CN109721627A - Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound and preparation method thereof - Google Patents
Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound and preparation method thereof Download PDFInfo
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- CN109721627A CN109721627A CN201811568849.3A CN201811568849A CN109721627A CN 109721627 A CN109721627 A CN 109721627A CN 201811568849 A CN201811568849 A CN 201811568849A CN 109721627 A CN109721627 A CN 109721627A
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Abstract
The present invention relates to a kind of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene 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 trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound and its
Preparation method, the compound contain the triple ignition-proof elements of phosphorus, nitrogen, sulphur, can be used as polyester, polyamide, epoxy resin, polyurethane,
The fire retardant of unsaturated-resin, polyvinyl alcohol and coating etc..
Background technique
With the progress of science and technology, organic synthesis high molecular material is widely applied in each field of society, however
High molecular material is a kind of combustible material, and combustion heating amount is big, and flame is easily propagated, and there is very big fire hazard in.
Therefore, people propose increasingly higher demands to the flame retardant property of high molecular material.With international increasingly strict fire-retardant vertical
Method, the successive of industry instruction are put into effect and the enhancing of environmental consciousness, and to novel, efficiently, the demand of environment friendly flame retardant is more compeled
It cuts.Phosphorus nitrogen system synergistic fire retardant has the features such as Halogen, low toxicity, decomposition temperature is high.Therefore, phosphorus-nitrogen containing flame retardant is in fire-retardant material
It is increasingly taken seriously in material research.
Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound disclosed by the invention belongs to more phosphorus
More nitrogen polysulfide structures, phosphorus, sulfur content are high, and there are also nitrogen, three element cooperative flame retardant efficiency are high.The product structure symmetry is good,
Aromatic is stablized, and decomposition temperature is high, good with high molecular material compatibility, adapts to the high temperature process of material, and raw material is cheap and easy to get,
Have a wide range of application, the prospect of marketing is very big.
Summary of the invention
It is an object of the present invention to propose a kind of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene
Phosphazene compound, physical and chemical performance is stablized, nontoxic, and flame-retarded efficiency is high, good with high molecular material compatibility, can overcome the prior art
In deficiency.
For achieving the above object, present invention employs following technical solutions:
A kind of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound, which is characterized in that should
The structure of compound is shown below:
Another object of the present invention is to propose a kind of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene
The preparation method of phosphazene compound, simple process are easy to large-scale production, and raw material is cheap and easy to get, and equipment investment is few, cost
It is cheap, this method are as follows:
By pentaerythrite dispersing and dissolving in organic solvent, then hexachlorocyclotriph,sphazene is added in three batches, controls chlordene ring three
Phosphonitrile and pentaerythrite molar ratio are 1: 3, are warming up to 90 DEG C of reaction 4h, until releasing without hydrogen chloride；Temperature is reduced to 30 DEG C, is added dropwise
With the phenylphosphonothioic dichloride of pentaerythrite equimolar amounts, process control temp is added dropwise and is not higher than 45 DEG C, after dripping off, is warming up to
It 100 DEG C~130 DEG C, reacts 8~11 hours, until being generated without hydrogen chloride；30 DEG C are cooled to hereinafter, being evaporated under reduced pressure out organic solvent
(recycling), adds the distilled water of relative product Theoretical Mass 2~3 times of volumes ml of grams, and stirring produces its solid
Product are dispersed in water, and filtering is drained, and filter cake vacuum drying obtains faint yellow solid trimerization O, O-2- loop coil phenylphosphonothioic acid diester
Trimethylene phosphonitrile.
Organic solvent as described above is dioxane, toluene, ethylene glycol diethyl ether and chlorobenzene, the volume of organic solvent
It ml is 3: 1~5: 1 with the ratio between hexachlorocyclotriph,sphazene and the quality grams summation of pentaerythrite.
Trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile of the invention is faint yellow solid, and decomposition temperature is
365 ± 2 DEG C, yield is 89.6%~94.6%, can be used as polyester, polyamide, epoxy resin, polyurethane, unsaturated-resin, gathers
The fire retardant of vinyl alcohol and coating etc..Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound
Preparation principle is shown below:
Compared with prior art, the invention has the beneficial effects that:
1. fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound structure novel of the present invention, phosphorus
Content is 17.8%, nitrogen content 4.1%, sulfur content 18.3%, and ignition-proof element total content is up to 40.2%.Symmetrical configuration
Good, stability is high, can be suitably used for the high temperature process of various engineering plastics, and three element cooperative flame retardant efficiency of nitrogen phosphate and sulfur is high, has
Good plasticity；
2. fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile of the present invention is halogen-free, be conducive to ring
It protects, belongs to the environmental-friendly fire retardant of intumescent；
3. the preparation method technique letter of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile of the present invention
Single, synthesis process does not introduce impurity without adding catalyst；Equipment is simple, low in cost, is suitable for large-scale production, has well
Application and development prospect.
Following spectrum data is provided in order to further illustrate the structure and performance spy of product.
1, the infared spectrum data of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile:
3080.3cm-1The absorption peak at place is the absorption peak on phenyl ring, 2962cm-1And 1459.1cm-1For the absorption peak of C-H on methylene,
1200.5cm-1For the stretching vibration absworption peak of phosphazene backbone P=N, 1050.4cm-1It is inhaled for the stretching vibration of P-N on phosphazene backbone
Receive peak, 1394.5cm-1For the absorption peak of P=S, 1190.5cm-1For the absorption peak of P-O, 913.6cm-1Place is the flexible of C-P key
Vibration peak.
2, the nuclear magnetic spectrum data of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile: δ 3.30-
3.45 be-N=P-O-CH2On the peak H；δ 3.55-3.85 is S=P-O-CH2On the peak H；δ 7.08-7.37 is on phenyl ring
The peak 5H.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 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, catch up with the air in most bottle with nitrogen, be added 12.24g (0.09mol) pentaerythrite and
120mL dioxane, stirring make the fully dispersed dissolution of pentaerythrite.3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, is stirred
Mix reaction 1h；3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, 1h is stirred to react；Add 3.48g (0.01mol) chlordene
Three phosphonitrile of ring is to slowly warm up to 90 DEG C, insulation reaction 4h, until releasing without hydrogen chloride；30 DEG C are then cooled to, 18.99g is added dropwise
(0.09mol) phenylphosphonothioic dichloride is added dropwise process control temp and is not higher than 45 DEG C, 100 DEG C is warming up to after dripping off, reaction
11h, until being released without hydrogen chloride；30 DEG C are cooled to hereinafter, vacuum distillation removing dioxane (recycling uses), adds 50mL
Water, stirring are dispersed in water its solid product, filter, drain, and filter cake vacuum drying obtains faint yellow solid trimerization O, O-2- spiral shell
Ring phenylphosphonothioic acid diester trimethylene phosphonitrile, decomposition temperature are 365 ± 2 DEG C, yield 89.6%.
Embodiment 2 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, catch up with the air in most bottle with nitrogen, be added 12.24g (0.09mol) pentaerythrite and
120mL toluene, stirring make the fully dispersed dissolution of pentaerythrite.3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, stirring is anti-
Answer 1h；3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, 1h is stirred to react；Add 3.48g (0.01mol) chlordene ring three
Phosphonitrile is to slowly warm up to 90 DEG C, insulation reaction 4h, until releasing without hydrogen chloride；30 DEG C are then cooled to, 18.99g is added dropwise
(0.09mol) phenylphosphonothioic dichloride is added dropwise process control temp and is not higher than 45 DEG C, 110 DEG C is warming up to after dripping off, reaction
10h, until being released without hydrogen chloride；30 DEG C are cooled to hereinafter, vacuum distillation removing toluene (recycling uses), adds 50mL water, stir
Mixing is dispersed in water its solid product, and filtering is drained, and filter cake vacuum drying obtains faint yellow solid trimerization O, O-2- loop coil benzene
Base phosphonothiolic acid diester trimethylene phosphonitrile, decomposition temperature are 365 ± 2 DEG C, yield 90.5%.
Embodiment 3 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, catch up with the air in most bottle with nitrogen, be added 12.24g (0.09mol) pentaerythrite and
120mL ethylene glycol diethyl ether, stirring make the fully dispersed dissolution of pentaerythrite.Add three phosphorus of 3.48g (0.01mol) chlordene ring
Nitrile is stirred to react 1h；3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, 1h is stirred to react；Add 3.48g
(0.01mol) hexachlorocyclotriph,sphazene is to slowly warm up to 90 DEG C, insulation reaction 4h, until releasing without hydrogen chloride；Then it is cooled to 30
DEG C, 18.99g (0.09mol) phenylphosphonothioic dichloride is added dropwise, process control temp is added dropwise and is not higher than 45 DEG C, heats up after dripping off
To 120 DEG C, 9h is reacted, until releasing without hydrogen chloride；Being cooled to 30 DEG C, (recycling makes hereinafter, vacuum distillation removes ethylene glycol diethyl ether
With), 50mL water is added, stirring is dispersed in water its solid product, filters, drains, and filter cake vacuum drying obtains pale yellow colored solid
Body trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile, decomposition temperature are 365 ± 2 DEG C, yield 94.6%.
Embodiment 4 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, catch up with the air in most bottle with nitrogen, be added 12.24g (0.09mol) pentaerythrite and
120mL chlorobenzene, stirring make the fully dispersed dissolution of pentaerythrite.3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, stirring is anti-
Answer 1h；3.48g (0.01mol) hexachlorocyclotriph,sphazene is added, 1h is stirred to react；Add 3.48g (0.01mol) chlordene ring three
Phosphonitrile is to slowly warm up to 90 DEG C, insulation reaction 4h, until releasing without hydrogen chloride；30 DEG C are then cooled to, 18.99g is added dropwise
(0.09mol) phenylphosphonothioic dichloride is added dropwise process control temp and is not higher than 45 DEG C, 130 DEG C is warming up to after dripping off, reaction
8h, until being released without hydrogen chloride；30 DEG C are cooled to hereinafter, vacuum distillation removing chlorobenzene (recycling uses), adds 50mL water, stir
Mixing is dispersed in water its solid product, and filtering is drained, and filter cake vacuum drying obtains faint yellow solid trimerization O, O-2- loop coil benzene
Base phosphonothiolic acid diester trimethylene phosphonitrile, decomposition temperature are 365 ± 2 DEG C, yield 92.4%.
1 preparation example main technologic parameters of table
Inventor is also by fire retardant trimerization O, O-2- the loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile of above-mentioned synthesis
It applied in PBT, is uniformly mixed according to certain proportion with PBT, then squeezes out batten, the size of batten with XJ-01 type extruder
For diameter 3mm, length 15cm.Then flame retardant property measurement is carried out to it, reference: GB/T2406-2008 " Plastics Combustion performance examination
Proved recipe method-oxygen index method " test sample item limit oxygen index.Test result is as shown in table 2:
2 trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile flame retardant property in PBT of table
It is generally acknowledged that the limit oxygen index of fire proofing, which reaches 27 or more, preferable flame retardant property.Work as known to table 2
When mass fraction of trimerization O, O-2- the loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile in PBT is 20%, LOI 33, and have
Good carbon-forming performance；Thus it can be seen that fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile is to PBT
With preferable flame-retarded efficiency.
Claims (3)
1. a kind of fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound, which is characterized in that the change
The structure for closing object is shown below:
2. fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound according to claim 1
Preparation method, which is characterized in that this method are as follows:
By pentaerythrite dispersing and dissolving in organic solvent, then hexachlorocyclotriph,sphazene is added in three batches, controls hexachlorocyclotriph,sphazene
It is 1: 3 with pentaerythrite molar ratio, is warming up to 90 DEG C of reaction 4h, until is released without hydrogen chloride；Reduction temperature is to 30 DEG C, dropwise addition and season
The phenylphosphonothioic dichloride of penta tetrol equimolar amounts is added dropwise process control temp and is not higher than 45 DEG C, after dripping off, is warming up to 100
DEG C~130 DEG C, it reacts 8~11 hours, until being generated without hydrogen chloride；30 DEG C are cooled to hereinafter, be evaporated under reduced pressure out organic solvent, then plus
Enter the distilled water of relative product Theoretical Mass 2~3 times of volumes ml of grams, stirring is dispersed in water its solid product, mistake
Filter is drained, and filter cake vacuum drying obtains faint yellow solid trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphonitrile.
3. fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound according to claim 2
Preparation method, it is characterised in that: the organic solvent be dioxane, toluene, ethylene glycol diethyl ether and chlorobenzene, it is organic molten
The volume ml of agent is 3: 1~5: 1 with the ratio between hexachlorocyclotriph,sphazene and the quality grams summation of pentaerythrite.
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| CN201811568849.3A CN109721627A (en) | 2018-12-10 | 2018-12-10 | Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound and preparation method thereof |
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| CN201811568849.3A CN109721627A (en) | 2018-12-10 | 2018-12-10 | Fire retardant trimerization O, O-2- loop coil phenylphosphonothioic acid diester trimethylene phosphazene compound and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596032A (en) * | 2009-07-14 | 2009-12-09 | 周卫银 | A kind of fast free strainer and using method |
| CN105348326A (en) * | 2015-12-15 | 2016-02-24 | 湖南工程学院 | N-P flameresistant material and preparation method thereof and application in textiles |
-
2018
- 2018-12-10 CN CN201811568849.3A patent/CN109721627A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596032A (en) * | 2009-07-14 | 2009-12-09 | 周卫银 | A kind of fast free strainer and using method |
| CN105348326A (en) * | 2015-12-15 | 2016-02-24 | 湖南工程学院 | N-P flameresistant material and preparation method thereof and application in textiles |
Non-Patent Citations (1)
| Title |
|---|
| HOMAID A. AL-MADFA ET AL.: "Phosphorus-Nitrogen Compounds. Part 68." The Reactions Of HexachlorocyClotriphosphazatriene And Octachlorocyclotetraphosphaza- Tetraene With Pentaerythritol", 《PHOSPHORUS, SULFUR AND SILICON AND THE RELATED ELEMENTS》 * |
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