfo
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- CN109912657A CN109912657A CN201910191427.7A CN201910191427A CN109912657A CN 109912657 A CN109912657 A CN 109912657A CN 201910191427 A CN201910191427 A CN 201910191427A CN 109912657 A CN109912657 A CN 109912657A
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Abstract
The present invention relates to a kind of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) 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 (the thio phosphono heterocycle methylene of silicon) ester compounds and its preparations
Method, and in particular to a kind of fire retardant tri o cresyl thiophosphate [1,1- dimethyl -1- sila -2,6- dioxa -4- sulfenyl -4- phosphine is miscellaneous -
(4)-methylene] ester, which is suitable as polyester, polyurethane, polyamide, epoxy resin, unsaturated-resin, polyolefin etc.
The fire retardant of material.
Background technique
With the fast development of high molecular material, fire proofing using more and more extensive, and due to people's awareness of safety
Enhancing, higher requirement is had also been proposed to fire retardant, emphasize fire proofing have good flame retardant property while, also want
Ask it that there is friendly to environment, thus non-halogen one of the hot spot for having become research of fire retardant, thereby promote phosphorus, nitrogen,
The development of the environmental types fire retardant such as silicon.Although traditional halogenated flame retardant has preferable flame retardant property, and moderate,
But the toxic gases such as its dioxin generated in burning can cause secondary hazards to the life security of people.Therefore, environment friend
The exploitation of good type 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 more valued by people, to the research of organic phosphine, silicon-series five-retardant
As most promising one of direction.
The invention discloses a kind of organic phosphine, silicon, sulphur fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) esters
Compound and preparation method thereof, preparation method are with phosphorus thiochloride and dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester for original
Material, one-step method prepare the compound, and simple process, equipment investment is few, easy to operate, are easily converted into industrialized production；The present invention
Fire retardant is more phosphorus, polycide, and introduces ignition-proof element sulphur, and phosphorus, silicon, sulphur element cooperative flame retardant effect are more preferable, have compared with
Good 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 (the thio phosphono heterocycle methylene of silicon) ester
Compound, physical and chemical performance is stablized, nontoxic, and phosphorus, silicon, sulphur element cooperative flame retardant efficiency are high, good with high molecular material compatibility,
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 (the thio phosphono heterocycle methylene of silicon) ester compounds, 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 tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester
The preparation method of compound, this method are single step reaction, and simple process, equipment investment is few, are easy to large-scale production, and raw material is honest and clean
Valence is easy to get, 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 thiochloride is added dropwise in organic solvent, control three
The molar ratio of chlorothion 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 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, 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 (the thio phosphono heterocycle methylene of silicon) ester.
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 sulfide cyclic ester quality grams.
Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester of the present invention is white solid, and product yield is
90.2%-94.6%, fusing point are 236 ± 2 DEG C, and decomposition temperature is 324 ± 5 DEG C.It is suitable as polyester, polyurethane, polyamide,
The fire retardant of the materials such as epoxy resin, unsaturated-resin, polyolefin, (the thio phosphono heterocycle of silicon is sub- for the fire retardant tri o cresyl thiophosphate
Methyl) 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 (the thio phosphono heterocycle methylene of silicon) ester compounds phosphorus content of the present invention is up to
13.4%, silicon content reaches 12.1%, and sulfur content reaches 18.4%, and effective ignition-proof element total amount is up to 43.9%, phosphorus, silicon, sulphur three
Element cooperative flame retardant efficiency is high, and product is stablized, and decomposition temperature is high.
2. the raw material diformazan that fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds of the present invention use
Inherently a kind of excellent response type organic phosphine silicon fire retardant of base silicic acid trihydroxy methyl phosphine sulfide cyclic ester, it is anti-with phosphorus thiochloride
The polarity of hydroxyl should be enclosed, make fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester without free hydroxyl
Base, overcomes the water imbibition of dimethyl silicic acid trihydroxy methyl phosphine sulfide cyclic ester, and increases the content of p and s ignition-proof element,
Polycyclic, polyester structure is formd, symmetry is good, polarity is moderate, and assigning product and material has preferable compatibility.
3. the preparation method of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds of the present invention is one
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 (the thio phosphono heterocycle methylene of silicon) ester；Fig. 1 shows
680cm-1It is the stretching vibration peak of P=S key；874cm-1It is the stretching vibration peak of C-P；2998cm-1And 2946cm-1It is c h bond
Stretching vibration peak；1000cm-1Place is the stretching vibration peak of Si-O-C key；1478cm-1It is the flexural vibrations peak of c h bond；1106cm-1Place is C-O key stretching vibration peak；740cm-1Place is the stretching vibration peak of C-Si key.
Fig. 2 is the nuclear magnetic spectrum figure of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester；Fig. 2 shows δ
It is the peak H on the methyl being connected with Si at 0.1-0.25；It is the peak H on the methylene being connected with S=P at δ 3.6-3.85；δ
It is the peak H on the methylene being connected with Si-O at 3.9-4.1；It is solvent peak at δ 7.25.
Fig. 3 is the differential thermal figure of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester；Fig. 3 shows that temperature is
324 DEG C of beginnings are weightless；When weight-loss ratio 50%, temperature is 478 DEG C；Still there are 19% residue, explanation when to 800 DEG C of final temperature
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, 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 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
(the thio phosphono heterocycle methylene of silicon) ester.Yield is 85.2%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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 (silicon
Thio phosphono heterocycle methylene) ester.Yield is 87.5%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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 (the thio phosphine of silicon
Acyl heterocycle methylene) ester.Yield is 88.4%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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 (the thio phosphine of silicon
Acyl heterocycle methylene) ester.Yield is 88.0%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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 (silicon
Thio phosphono heterocycle methylene) ester.Yield is 89.5%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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
(the thio phosphono heterocycle methylene of silicon) ester.Yield is 88.6%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 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 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
110 DEG C, insulation reaction 12h 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
(the thio phosphono heterocycle methylene of silicon) ester.Yield is 90.6%, and fusing point is 236 ± 2 DEG C, and decomposition temperature is 324 ± 5 DEG C.
Table 1 prepares embodiment main technologic parameters
Inventor uses in fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester application epoxy resin
The glass epoxy of 3mm thickness is made in mold, then is cut into the batten that long 15mm, 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:
2 tri o cresyl thiophosphate of table (the thio phosphono heterocycle methylene of 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 33%, this says
Bright product tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester has good fire-retardant effectiveness to epoxy resin.
Claims (3)
1. a kind of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds, which is characterized in that the compound
Structure be shown below:
2. the preparation of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds according to claim 1
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 sulfide cyclic ester and organic is added
After dimethyl silicic acid trihydroxy methyl phosphine sulfide 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 sulfide 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
(the thio phosphono heterocycle methylene of silicon) ester；
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 of fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds according to claim 2
Method, it is characterised in that: organic solvent as described above is diethylene glycol dimethyl ether, methyl phenyl ethers anisole, dimethylbenzene, chlorobenzene, diformazan Asia
Sulfone or ethylene glycol diethyl ether, dosage volume ml are the 3- of dimethyl silicic acid trihydroxy methyl phosphine oxide cyclic ester quality grams
5 times.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910191427.7A CN109912657A (en) | 2019-03-04 | 2019-03-04 | Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910191427.7A CN109912657A (en) | 2019-03-04 | 2019-03-04 | Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109912657A true CN109912657A (en) | 2019-06-21 |
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| CN201910191427.7A Withdrawn CN109912657A (en) | 2019-03-04 | 2019-03-04 | Fire retardant tri o cresyl thiophosphate (the thio phosphono heterocycle methylene of silicon) ester compounds and preparation method thereof |
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Application publication date: 20190621 |